JPS5962544A - Preparation of phenol adduct of 2,2-bis(4-hydroxyphenyl) propane - Google Patents

Abstract

PURPOSE:To prepare the titled compound in high quality with preventing adhesion of crystal to the face of an inner wall of a reactor, by reacting phenol with acetone in the presence of an acidic catalyst while the raw materials are jetted from a nozzle set at the top of the level of the liquid phase of the reactor to the inner wall of the reactor. CONSTITUTION:In preparing the titled adduct by reacting phenol with acetone in the presence of a soluble acidic catalyst to form a slurry reaction mixture containing crystal of the titled adduct, the reaction is carried out while the raw materials to be fed to the reactor are at least partially jetted from a nozzle set at the top of the liquid level of the reactor to the inner wall of the reactor. The ratio of the raw materials while jetted from the nozzle is preferably 0.4-1, and preferably the feed raw materials by jetting are supplied in such a way that they are distributed to the whole face of the inner wall of the reactor. Consequently, the contact state of the raw materials is improved, and the reaction rate is raised.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention produces 2,2-bis(4-hydroxyphenyl)propane (hereinafter abbreviated as p, p'-BPA) by reacting phenol and acetone in the presence of an acidic catalyst. ) phenol adducts (hereinafter p, p' −
It is abbreviated as BPA-PhOH. ), in which the p, p'-BPA-P is applied to the inner wall surface above the liquid phase surface of the reactor.
Prevents the adhesion of hOH crystals, resulting in high quality p,p
' -BPA-PhOH is provided by a method capable of producing it.

p,p'-BPA has been conventionally used as a raw material for polycarbonate, epoxy resin, and the like.

This 1. As the uses and demand for these resins expand, high-quality resins are required, and as a result, p, p'-BPA, which is the raw material for these resins, has a high purity and good color. There is a growing demand for quality products. In particular, p, p' of raw materials for polycarbonate
-BPA must be of high quality, e.g. purity 99.9
% or more and has a melting hue of 30 AP[(A or less).In addition, such high quality p, p'-BPA can be rationally and economically absorbed. Of course, it is also required that the product be manufactured in a timely manner. Swirl the requests of Kori, et al., p' -1
31) In order to economically produce A, it is necessary to react the raw materials phenol and acetone at a high conversion rate in one contact, and selectively apply p to the reacted raw materials.
, it is necessary to produce p'-BPA ligation, and it is necessary that the produced p, p'-BPA can be purified by an easy method.
- It is also required that BPA be of high quality, high yield, and low cost2. By the way, when reacting phenol and acetone, it is necessary to have a low conversion rate, for example, a conversion rate of acetone of 55% or less. In some cases, or when the molar ratio of phenol to acetone is high, Tl'-BPA is completely dissolved in the reaction mixture and the reaction mixture, excluding the catalyst system in the reaction system, is a homogeneous phase. It is. However, even if the reaction is carried out at such a low rate of change, p,p'-BPA cannot be economically produced and the above requirements cannot be met.

In order to improve this drawback, if the reaction is carried out by using an excess of phenol relative to acetone to increase the conversion rate of acetone, p,p'-BPA becomes p,p'-BPA・P
The crystals of p,p'-BPA-PhOH in this slurry reaction mixture crystallize as crystals of hOH, and the reaction mixture forms a slurry reaction mixture.
Scattering due to stirring, condensation of the vapors of raw material phenol, acetone, and acidic catalyst on the vessel wall, and the resulting condensation reaction occurring on the vessel wall, or other causes, the inner wall above the liquid phase surface in the reactor. and adheres to the stirring rod in a hard layer.1 This phenomenon of wall adhesion becomes more noticeable as the reaction time progresses when the reaction is carried out in a continuous method. If this phenomenon of wall adhesion becomes severe, it may become impossible to operate the reactor, or the deposits may peel off in large chunks, clogging the lines in the reaction system, resulting in a long-term continuous reaction. unable to continue. As a result, in addition to the need for troublesome operations such as periodically interrupting the reaction and removing impurities from inside the reactor, when this wall build-up becomes significant, colored by-products accumulate. Further formation of colored by-products occurs when air (oxygen) is introduced into the reaction mixture, either by heating the reactor to remove this deposit, or by opening it and mechanically removing the deposit. However, there is a drawback that it is difficult to obtain high quality p,p'-BPA from such p,p'-BPA-PhOH. When the above reaction is carried out in a continuous manner using hydrochloric acid or hydrogen chloride as an acidic catalyst, the reaction occurs due to the catalytic action of hydrogen chloride vaporized above the liquid phase surface in the reactor, so the above-mentioned The tendency is for r to become even larger.

Conventionally, many methods have been proposed and known for producing p,p'-BPA.PhOH by reacting phenol and acetone in the presence of acidic Ml. For example, when reacting phenol and acetone, a method using a catalyst and hydrochloric acid or hydrogen chloride, and p, p'-
A method for purifying and separating BPA is disclosed in Japanese Patent Publication No. 27-5367.

Special Publication No. 36-23335, Special Publication No. 68-4875
No. 40-7186.

Japanese Patent Publication No. 42-6333, Japanese Patent Publication No. 3379-1979, and Japanese Patent Publication No. 10384-1984.

Japanese Patent Publication No. 50-128428, Japanese Patent Publication No. 48-978
No. 55, JP-A-49-95347, JP-A-4
It has been proposed in JP-A-9-82651, 1% JP-A-53-101347, JP-A-54-98748, JP-A-54-98749, and others. In any of these prior art documents, the p,
No prescription has been made to improve the aforementioned problems due to wall adhesion of p'-BPA.PhOH.

The present invention has been made in view of the above-mentioned problems existing in the technical field of manufacturing T), T)'-BPA-PbOH and the current state of the prior art in the field. The purpose of this method is to produce a slurry reaction mixture containing crystals of p,p'-BPA-PhOH by reacting euphenol and acetone in the presence of an acidic catalyst. By suppressing the phenomenon of p,p'-BPA/PhOH crystals and other solids adhering to the upper inner wall, the reverse reaction rate is accelerated, long-term continuous reaction is possible, and high boiling point is achieved. High quality p,p'-BPA-P with low content of by-products and colored by-products
The purpose of the present invention is to provide a method for economically producing hOH, and more specifically, to provide a method for producing hOH economically. This is based on the discovery that the above object can be achieved by carrying out the reaction while spraying onto the inner wall of the vessel.

Briefly, the present invention involves reacting phenol and acetone in the presence of a soluble acidic catalyst to form a slurry reaction mixture containing crystals of p, p'-BPA-, PhOH. Naru p,
In the method for producing p'-BPA-PhOH, the reaction is carried out while injecting at least a part of the raw material supplied to the reactor onto the inner wall of the reactor from a nozzle provided above the liquid level of the reactor. Features p, p' -B
This is a method for producing PA-PhOH.

In the method of the present invention, phenol and acetone are i]
The reaction is carried out in the presence of a soluble acidic catalyst, and within the reaction system, the reaction mixture forms a slurry reaction mixture containing crystals of p,p'-BPA-PhOH. In the method of the present invention, the soluble acidic catalyst, reaction conditions, and reaction method used for the condensation reaction of phenol and acetone are as follows:
p, p'-BP produced in the reaction system and in the reaction mixture
It is not particularly limited as long as it forms a slurry reaction mixture containing crystals of A-PhO[(. -BP8・Pkl
Besides oH, 2-(2-hydroxyphenyl)-2-(
4-hydroxyphenyl)propane (hereinafter o, p'-
4-(4-hydroxyphenyl)-2,2 ,4-)limethylchroman (both 2-)
11), 2,4-bis(α,α-dimethyl-4-hydroxybenzyl)phenol (hereinafter referred to as BPX
), 2-(2-hydroxyphenyl) -2
,4,4-)limethylchroman (hereinafter abbreviated as o-dimer), 5-hydroxy-3-(4-hydroxyphenyl)-'1,1,3-)limethylindan (hereinafter referred to as I
High boiling point by-products such as PEP cyclic 2M form), 2,4-bis(4-hydroxyphenyl)-4-methyl-1-pentene (hereinafter abbreviated as IPEP linear 2M form); structure By-products such as unknown colored by-products are formed. Most of the target product p,p'-BPA forms adducts with phenol.

In the method of the present invention, the slurry reaction mixture formed by the condensation reaction comprises p as suspended solid components;
This is a slurry reaction mixture containing crystals of p'-BPA-PhOH as a main component and t-.

The slurry reaction mixture includes p, p'-BPA
The above-mentioned by-products may be included in addition to the -PhOH crystals. The mother liquor component constituting this slurry reaction mixture is p,p'-BPA or p,p'-BP.
A-PhOH.

Unreacted phenol, unreacted acetone, and the by-product Q'zl
It is a homogeneous phase mother liquor containing produced water, acidic catalyst, etc. 1
There are cases where p, p' -BPA or p, p'
-BPA・phoH1 unreacted phenol, unreacted acetone, oil one-phase mother liquor consisting of the above-mentioned by-products, acidic catalyst aqueous solution, unreacted phenol, unreacted acetone, trace amount of p
l r'' -BPA or p, p' -13PA -P
In some cases, it is a two-liquid phase mother liquor consisting of both an aqueous phase mother liquor consisting of h011 and the like. In order to increase the conversion rate of acetone and the selectivity to p,p'-BPA and its yield, the mother liquor components constituting the slurry reaction mixture should form the two-liquid phase mother liquor. It is preferable that the weight ratio of the aqueous phase mother liquor to the oil phase mother liquor is usually o, oi to 2, preferably 0.03 to 1.2.
is within the range of

In the method of the present invention, the reaction is carried out while injecting at least a portion of the raw material supplied to the reactor onto the inner wall of the reactor from a nozzle provided above the liquid phase surface of the reactor.

As a result, the contact state of the raw materials is improved, and the reaction rate is also improved. Examples of raw materials supplied to the reactor include raw material acetone, raw material phenol, acidic catalyst, and mother liquor for circulation described below. There are no particular limitations on the proportion of the raw materials that are injected onto the inner wall of the reactor from a nozzle provided above the liquid phase surface in the predispensing method of the present invention to the total raw materials supplied to these reactors. ,
Usually in the range of 0.2 to 1, preferably 0.4 to 1. As for the injection supply method, a nozzle installed at an arbitrary position above the liquid phase surface in the reactor is used. A method is adopted in which the feedstock is injected onto the inner wall surface of the reactor from the inside of the reactor.In this case, it is preferable to supply the injected feedstock so that it is distributed over the entire inner wall surface of the reactor.To do this, it is necessary to Provide multiple injection ports to spray in the surrounding direction, or
This is achieved by installing a rotatable nozzle that has at least one injection port at its tip so as to be able to spray water toward the inner wall surface.

In the latter method of spraying and supplying water to the nozzle and 1-,
Rotational force - A method is adopted in which the raw material is supplied to the hollow stirring shaft of the ban machine and injected from a supply nozzle installed at any position on the liquid phase surface of the hollow stirring shaft or stirring blade, and supplied while rotating. You can also. Further, the injection supply state 7 may be any state as long as the cleaning effect on the inner wall surface of the reactor can be sufficiently exerted, and the supply state is not particularly limited. For example, various methods such as a method of supplying in a spray state and a method of supplying in a jet state can be adopted.

In the method of the present invention, phenol and acetone are usually reacted by the following method. Examples of the soluble acidic catalyst used in the reaction include ordinary strong acidic protonic acids, preferably strong acidic inorganic acids. Specific examples of strong acidic inorganic acids include hydrogen fluoride, hydrofluoric acid, hydrogen chloride, hydrochloric acid, hydrogen bromide, hydrobromic acid, hydrogen halides, hydrohalic acids, sulfuric acid, nitric acid, etc. can do. Of these strongly acidic protic acids, it is particularly preferred to use hydrogen chloride or hydrochloric acid, particularly when a hydrochloric acid-containing catalyst is used to convert the reaction mother liquor of the slurry reaction mixture into an oil as described above. A two-liquid phase mother liquor consisting of a phase mother liquor and an aqueous phase mother liquor is formed [7 preferably 1. The proportion of soluble catalyst used is 1 in the slurry reaction mixture 10002.
The amount of protonic acid used is usually 0.5 to 5 mol, preferably 1 to 15 mol. In the method of the present invention, the soluble acidic catalyst alone can be used as the acidic catalyst, but a soluble acidic catalyst and other promoter components can also be used in combination. Conventionally known cocatalyst components are used, and usually a sulfur-containing compound soluble in the reaction mixture is used, and either gaseous, liquid or solid sulfur compounds are used. I can do J. Specifically, these promoters include - inorganic sulfur compounds such as sulfur chloride, sulfur dichloride, thiosulfate, potassium thiosulfate, and hydrogen sulfide:
Methyl mercaptan, n-propyl mercaptan, n-
Alkyl mercaptans such as butyl mercaptan; thiophenols such as thiophenol, p-methylthiophenol, p-ethylthiophenol, p-chlorothiophenol, thiohydroquinone, thionaphthol; thioglycolic acid, thioacetic acid, thiofol.

Mercapto-substituted aliphatic carboxylic acids such as robionic acid;
the alkyl mercaptans, the thiophenols,
Examples include the alkali metal salts of the mercapto-substituted aliphatic carboxylic acids; mercaptals and mercapdols derived from the mercaptans.

When these sulfur compounds are used as co-catalysts, the molar ratio to the soluble acidic catalyst in the reaction system is usually 1/2000 to 1/30, preferably 1/30.
It ranges from 1000 to 1150. The molar ratio of total phenol to total acetone supplied to the trap reactor during the reaction is usually 4 to 20, preferably 5 to 10.
is within the range of

It is preferable that the molar ratio of total phenol to total acetone be within this range, since this will result in a slurry reaction mixture with good properties.

ift:, during Li reaction, the rate of change of acetone is usually 9Q
The reaction is carried out until a value of 1 or more is reached, preferably 95 or more.

The higher the conversion rate of acetone during the reaction, the better the properties of the slurry reaction mixture will be obtained. The temperature during the reaction is usually 25 fJ.

70°C, preferably in the range of 30 to 60'C.

In the process of the invention, unreacted phenol and unreacted acetone separated from the slurry reaction mixture can also be fed as part of the feedstock of the process of the invention.

In addition, all or part of the reaction mother liquor separated from the slurry reaction mixture and containing the acidic catalyst and the by-products may be added to the reaction system with the raw materials in step 1. It can also be supplied.

Next, an outline of an example of a process diagram for carrying out the method of the present invention will be explained with reference to FIG. FIG. 1 is an example of a system diagram of a continuous condensation reactor for carrying out the method of the present invention. Replenishment raw material tanks 1 and 2, circulating oil phase mother liquor tank 3, and circulating water phase mother liquor tank 4 supply raw materials to a serial multistage reactor consisting of a first reaction tank 11, a second reaction tank 12, and a fifth reaction tank 13 in the reaction process. When the continuous condensation reaction of the reaction step is carried out in the serial multistage reactor, a slurry reaction mixture is formed, and the slurry reaction mixture is collected in the receiver 14. . The slurry reaction mixture is passed through a centrifugal separator 15 in the next separation step to a crude p+p'
-BP8.PhOH and a two-liquid phase reaction mother liquor are separated, and the two-liquid phase reaction c liquid is further separated into an oil phase mother liquor and an aqueous phase mother liquor in an oil-water separator 16 in the next circulation step. A portion of the separated oil phase mother liquor and aqueous phase mother liquor was added to 17 pkg as needed.
After discharging from 8, the remaining mother liquors are recycled to the reactor of the reaction step.

During the circulation of the aqueous phase mother liquor, the HC supplied in the HC1 absorption tank 5
It is saturated or supersaturated with t gas 6 and then circulated.

Next, the method of the present invention will be specifically explained using examples. In addition, in Examples and Comparative Example 0, the rate of change of acetone and the amount of n'-soluble acidic catalyst contained in 1000 r of the reaction mixture in the reaction system were measured by the following method t (therefore, crude T). , p'-BPA-PhOH
Circulating oil phase mother liquor, p' containing water in circulating water phase mother liquor,
The compositions of p'-BP8, phenol, water, HCA, and by-products were measured using the following methods.1. Ta.

1. Method for quantifying unreacted acetone The conversion rate of acetone was determined by dissolving the reaction mixture in an ethanol solvent, neutralizing it, and quantifying unreacted acetone using gas chromatography.

2. Determination of phenol and p'-BPA Phenol, p'-BPA were determined using rat gas chromatography.

3. Quantification method of HC/ HCt was determined by dissolving the sample in ethanol solvent and then using the usual neutralization titration method.

4. Assay method for by-products By-products are determined by dissolving the sample in ethanol and neutralizing it.
was determined using high performance liquid chromatography].

5. Circulating oil phase mother liquor and coarse, I)' -BPA-
Measurement of coloration degree of PhOH A sample was placed in a volumetric flask and diluted with ethanol.The diluted liquid was filled into a 10 crn cylindrical glass cell and the sample was placed in a volumetric flask for 70 spectrophotometric measurements.
Baush & T(om)
b) absorbance (or transmittance) at 360 nm and 48·Onm was measured. The concentration of the sample used for measurement was changed as appropriate depending on the color and color of the sample phase.

The degree of attachment of the sample was expressed by the following formula K. ,here,
A - Absorbance, C - Concentration of sample (w/v), b - Cell length (optical path length) (6n) In addition, 1 coefficient E480 described in the following examples and comparative examples is < til + constant wavelength 480 Elcln in nm is shown.

i, Figures 2 and 6 show the circulating oil phase mother liquor and coarse;
Reaction time (hr) of Tl'-BPA-PhOH (
41 axis) and the degree of coloration at 4 B Onm (E
11 coefficient m x 10') (vertical axis) is shown in a graph.

(in) Robert, M% Silverstein (Ro
bert, M. 5ilverstein),
G, Kratom, Bathosura (G, C1ayt
o+n Ba5sler), translated by Shun Araki and Yoichi Mashiko (Tokyo Kagaku Dojin), ``I. Spectral identification method of organic compounds''& Reaction tank for measuring the weight ratio of aqueous phase mother liquor to oil phase mother liquor in a slurry reaction mixture The slurry reaction mixture flowing out is received in a storage tank maintained at the same temperature as the j× reaction tank.

Once the reaction mixture had a certain amount in the reservoir, it was placed in a centrifuge kept at the same temperature as the reaction vessel and spun until the cake was almost dry. The mother liquor discharged from the centrifugal separator was led to a standing tank to separate oil and water. Next, the volume and specific gravity of each phase are measured, and the ratio of the water phase mother liquor to the oil phase mother liquor is
The quantitative ratio was determined.

Z Quality assay method for purified Tl, p'-BP (1)a
A sample and an immersion line thermometer (ASTM102) were input into a solid point measurement tube, cooled in a constant temperature bath at 140°C, and measured according to a conventional method.

(2) Analysis of organic impurities Analysis was performed using the same high performance liquid chromatography as in 4 above.

(3) Measurement of coloration degree E360 and E480 Samples were diluted with ethanol to 20 w/v %, and absorbance (transmittance) was measured in the same manner as in 5 above.

Example 1 Using the reaction apparatus shown in FIG. 1, a mother liquor circulation type continuous reaction was carried out. Of the six reaction vessels used in the reactor, the interior of the first reaction vessel has a distance of % of the height of the ceiling of the reactor lid from the liquid level in the gas phase above the liquid level. In any case, the stirring shaft is rotated at the same speed as the stirring shaft in the 1tf angular direction j~, and a portion of the liquid raw material (1) to be supplied is supplied to the upper surface of the 1"11 turning plate j' (1, (7) An elliptical plate (outer diameter is % of the reactor inner diameter) is installed on the stirring shaft so that the supplied liquid raw material can be injected onto the inner wall of the reactor by centrifugal force.

The temperatures of the first reaction tank, second reaction tank, third reaction tank, centrifugal separator, and oil/water separator were cooled and kept at 50°C.The first reaction tank was replenished with acetone 24.6f/hr % supplemented with phenol 143f /br, 15% sodium methyl mercaptan aqueous solution 1.0 f/hr.

The circulating aqueous phase mother liquor was charged continuously at a rate of 12 s r/brs and supplementary HC/-gas 5 t/hr. Regarding the circulating oil phase mother liquor, a 26q y/hr
The gas was supplied at a speed of 1, and was injected over the entire inner wall of the gas phase.

Here, the ratio of the injection supply liquid to the total supply liquid raw material is 0.48.

Continuous reactions were carried out, and as a result, the slurry reaction mixture flowing out from the fifth reaction tank was intermittently fed into a centrifugal separator for solid-liquid separation. The amount in excess of the predetermined amount to be supplied was extracted from the system, and the remainder was circulated to the first reaction tank and reused.

The reaction conditions for this continuous reaction are summarized in Table 1.

Table 1 The compositions of the circulating oil phase mother liquor and circulating water phase mother liquor in the continuous reaction were as shown in Table 2.

Table 2 When this continuous reaction experiment was conducted for 350 hours, there was no observed growth of solids on the inner walls of the gas phase and gas-liquid interface in the reaction tank, and stable continuous operation was possible. Ta. Dimensions, circulating oil phase mother liquor and centrifuged cake [crude pl
p' -BPA-·pho+-r] The degree of coloring expressed by E480 changed over time as shown in FIG. This figure shows that the degree of coloration of Chiri Sore tends to increase with repeated circulation of the mother liquor, but eventually reaches a plateau.
It can be seen that it will not increase any further.

1, similarly oil phase mother liquor and centrifuged cake (crude 1),
The concentration of by-products in D'-BPA-phoH) also settled down to a constant value. At this time, the concentrations of the by-products 'I Hcz and H20 contained in the oil phase mother liquor and the centrifuged cake, and the degree of coloration were as shown in Table 3.

Table 3 Quality of circulating oil phase mother liquor and centrifuged cake Also, the acetone conversion rate at the third reaction detection port was 99.5%, 350%
Acetone reference p+p' over time BP8・Ph
The total yield of OH was 99.7 mol. In addition, 1) + p' -BPA -PhO obtained as a result of the continuous reaction
The total average yield of H is 1462 per hour and t(, -
1 Example 2 In Example 1, the rotary agitator of the first reaction tank was changed to υ (()). With the modification, a mother liquor circulation type continuous reaction was carried out using exactly the same reaction conditions as in Example 1.As a long method of injecting and supplying the circulating oil phase mother liquor, rotation 751 The oil phase mother liquor was supplied to the hollow stirring shaft of the reactor, and was injected from a supply nozzle installed at the top of the reaction tank in the infant phase section of the reactor, washing away the entire inner wall surface while rotating.

In this way, a continuous reaction experiment was carried out for 350 hours (11), and as with the results of Example 1, no solid matter was observed to adhere to the inner wall surface of the gas phase section of the reaction tank, and a stable condition was observed. Continuous operation was possible.

1k, circulating oil phase mother liquor and centrifugation cake after 350 hours of continuous reaction [crude p, p'-BPA-photo(
'] Product a1 Change rate of acetone and p+ o/ -BP
The total yield of A-PhOH was exactly the same as in Example 1.

Example 3 In Example 1, the continuous reaction was carried out for 350 hours by changing the injection feed from the oil phase mother liquor to supplemented phenol. In this case, the ratio of the injection supply liquid to the raw material is 0.
It is 25.

Continuous reaction was carried out in this way for 350 hours, and as with the results of Example 1, no growth of solids on the inner wall surface of the gas phase portion of the reaction tank was observed. Stable continuous operation was possible.

Also, the circulating oil phase mother liquor and centrifugation cake after 350 hours of continuous reaction [crude p, 'Or-BPA-phoH
] quality, acetone conversion rate and p, p' -BPA
-Ph1) (The total yield was exactly the same as in Example 1.

Comparative Example 1゜In the continuous reaction of Example 1, the circulating oil phase mother liquor was injected and supplied to the inner wall of the gas phase section in the reactor, except that Example 1 was not carried out.
Continuous experiments are carried out under the same reaction conditions as above, while circulating the reaction mother liquor. After 40 hours have elapsed since the start of the continuous reaction, hard solids that have grown on the inner wall of the gas phase part of the first reaction tank and the inner wall of the gas-liquid interface fall into the reaction mixture.
Small pieces of solid proboscis were deposited in the reaction tank. the result,
Faulty V-circuits and blockage of overflow lines have become a problem. Therefore, the supply of replenishing acetone, replenishing phenol, circulating odor solution, etc. to the reaction system was stopped for 30 minutes]7. The temperature inside 1 was temporarily raised to 80°C to dissolve small pieces of solid matter. Then, 50℃
The mixture was gradually cooled at 1, then returned to the original reaction temperature at 7, and feeding was started to resume continuous reaction.

Thereafter, dissolving the solid matter was carried out at such intervals, and the top of the plate was continuously carried out for 350 hours in the same manner as in Example 1. E480 of Kl'-BpA-phoH]
The degree of coloration, expressed as , changed over time as shown in Figure 3. As is clear from FIG. 3, the change in E a so over time either settles to a constant value after 300 hours as in Example 1, or the value of @ @, III is about 5 times that of Example 1. It is. Table 4 shows the quality of the circulating oil phase mother liquor and centrifuged cake after 350 hours of continuous reaction. The total average yield of crude p1p'-BPA-PhOH obtained as a result of the continuous reaction was 1411 per hour.

Table 4 As is clear from comparing the quality of the circulating oil phase mother liquor and the centrifuged cake, the present invention has better results than the comparative example in terms of continuous operation time, yield, purity, etc. is obtained.

This is an especially remarkable effect in mass-produced products such as the object of the present invention.

[Brief explanation of drawings]

FIG. 1 is a system diagram of an m-liquid circulation type continuous condensation reaction pupil used in one embodiment of the present invention. 2nd part)
In Example 1 of the present invention, and in FIG. 3, Comparative Example υ
(In both cases, the circulating oil phase mother liquor and O'fL p,
Reaction time of p'-BpA-phon and 480 nm
It is a graph showing the relationship between the coloring degree and the degree of coloring. 1 and 2: Replenishment raw material tank, 6: Circulating oil phase 1ζ)'
Liquid tank, 4: Circulating water phase mother liquor tank, 11-13:
reaction tank, 14: receiver, 15: centrifugal separator, 16:
Oil/Water Separator/1st Permit Applicant Mitsui Petrochemical Industries Co., Ltd. Honshu Kagaku Kogyo Co., Ltd. Agent Hirotoshi Nakamoto Akio Benjo / Diagram

Claims (1)

[Claims] 1. Reacting phenol and acetone in the presence of a soluble acidic catalyst to form a slurry reaction mixture containing crystals of a phenolic adduct of p,2,2-bis(4-hydroxyphenyl)propane. consisting of 2
, a method for producing a phenolic compound of 2-bis(4-hydroxyphenyl)propane, in which at least a part of the raw material supplied to the reactor is supplied to the reactor from a nozzle provided above the liquid phase surface of the reactor. The characteristic is that the reaction is carried out while spraying it onto the inner wall.