KR20080094226A - Method for preparing bisphenol ap - Google Patents

Abstract

A method for preparing bisphenol AP is provided to obtain bisphenol AP in an economical and highly efficient manner while avoid a need for expensive starting materials or HCl gas. A method for preparing bisphenol AP represented by the following formula 1 comprises a step of reacting acetophenone with phenol in the presence of zinc chloride supported on a clay carrier as a catalyst. In the reaction, acetophenone and phenol are used in an equivalent ratio of 1:5-1:30. The zinc chloride catalyst is used in an amount of 1-10 mol% based on acetophenone. The reaction is carried out at a temperature of 40-100 deg.C.

Description

Manufacturing method of bisphenol APD {METHOD FOR PREPARING BISPHENOL AP}

[Industrial use]

The present invention relates to a method for producing bisphenol AP, and more particularly, to a method for efficiently producing bisphenol AP used in raw materials of engineering plastics such as polycarbonate resins and epoxy resins and color developers for thermal recording paper. It is about.

[Prior art]

Bisphenols, which are condensation products of phenols and carbonyl compounds, are widely used as starting materials or intermediates for the preparation of many commercial products.

Bisphenol AP, one of the bisphenols, is 1,1-bis- (4-hydroxyphenyl) -1-phenylethane (1,1-bis- (4-hydroxyphenyl) -1-phenylethane; BHPE), 4,4 '-(1-phenylethylene) bisphenol (4,4'-(1-phenylethylidene) bisphenol) and 1-phenylethylidene-4,4'-bisphenol (1-phenylethylidene-4,4'-bisphenol It is called the name.

In general, the bisphenol AP is prepared by condensation of acetophenone and phenol in the presence of zinc chloride (ZnCl ₂ ) and hydrochloric acid (HCl) gas. However, the hydrochloric acid gas, which is difficult to handle, must be used, the reaction time is 40 hours or more, and the yield is not high.

US Patent No. 5,136,110 discloses a method for preparing bisphenol AP by reacting 1,1-dichloroethylbenzene with phenol. However, 1,1-chlorobenzene as a reactant is an expensive compound, so it is not economical, and a large amount of chlorine (Cl ₂ ) gas is generated during the reaction, and there is a problem such as the need to add a facility to remove it.

In order to solve the problems of the prior art as described above, an object of the present invention is to provide a method for producing bisphenol AP economically and efficiently without using expensive raw materials or hydrochloric acid gas.

In order to achieve the above object, the present invention is a method for producing a bisphenol AP represented by the following formula (1) by reacting acetophenone and phenol, the production of bisphenol AP using a zinc chloride supported on a clay carrier as a catalyst Provide a method.

[Formula 1]

It is preferable that the equivalence ratios of the said acetophenone and a phenol are 1: 5-1: 30.

In addition, the zinc chloride is preferably 1 to 10 mol% based on acetophenone.

In the said reaction, the range of reaction temperature is 40 degreeC-100 degreeC, and it is preferable to become under nitrogen stream.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a method for producing bisphenol AP represented by the following Chemical Formula 1, and is characterized by increasing the production efficiency of bisphenol AP using zinc chloride supported on a clay carrier as a reaction catalyst:

[Formula 1]

Bisphenol AP of the present invention is prepared by reacting acetophenone and phenol, as shown in Scheme 1 below.

Scheme 1

In the above reaction, the zinc chloride catalyst further promotes the reaction of acetophenone and phenol by having an effect of widening the reaction surface area in contact with the reactants acetophenone and phenol supported on a porous clay carrier. In addition, the zinc chloride supported on the clay carrier is easier to handle than the powdered zinc chloride, is recyclable, and the method is also easy and economical. The clay used as a carrier here does not directly participate in the reaction because it serves as an inert support.

The present invention is characterized in that in the method for producing bisphenol AP, zinc chloride supported on a clay carrier is added as a catalyst.

It is preferable that the acetophenone and phenol are 1: 5 to 1:20 in an equivalent ratio, and more preferably 1: 7 to 1:10. If the content of phenol is less than 1: 5, the amount of phenol used as the reactant and the polymerization solvent is small, so that the yield is low. If the amount is greater than 1: 20, it takes a long time to recover the excess phenol. .

The zinc chloride is preferably 1 to 10 mol% based on acetophenone, and when zinc chloride is less than 1 mol% with respect to acetophenone, the effect as a catalyst is insignificant. The use of a catalyst is not economical and undesirable.

The zinc chloride catalyst supported on the added acetophenone, phenol and clay carrier is sufficiently stirred under a stream of nitrogen to react evenly at 40 ° C. to 100 ° C. and reacted for 4 hours. More preferably, the reaction temperature is 80 ° C.

After 4 hours of reaction, the reaction product is purified to obtain bisphenol AP in a crystalline state.

On the other hand, the catalyst used in the reaction is filtered and then reused by removing the water contained in the catalyst by raising it to the reflux temperature in a nonpolar solvent such as toluene.

Hereinafter, the configuration and effects of the present invention will be described in more detail with reference to specific examples and comparative examples in order to help understanding of the present invention. However, the following examples are only intended to more clearly understand the present invention, and are not limited to the following examples of the present invention.

EXAMPLE

Example 1

First, 120 g (1 mol) of acetophenone, 940 g (10 mol) of phenol, and 6.8 g (5 mol%) of EPZ10 catalyst (manufactured by Contract Chemical Co., Ltd.) were added to a four-necked flask equipped with a stirring device, a reflux cooler and a thermometer. 4 hours after raising the temperature to 80 ° C under a nitrogen stream Was stirred.

The reaction was terminated after confirming that the reaction conversion rate was 98% as a result of gas chromatography (GC) analysis.

After the reaction was completed, the reactant was cooled to 25 ° C, and the EPZ10 catalyst was filtered.

Next, the filtrate was distilled under reduced pressure, and excess phenol was distilled off, and 500 ml of methanol was added thereto, followed by cooling to 15 ° C. to obtain 269.7 g of bisphenol AP (93% yield of acetophenone) having a purity of 99.4% of white crystals.

Example 2

Bisphenol AP was prepared in the same manner as in Example 1, except that 1410 g (15 mol) was used instead of 940 g (10 mol) of phenol.

Example 3

Bisphenol AP was prepared in the same manner as in Example 1, except that 13.6 g (10 mol%) of EPZ10 catalyst was used instead of 13.6 g (10 mol%) of the EPZ10 catalyst.

Comparative Example 1

First, 240 g (2 mol) of acetophenone, 400 g (4.26 mol) of phenol, 27 g (0.2 mol) of zinc chloride, and 0.24 g (0.66 mol) of hydrochloric acid gas were added to a four-necked flask equipped with a stirring device, a reflux cooler and a thermometer. , 8 hours at 60 ℃ Was stirred.

Thereafter, 0.24 g (0.66 mol) of hydrochloric acid gas was added again, followed by 40 hours of reaction, and the reaction was terminated.

500 g of hot water was added to the reaction product after the reaction was completed, and the resulting crystals were filtered to obtain 550 g of light brown crystals.

This crystal was dissolved in 600 ml of 1,2-dichloroethane and recrystallized to obtain 490 g of bisphenol AP.

Comparative Example 2

Bisphenol AP was prepared in the same manner as in Example 1, except that 282 g (3 mol) was used instead of 940 g (10 mol) of phenol.

Comparative Example 3

Bisphenol AP was prepared in the same manner as in Example 1, except that 3290 g (35 mol) was used instead of 940 g (10 mol) of phenol.

Comparative Example 4

Bisphenol AP was prepared in the same manner as in Example 1, except that 0.68 g (0.5 mol%) was used instead of 13.6 g (10 mol%) of the EPZ10 catalyst.

Comparative Example 5

Bisphenol AP was prepared in the same manner as in Example 1, except that 47.6 g (35 mol%) was used instead of 13.6 g (10 mol%) of the EPZ10 catalyst.

The preparation conditions of the Examples 1 to 3 and Comparative Examples 1 to 5 and the yield of the prepared bisphenol AP are shown in Table 1 below.

TABLE 1

Acetophenone [mole] Phenolic [mole] Zinc Chloride [mol%] Yield [%] Example 1 One 10 5 93 Example 2 One 15 5 91 Example 3 One 10 10 93 Comparative Example 1 2 4.26 0.2 84 Comparative Example 2 One 3 5 78 Comparative Example 3 One 35 5 86 Comparative Example 4 One 10 0.5 79 Comparative Example 5 One 10 35 83

As shown in Table 1, Examples 1 to 3 in which a certain amount of zinc chloride catalyst supported on a clay carrier were added to a reactant for synthesizing bisphenol AP using a certain amount of acetophenone and phenol were added to the bisphenol AP in a conventional manner. It shows an excellent yield compared to Comparative Example 1 prepared. In addition, it can be seen from the above examples and comparative examples that the content ratio of phenol and zinc chloride to acetophenone. Therefore, it can be seen that the synthesis method using the zinc chloride catalyst supported on the clay carrier of the present invention is an economical and efficient method for producing bisphenol AP.

As described above, according to the manufacturing method of the bisphenol AP according to the present invention, by using a zinc chloride catalyst supported on a clay carrier, it has excellent reactivity, high yield, easy reuse and economical effects.

Claims (5)

In the method for producing a bisphenol AP represented by the following formula (1) by reacting acetophenone and phenol, A method for preparing bisphenol AP using zinc chloride supported on a clay carrier as a catalyst: [Formula 1]

The method of claim 1, The equivalent ratio of the acetophenone and phenol is 1: 5 to 1: 30 is a method for producing a bisphenol AP. The method of claim 1, The zinc chloride is a method for producing a bisphenol AP of 1 to 10 mol% based on acetophenone. The method of claim 1, The temperature range of the reaction is a method for producing a bisphenol AP is 40 ℃ to 100 ℃. The method of claim 1, And said reaction is under a stream of nitrogen.