JP3401027B2 - Method for producing bisphenols - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing bisphenols.

[0002]

2. Description of the Related Art Conventionally, as a method for producing bisphenols, a compound containing sulfur is often used as a cocatalyst in order to improve the activity of the catalyst. For example, US Pat. No. 2,775,62
No. 0, 2,2-di- (reacted by reacting phenol and dimethyl ketone in the presence of an acid catalyst consisting of a strong mineral acid such as hydrogen chloride and a co-catalyst methyl mercaptan. A method of making hydroxyphenyl) propane is disclosed. US Patent No. 2,46
No. 8,982 discloses phenol and ketone in the presence of an acidic condensing agent such as sulfuric acid, hydrogen chloride or aluminum chloride and a carboxylic acid substituted with a mercapto group such as mercaptoacetic acid or mercaptopropionic acid. A method of reacting to produce bisphenol is disclosed. U.S. Pat. No. 2,623,908 discloses 4,4 'by reacting phenol with acetone in the presence of an acidic condensing agent such as hydrogen chloride, hydrochloric acid, hydrogen bromide and the like.
-A method for producing isopropylidenephenol is disclosed, and it is described that coexistence of a volatile sulfur-containing catalyst such as mercaptocarboxylic acid with the acidic condensing agent increases the condensation rate of phenol and acetone.

However, in these methods,
There is a problem that the catalyst is not easily recovered, the product is contaminated with sulfur compounds, and there are many by-products.

On the other hand, in US Pat. No. 3,394,089, an acid type insoluble strong acid cation exchange resin modified by partial neutralization with mercaptoamine is used as a catalyst in the presence of this catalyst, and a phenol and a ketone. An invention for producing bisphenol by reacting with is described.

However, according to the studies by the present inventors, the modified resin itself is unstable,
It was found that there is a problem that the reaction medium is washed away in the course of the reaction.

As a method for producing bisphenol, there is a technique described in Japanese Patent Publication No. 37-981. The method for producing bisphenols described in this publication describes that "phenol and acetone are substantially anhydrous under the presence of a substantially insoluble cation exchange resin at 30 to 125 ° C.
And contacting the effluent from the reaction zone with 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane-phenol adduct, reaction side. Separation into two streams, a stream containing organisms and phenols and a stream containing acetone, water and phenols, removing reaction by-products from the first stream, 2,2-bis (4-hydroxyphenyl) propane Is recovered and the reaction by-products, phenol and acetone are recycled to the reaction zone, and a substantially insoluble cation exchange resin is catalyzed by acetone and phenol present in excess of the stoichiometric amount. It is characterized in that it exists and reacts. " Then, as the cation exchange resin in this method, a cation exchange resin in which a cation exchange group is partially esterified with mercapto alcohol can be used, and thus a partially esterified cation exchange resin is used. The use is disclosed to have the advantage of promoting the reaction without contaminating the product.

However, even if a cation exchange resin in which a cation exchange group is partially esterified with mercapto alcohol is used, satisfactory results in terms of reaction results and catalyst life have not been obtained.

The method for producing bisphenols described in Japanese Patent Publication No. 45-10337 discloses "Phenol and ketone in the presence of a phenol-soluble mercaptan and a solid insoluble ion-exchange resin having sulfonic acid groups suspended. A method for producing bisphenols by reacting with an ion exchange resin, wherein the amount of mercaptan is about 0.05 to about 1% by weight based on the total weight of phenol and ketone, and Is about 0.1 to about 1 equivalent per mole of acetone ”. In this production method, an ion exchange resin is used as a catalyst, and a mercaptan containing ethyl mercaptan is used as a cocatalyst.

However, when these mercaptans are used alone, the reaction results can be satisfied to some extent, but the catalyst life is not industrially satisfactory.

An object of the present invention is to eliminate the above-mentioned conventional problems. That is, it is an object of the present invention to provide a method for producing bisphenols capable of extending the catalyst life by using an alkyl mercaptan mixed with a mercaptocarboxylic acid as a cocatalyst.

[0011]

The invention according to claim 1 for solving the above-mentioned problems is a ketone and a phenol in the presence of a sulfonic acid cation exchange resin, an alkyl mercaptan and a mercaptocarboxylic acid. A method for producing bisphenols, which is characterized by reacting with
The invention according to claim 2 is the method for producing bisphenols according to claim 1, wherein the alkyl mercaptan is ethyl mercaptan and the mercaptocarboxylic acid is 3-mercaptopropionic acid.

The method of the present invention will be described in detail below. In the method of the present invention, phenols and ketones are reacted. The phenols can be represented by Chemical Formula 1.

[0013]

[Chemical 1]

(In the formula, R _{1 to} R ₄ may be the same as or different from each other, and are a hydrogen atom and a carbon number of 1 to 1.
4 represents an alkyl group or a halogen atom. ) Preferable phenols include alkylphenols such as phenol, orthocresol, metacresol, 2,6-dimethylphenol, tetramethylphenol, 2,6-ditertiarybutylphenol, orthochlorophenol, metachlorophenol, 2 And halogenated phenols such as 6-dichlorophenol.

The ketones can be represented by R ₅ COR ₆ . In the formula, R ₅ and R ₆ may be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or a carbon number 6
To 14 aryl groups, C7 to C20 aralkyl groups,
It represents an alkylaryl group having 7 to 20 carbon atoms.

The preferred ketones have 1 carbon atom such as dimethyl ketone, methyl ethyl ketone, methyl-n-propyl ketone, and methyl isobutyl ketone.
Saturated fatty acid ketone having 2 or less, preferably 6 or less alkyl groups, aromatic ketones such as phenyl methyl ketone,
Examples thereof include unsaturated ketones such as mesityl oxide, and cycloaliphatic ketones such as cyclohexanone and methylcyclohexanone.

In the method of the present invention, the phenols and the ketones are reacted in the presence of a sulfonic acid cation exchange resin, an alkyl mercaptan and a mercaptocarboxylic acid.

The sulfonic acid cation exchange resin may be a strong acid cation exchange resin having a sulfonic acid group, and specific examples thereof include sulfonated styrene.
Examples thereof include divinylbenzene copolymer, sulfonated crosslinked styrene polymer, phenolformaldehyde-sulfonic acid resin and benzeneformaldehyde-sulfonic acid resin. These may be used alone or in combination of two or more.

Examples of the alkyl mercaptan include methyl mercaptan, ethyl mercaptan, propyl mercaptan, cyclohexyl mercaptan and the like. Of these, ethyl mercaptan is particularly preferable. In addition, these alkyl mercaptans can be used individually by 1 type, and can also use 2 or more types together.

The mercaptocarboxylic acid can be represented by the general formula (HS) _n -R-COOH. Here, n in the general formula represents an integer of 1 to 3, preferably 1. R in the general formula may have a substituent, and may be saturated or unsaturated, having 1 to 5 carbon atoms.
Represents an aliphatic hydrocarbon group.

Preferred examples of the mercaptocarboxylic acid include mercaptoacetic acid, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid and 4-mercaptobutyric acid. Of these,
3-Mercaptopropionic acid is particularly preferred. The mercaptocarboxylic acid may be used alone or in combination of two or more.

In the present invention, it is considered that the sulfonic acid cation exchange resin is the main catalyst, and the alkyl mercaptan and the mercapto carboxylic acid act as co-catalysts. Then, by using the alkyl mercaptan and the mercaptocarboxylic acid used for the co-catalyst, it is possible to prevent the activity of the catalyst from being lowered.

The mixing ratio of the alkyl mercaptan and the mercapto carboxylic acid is usually 99: 1 to 1: 1 in terms of the molar ratio of the alkyl mercaptan and the mercapto carboxylic acid.
99, preferably 97: 3 to 40:60.

In the present invention, the phenols and the ketones are reacted in the presence of the sulfonic acid cation exchange resin, the alkyl mercaptan and the mercaptocarboxylic acid to produce bisphenol. This reaction is represented by Chemical Formula 2.

[0025]

[Chemical 2]

The reaction method in this reaction is not particularly limited, but a fixed bed continuous reaction or a batch reaction is desirable. For example, when conducting a fixed bed continuous reaction, LHSV is usually
0.2 to 30 / Hr ^-1, preferably 0.5~6Hr ^-1.

As the reaction conditions in this reaction, the molar ratio of phenols to ketones is usually 3: 1 to 30: 1 phenol: ketone, preferably 5: 1 to 1: 1.
It is 5: 1.

The reaction temperature is usually 40 to 150 ° C, preferably 60 to 110 ° C. If the reaction temperature is lower than 40 ° C., the phenol phase may be solidified, and if the reaction temperature is higher than 150 ° C., a gas phase reaction occurs, which makes it difficult to control the reaction system.

Water is preferably absent in the reaction system, but the permissible water content is usually 1% or less, preferably 0.2% or less.

The molar ratio of mercaptan to acetone is usually 1: 100 to 20:10 mercaptan: acetone.
It is 0, preferably 3: 100 to 10: 100.

According to the method of the present invention, bisphenol is preferably produced by suppressing the deterioration of the catalyst.

[0032]

EXAMPLES Next, the present invention will be described more specifically by showing Examples and Comparative Examples of the present invention.

Example 1 A fixed bed filled with an ion exchange resin {sulfonated styrene-divinylbenzene copolymer, manufactured by Mitsubishi Kasei Co., Ltd., trade name; Diaion SK-104H} swollen in advance with phenol (1. 3cmφ ×
64 cm), at atmospheric pressure at 75 ° C., phenol 440 g
/ Hr and acetone solution 29g / Hr are mixed and oil is passed,
A continuous reaction was performed.

The acetone solution is 100 mol of acetone.
1, 4.5 mol of ethyl mercaptan as a co-catalyst, and 0.5 mol of 3-mercaptopropionic acid (hereinafter, also referred to as 3-MPA).

When the reaction mixture was analyzed over time and the phenol conversion rate was calculated, what was 11.6% at the start of the reaction was 10.3% after passing oil for 500 hours.
At this time, the conversion rate of the phenol conversion rate is 1.5% /
1,000 g / g-cat. Met.

Example 2 A fixed bed filled with an ion exchange resin {sulfonated styrene / divinylbenzene copolymer, manufactured by Mitsubishi Kasei Co., Ltd., trade name; Diaion SK-104H} previously swollen with phenol (1. 3cmφ ×
64 cm), at atmospheric pressure at 75 ° C., phenol 440 g
/ Hr and acetone solution 29g / Hr are mixed and oil is passed,
A continuous reaction was performed.

The acetone solution is 100 mol of acetone.
l, 4.95 mol of ethyl mercaptan as a cocatalyst,
And 0.05 mol of 3-MPA.

When the reaction mixture was analyzed over time and the phenol conversion rate was calculated, what was 12.4% at the start of the reaction was 10.2% after passing oil for 500 hours.
Phenol conversion rate at this time is 2.5% / 1,
000 g / g-cat. Met.

(Comparative Example 1) The procedure of Example 1 was repeated, except that only ethyl mercaptan was used as a cocatalyst and the acetone solution was 100 mol of acetone and 5 mol of ethyl mercaptan.

When the reaction mixture was analyzed over time and the phenol conversion rate was calculated, it was found that the rate of 11.7% at the start of the reaction was 9.4% after passing oil for 500 hours. At this time, the rate of decrease of the phenol conversion rate is 2.9% / 1,0.
00 g / g-cat. Met.

(Comparative Example 2) In Example 1, using only ethyl mercaptan as a co-catalyst, an acetone solution of 100 mol of acetone and ethyl mercaptan of 4.5 mo were used.
The same procedure as in Example 1 was carried out except that 1 was used.

When the reaction mixture was analyzed with time and the phenol conversion rate was calculated, what was 11.2% at the start of the reaction was 8.8% after passing oil for 500 hours. At this time, the rate of decrease of the phenol conversion rate is 2.8% / 1,0.
00 g / g-cat. Met.

From the results of Examples 1 and 2 and Comparative Examples 1 and 2 described above, in the method of the present invention, as compared with the case where the cation exchange resin as the catalyst and the ethyl mercaptan as the cocatalyst were combined, It can be said that the rate of decrease of the phenol conversion rate is suppressed to be small, and thus the rate of deterioration of the catalyst is small.

[0044]

According to the method of the present invention, it is possible to provide a method for producing phenol which has a low catalyst deterioration rate and is therefore suitable for continuous production for a long time.

Further, in the method of the present invention, the cation exchange resin itself as a catalyst is stable and is not washed out by the reaction medium. It also has the great advantage that there is no increase in product.

Continuation of the front page (56) Reference JP-A-2-17144 (JP, A) JP-A-1-157927 (JP, A) JP-A-4-1149 (JP, A) JP-A-54-19951 (JP , A) JP 56-46831 (JP, A) JP 57-118528 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 39/00 C07C 37/00

Claims (2)

(57) [Claims] 1. A process for producing bisphenols, which comprises reacting a ketone with a phenol in the presence of a sulfonic acid type cation exchange resin, an alkylmercaptan and a mercaptocarboxylic acid. 2. The method for producing bisphenols according to claim 1, wherein the alkyl mercaptan is ethyl mercaptan, and the mercaptocarboxylic acid is 3-mercaptopropionic acid.