JP6074902B2 - Method for producing purified phenolic compound - Google Patents

Description

  The present invention relates to a method for producing a purified phenol compound in which impurities remaining in the production process of a phenol compound are removed using a sulfonic acid type cation exchange resin.

Phenol is a very important compound that is used as a raw material for producing polycarbonate resin and epoxy resin, as well as a raw material for producing bisphenol A, which is industrially useful as an antioxidant, etc. Manufactured by. In the cumene method, benzene and propene are subjected to addition reaction by Friedel-Crafts reaction to produce cumene (isopropylbenzene) (the following reaction formula (i)), which is oxidized to cumene hydroperoxide, and further rearranged with an acid. To produce acetone and phenol (reaction formula (ii) below))
C ₆ H ₆ + CH ₂ = CHCH ₃ → C ₆ H ₅ CH (CH ₃ ) ₂ (i)
C ₆ H ₅ CH (CH ₃ ) ₂ + O ₂ → C ₆ H ₅ C (OOH) (CH ₃ ) ₂
→ C ₆ H ₅ OH + (CH ₃ ) ₂ C═O (ii)

  Bisphenol A is synthesized by the reaction of 2 equivalents of phenol and 1 equivalent of acetone (the following reaction formula (iii)), and in this reaction, a sulfonic acid type cation exchange resin modified with a thiol compound as a promoter. Is used as a catalyst (Patent Document 1).

The phenol obtained by the cumene method contains acetol (hydroxyacetone), mesityl oxide, benzaldehyde, acetophenone, (methyl) benzofuran, α-methylstyrene and the like as impurities. When phenol containing these impurities is used as a raw material for producing phenol derivatives,
(1) Deteriorating the thiol compound as a cocatalyst and reducing the catalytic activity.
(2) The resulting phenol derivative is colored.
There is a problem. In particular, the point (2) is a serious problem in phenol derivatives as raw materials for producing polycarbonate resins. That is, since the polycarbonate resin is suitably used for optical applications by taking advantage of its excellent transparency, its coloring is a serious drawback. Therefore, both the starting material phenol and the phenol derivative (bisphenol A) have a problem in hue.

  However, the impurities in phenol as described above have a boiling point close to that of phenol, and it is difficult to separate these impurities by distillation.

Conventionally, as a method for purifying phenol by removing these impurities in phenol used as a raw material for producing bisphenol A, a method of bringing phenol into contact with a sulfonic acid type cation exchange resin has been proposed (Patent Document 2).
When a phenol containing impurities is brought into contact with a sulfonic acid type cation exchange resin, the catalytic action of the sulfonic acid type cation exchange resin increases the molecular weight of the phenol by reacting impurities such as acetol with phenol, making it easy to phenol. Can be separated by distillation.

Patent Document 2 describes that the sulfonic acid type cation exchange resin to be used may be either a gel type or a porous type, and that the degree of crosslinking can be 2 to 8%. Specifically, In addition, a sulfonic acid type cation exchange resin “Diaion (registered trademark) SK104 (current name is“ SK104H ”)” manufactured by Mitsubishi Chemical Corporation is used.
This “SK104” is a gel cation exchange resin having an average particle size of 750 μm, a uniformity coefficient of 1.5, a large average particle size, and a large uniformity coefficient.

JP 2011-98301 A JP-A-57-72927

  According to the study by the present inventors, the gel-type sulfonic acid-type cation exchange resin specifically used in Patent Document 2 does not have a sufficient catalytic effect on the reaction between impurities such as acetol and phenolic compounds, Due to the slow reaction rate, it was found that the impurities in the phenolic compound could not be removed in a short time. Further, the durability of the catalyst is not satisfactory, and a problem has been found that the catalyst is deteriorated at an early stage and the catalytic activity is lowered.

  The present invention solves the above-mentioned conventional problems and enhances the reaction rate between these impurities and the phenolic compound when removing impurities such as acetol in the phenolic compound using the sulfonic acid type cation exchange resin. Another object of the present invention is to provide a method for producing a purified phenol compound that efficiently purifies a phenol compound in a short time.

  As a result of intensive studies to solve the above problems, the present inventor used a porous type sulfonic acid type cation exchange resin having a degree of cross-linking of a predetermined value or less, thereby allowing impurities such as acetol and phenolic compounds to be used. It has been found that the reaction rate with the compound can be increased, and that the catalyst life can be extended with a porous cation exchange resin.

  The present invention has been achieved based on such findings, and the gist thereof is as follows.

[1] In the method for producing a purified phenol compound, which is purified by bringing a phenol compound represented by the following formula (1) into contact with a sulfonic acid type cation exchange resin, the sulfonic acid type cation exchange resin has an average particle size It is a porous cation exchange resin having a diameter of 10 to 850 μm, a crosslinking degree of 1.0% or more and 4.5 % or less, and the sulfonic acid group of the sulfonic acid type cation exchange resin and pyridineethanethiol form an ionic bond. A method for producing a purified phenolic compound, characterized by comprising:

(In the above formula (1), R ₁ and R ₂ may be the same or different from each other, and each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or a haloalkyl group having 1 to 3 carbon atoms.)

[2] Oite to [1], exchange capacity of the sulfonic acid type cation-exchange resin which corresponds to the neutral salt decomposition capacity of the sulfonic acid groups per resin 1mL is, 0.2~1.3meq / mL- resin A process for producing a purified phenolic compound, characterized in that

[3] [1] or Oite in [2] The method of purifying phenol compound uniform coefficients of the sulfonic acid type cation-exchange resin is equal to or 1.4 or less.

[ 4 ] In any one of [1] to [ 3 ], a part of the sulfonic acid group of the sulfonic acid type cation exchange resin is modified with pyridine ethanethiol, and the modification rate is 1 to 40 mol%. A method for producing a purified phenolic compound, characterized in that it exists.
[5] In any one of [1] to [4], when the phenolic compound represented by the formula (1) is subjected to purification, the sulfonic acid type cation exchange resin is brought into contact with the phenolic compound before use. A method for producing a purified phenolic compound, characterized by performing conditioning.

[ 6 ] In any one of [1] to [ 5 ], the phenolic compound is brought into contact with the sulfonic acid type cation exchange resin and the anion exchange resin.

  ADVANTAGE OF THE INVENTION According to this invention, the reaction rate of impurities, such as acetol in a phenolic compound, and a phenolic compound can be raised, and the impurity content in a phenolic compound can be reduced efficiently in a short time.

  In addition, the gel type cation exchange resin reacts mainly on the resin surface, whereas the porous cation exchange resin causes the phenolic compound and impurities to diffuse into the resin and the reaction also occurs inside the resin. As a result, the resin life until the catalytic action is deteriorated can be extended, and the cation exchange resin can be effectively used for a long time.

  Hereinafter, embodiments of the method for producing a purified phenol compound of the present invention will be described in detail. However, the present invention is not limited to the following description, and can be arbitrarily modified without departing from the gist of the present invention. Can be implemented. In addition, in this specification, when expressing by putting a numerical value or a physical-property value before and behind using "-", it shall use as what includes the value before and behind.

  The method for producing a purified phenol compound according to the present invention is a method for producing a purified phenol compound in which a phenol compound represented by the following formula (1) is purified by contacting with a sulfonic acid type cation exchange resin. The type cation exchange resin is a porous cation exchange resin having a crosslinking degree of 6.0% or less.

(In the above formula (1), R ₁ and R ₂ may be the same or different from each other, and each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or a haloalkyl group having 1 to 3 carbon atoms.)

Examples of the halogen atom for R ¹ and R ² include a fluorine atom, a chlorine atom, and a bromine atom. Among these, a fluorine atom is preferable. Examples of the alkyl group having 1 to 3 carbon atoms of R ¹ and R ² include a methyl group, an ethyl group, and a propyl group. Among these, a methyl group is preferable. The haloalkyl group having 1 to 3 carbon atoms of R ¹ and R ² is preferably a haloalkyl group having 1 carbon atom, and more preferably a trifluoromethyl group. Among R ¹ and R ² listed above, preferred are a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, etc. Among them, a hydrogen atom is most preferred. Incidentally, when R ¹ and R ² is a substituent other than a hydrogen atom, it is preferred substituents R ¹ and R ² are the same. The position of the substituent is preferably the ortho position.

  The method for producing a purified phenolic compound according to the present invention increases the reaction rate between the phenolic compound and impurities such as acetol in the phenolic compound, and efficiently reduces the impurity content in the phenolic compound in a short time. It has the feature of being able to. This is because the sulfonic acid type cation exchange resin used in the present invention easily diffuses phenolic compounds and impurities into the resin, and as a result, a gel type sulfonic acid type cation in which the reaction proceeds mainly on the resin surface. This is considered to be because the reaction rate can be increased by improving the reactivity of the phenolic compound and impurities in the cation exchange resin as compared with the exchange resin.

[Phenolic compounds]
The phenolic compound to be purified in the present invention is a phenolic compound represented by the above formula (1) and usually produced by the cumene method. Acetol (hydroxyacetone), mesityl oxide, benzaldehyde, acetophenone, (methyl) benzofuran , (Α) -methylstyrene and the like as impurities. However, the phenolic compound to which the method for producing the purified phenolic compound of the present invention is applied is not limited to that produced by the cumene method, and any phenolic compound containing impurities as described above may be used. The present invention can also be suitably used for the obtained one. In the present invention, the phenolic compound represented by the formula (1) may be simply referred to as “phenolic compound”.

  Usually, the above-mentioned impurities are contained in the phenolic compound to be purified in the present invention in an amount of about 1 to 300 ppm, for a total of about 10 to 1000 ppm.

[Sulfonic acid type cation exchange resin]
<Porous cation exchange resin>
In the present invention, the sulfonic acid cation exchange resin used for the purification of the phenolic compound is a porous cation exchange resin. Whether the cation exchange resin is a gel type or a porous type can be easily discriminated visually, and the porous type has an opaque appearance due to its porosity compared to a transparent gel type cation exchange resin.

  The porous cation exchange resin can be produced using a porosizing agent according to a conventional method such as a production method described in JP-A-5-239237.

  Examples of the porosifying agent include linear or branched hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane, dodecane, isooctane, gasoline and mineral oil; n-butanol, s-butanol, t-butanol, Alcohols having 4 or more carbon atoms and linear or branched alkyl chains such as pentanol, hexanol, octanol, methyl isobutyl carbinol; toluene, xylene (ortho, meta, para), benzene, chlorobenzene, dichlorobenzene, nitrobenzene, bromo Aromatic hydrocarbons which may have substituted aromatic rings such as benzene, aniline, ethylbenzene and diethylbenzene; Halogenated hydrocarbons such as dichloromethane, chloroform and dichloroethane; polystyrene, polyethylene and polypropylene Polyester, and polymers such as polyurethane. These may be used individually by 1 type and may be used in combination of 2 or more type.

  In addition, the sulfonic acid type cation exchange resin used in the present invention is usually in a particle shape (granular). Specific shapes include various shapes such as a spherical shape, a substantially spherical shape, a polyhedral shape, and an aggregate shape, but are not particularly limited.

<Degree of crosslinking>
The degree of crosslinking of the sulfonic acid type cation exchange resin used in the present invention is 6.0% or less. The degree of crosslinking is preferably 1.0% or more, more preferably 1.5% or more, still more preferably 2.0% or more, and particularly preferably 2.5% or more. On the other hand, it is preferably 5.5% or less, more preferably 5.0% or less, and further preferably 4.5% or less. The degree of crosslinking referred to here is determined by the weight percentage of the crosslinkable aromatic monomer with respect to the total weight of all charged polymerizable monomers used in the production of the sulfonic acid type cation exchange resin.

  It is preferable for the degree of crosslinking to be not more than the above upper limit value because the diffusion resistance in the cation exchange resin is lowered and the catalytic activity is improved. On the other hand, when the degree of crosslinking is not less than the above lower limit value, it is preferable from the viewpoint of maintaining the strength of the cation exchange resin, and when used for purification of the phenolic compound, it is used for conditioning by contacting with the phenolic compound before use. It is preferable because swelling and shrinkage can be suppressed and crushing of the cation exchange resin can be prevented.

  In the present invention, “catalytic activity” and “catalytic effect” of a sulfonic acid type cation exchange resin refer to catalytic activity and catalytic effect for the reaction between a phenolic compound and impurities such as acetol in the phenolic compound. .

<Average particle size>
The sulfonic acid type cation exchange resin used in the present invention preferably has an average particle size in the following range.

In the continuous reaction tank, the average particle diameter is preferably 10 μm or more from the viewpoint of filterability of the resin, more preferably 50 μm or more, and in the fixed bed, the average particle diameter is from the viewpoint of suppressing pressure loss during liquid passage. The particle size is preferably 200 μm or more, and more preferably 400 μm or more.
On the other hand, the average particle size is preferably 850 μm or less, more preferably 750 μm or less, further preferably 700 μm or less, and particularly preferably 600 μm or less from the viewpoint of catalytic activity and suppression of product crushing. preferable.

  The average particle diameter of the sulfonic acid type cation exchange resin is measured and calculated by the method described in the Examples section described later.

<Uniformity coefficient>
The sulfonic acid type cation exchange resin used in the present invention preferably has a sharp particle size distribution, and preferably has a uniformity coefficient of 1.4 or less, particularly 1.2 or less, especially 1.1 or less. Is preferred. When the uniformity coefficient is less than or equal to the above upper limit, the catalytic activity is improved and the pressure loss when the phenolic compound is passed through the packed layer of the sulfonic acid type cation exchange resin is preferable. The smaller the uniformity coefficient, the better. The lower limit of the uniformity coefficient is 1.0.

In the present invention, “homogeneous coefficient” means the ratio of the particle size through which 40% of the total resin passes to the particle size through which 90% of the total resin passes in the cumulative particle size distribution of the resin. The uniformity coefficient of the type cation exchange resin is measured and calculated by the method described in the Examples section below.
A smaller uniformity coefficient means higher particle uniformity, and a uniformity coefficient of 1.0 represents completely uniform particles.

  In addition, as a method of making the sulfonic acid type cation exchange resin used in the present invention a resin having a low uniformity coefficient, a method of classifying resin particles is also known, and in the production of a polymer constituting the resin, a spray method is used. A method is also known in which uniform resin particles are produced in advance by, for example, and then sulfonated. In the examples of the present invention, the resin is produced by the classification method, but the method of making the resin having a low uniformity coefficient is not limited to the classification methods shown in the examples of the present invention.

<Exchange capacity (neutral salt decomposition capacity)>
The sulfonic acid type cation exchange resin used in the present invention is preferably a sulfonic acid type strongly acidic cation exchange resin, and the exchange capacity corresponding to the neutral salt decomposition capacity of the sulfonic acid group per 1 mL of the resin is 0.00. 2 meq / mL-resin or more is preferable, 0.6 meq / mL-resin or more is more preferable, and 1.8 meq / mL-resin or less is preferable, and 1.3 meq / mL-resin or less is more preferable. When the exchange capacity is not less than the above lower limit value, the catalyst activity is sufficient, and when the exchange capacity is not more than the above lower limit value, it is preferable in terms of catalyst activity and catalyst life.

  The exchange capacity of this sulfonic acid type cation exchange resin can be determined, for example, by the following method. When a commercially available sulfonic acid type cation exchange resin is used, a catalog value is adopted.

Take 10.00 mL of sample. It is transferred to a filter tube with demineralized water, and excess demineralized water is drained until the water surface is about 10 mm above the sample.
280 mL of 2N HCl and then about 1 L of demineralized water are sequentially passed through the filter tube with downflow SV30 hr ⁻¹ to regenerate and wash the resin.
Next, 250 mL of 5 wt% NaCl is allowed to flow at SV30 hr ⁻¹ , and the entire amount of the effluent is collected in a 250 mL volumetric flask.
This solution is titrated with a 0.1N NaOH aqueous solution (force value: F) using a methyl red / methylene blue mixed indicator to obtain a titer a (mL).
The exchange capacity (meq / mL-resin) is calculated by the following formula.
Exchange capacity (meq / mL-resin) = [a (mL) × 0.1 × F] / 10

<Thiol modification>
The sulfonic acid type cation exchange resin used in the present invention may have a part of its sulfonic acid group modified with a thiol compound. If such a thiol-modified sulfonic acid type cation exchange resin is used, it depends on the thiol compound. The reaction rate between the phenolic compound and impurities can be further increased by the cocatalyst effect.

  The thiol compound used for modification of the sulfonic acid type cation exchange resin is not particularly limited as long as it is a compound that forms an ionic bond with the sulfonic acid group of the cation exchange resin. Examples of such a thiol compound include aminoalkanethiols such as 2-aminoethanethiol, 3-aminopropanethiol, N, N-dimethylaminopropanethiol; 4-aminobenzenethiol; 4-pyridinethiol; 3-pyridine Pyridine alkanethiols such as methanethiol and pyridineethanethiol; thiazolidines such as thiazolidine, 2,2-dimethylthiazolidine, 2-methyl-2-phenylthiazolidine, and 3-methylthiazolidine, and these thiol groups are protected. Derivatives thereof. Of these, pyridine ethanethiol such as 2- (2-pyridine) ethanethiol and 4- (2-pyridine) ethanethiol is preferred because of its excellent promoter activity. These may be used alone or in combination of two or more.

  The ratio (modification rate) of modifying the sulfonic acid type cation exchange resin with the thiol compound is preferably 40 mol% or less, more preferably 30 mol% or less of the total sulfonic acid groups of the sulfonic acid type cation exchange resin. , 25 mol% or less is more preferable, and 20 mol% or less is particularly preferable. On the other hand, the modification rate is preferably 1 mol% or more, and more preferably 5 mol% or more.

  When the modification rate by the thiol compound is in the above range, the group derived from the thiol compound acts as a co-catalyst without causing a decrease in the catalytic activity due to a decrease in the amount of the sulfonic acid group required for the reaction between the phenolic compound and the impurity. Can be expressed to the maximum. When the modification rate is too small, the effect of improving the reaction rate tends to be low, and the activity and life as a catalyst tend to be insufficient. On the other hand, when the modification rate is too large, the reaction rate is improved, but the amount of the sulfonic acid group involved in the reaction is decreased, so that the reactivity tends to decrease. Moreover, since many expensive thiol compounds are used, it is not economically preferable.

  Modification of the sulfonic acid type cation exchange resin with a thiol compound can be performed according to a conventional method described in JP-A No. 2010-1119995.

In addition, in this invention, the modification | denaturation rate by a thiol compound can be calculated | required by the method of measuring the quantity of SH group after carrying | support by iodine titration (redox titration) based on following reaction formula (iv) and (v) ( R in the following reaction formula (v) is a sulfonic acid type cation exchange resin.) More specific methods are described in the examples below.
IO ₃ ⁻ + 5I ⁻ + 5H ⁺ → 3I ₂ + 3H ₂ O (iv)
_{2R-SH + I 2 → R} -S-S-R + 2HI ... (v)

  The sulfonic acid type cation exchange resin used in the present invention may be only a modified sulfonic acid type cation exchange resin as described above, or may be only an unmodified sulfonic acid type cation exchange resin. The cation exchange resin and the unmodified sulfonic acid cation exchange resin may be used in combination. When a phenolic compound is passed through a resin layer filled with a modified sulfonic acid type cation exchange resin and an unmodified sulfonic acid type cation exchange resin, the arrangement of both resins can be performed even in a mixed state of both resins. It may be a two-layer structure. In the latter case, in order to minimize deterioration of the modified resin due to impurities, it is preferable to dispose the unmodified resin upstream and the modified resin downstream. The sulfonic acid type cation exchange resin used in the present invention may be a mixture of two or more kinds of modified sulfonic acid type cation exchange resins having different crosslinking degrees, average particle diameters, and thiol compounds used for modification. . However, in the present invention, in order to obtain the above-mentioned effect by using a sulfonic acid type cation exchange resin having a small uniformity coefficient, when using a mixture of two or more sulfonic acid type cation exchange resins, The uniformity coefficient of the sulfonic acid type cation exchange resin is preferably 1.4 or less.

  In the present invention, the sulfonic acid type cation exchange resin having the above-mentioned preferred physical properties can be produced and used. However, a commercially available product having a crosslinking degree and a sulfonic acid group amount within the above preferred range can be classified by classification as required. You may use it, adjusting an average particle diameter and a uniform coefficient, or carrying out thiol modification | denaturation as needed. Examples of commercially available porous sulfonic acid cation exchange resins suitably used in the present invention include “Diaion (registered trademark) PK206H” and “Diaion (registered trademark) PK208H” manufactured by Mitsubishi Chemical Corporation. “Diaion (registered trademark) PK210H” and the like.

[Method of contact with sulfonic acid type cation exchange resin]
There is no particular limitation on the method of bringing the phenolic compound used for purification into contact with the sulfonic acid type cation exchange resin. After the phenolic compound and the sulfonic acid type cation exchange resin are mixed with stirring, the sulfonic acid type cation exchange resin is mixed. A method of filtering and separating the resin, a method of extracting the treatment liquid while supplying the phenolic compound to the stirring tank containing the cation exchange resin, a downward flow of the phenolic compound to the packed bed of the sulfonic acid type cation exchange resin, or For example, a method of flowing in an upward flow can be used.

When the phenolic compound is passed through the packed layer of the sulfonic acid type cation exchange resin, the liquid passing rate is preferably SV 0.5 to 50 hr ⁻¹ , particularly preferably ¹ to 15 hr ⁻¹ . If the flow rate is too high, the pressure loss during the flow will increase, or the phenolic compound and impurities cannot react sufficiently, and if it is too low, the processing efficiency tends to decrease.

  The higher the temperature (treatment temperature) of the phenolic compound brought into contact with the sulfonic acid type cation exchange resin, the higher the reaction rate, but the resin life tends to be shorter. The treatment temperature is not lower than the melting point (40 ° C.) of the phenolic compound and not higher than the heat resistance temperature of the sulfonic acid type cation exchange resin, and is usually 50 to 120 ° C., preferably 60 to 80 ° C.

[Anion exchange resin]
In the present invention, the phenolic compound may be further treated with an anion exchange resin, and by using the anion exchange resin, among the impurities in the phenolic compound due to the catalytic effect of the anion exchange resin, Ketones such as acetol and mesityl oxide, and carbonyl derivatives of aldehydes can be made high molecular weight by aldol condensation reaction to enhance the distillation separation from phenolic compounds.

  Here, examples of the anion exchange resin include strong basic anion exchange resins from the viewpoint of catalytic activity, but weakly basic anion exchange resins are preferable from the viewpoint of heat resistance and life. For example, “Diaion (registered trademark) WA30 (weakly basic resin having a dimethylamino group)”, “Diaion (registered trademark) WA20”, “Diaion (registered trademark) CR20 (polyalkylene) manufactured by Mitsubishi Chemical Corporation. Weakly basic resin having a polyamino group) ”and the like.

  When the phenolic compound is treated by contacting with an anion exchange resin, a mixed bed of the anion exchange resin and the sulfonic acid type cation exchange resin is formed, and the phenolic compound is passed through this, The treatment with the anion exchange resin and the treatment with the sulfonic acid type cation exchange resin may be performed simultaneously.

  When the treatment with the anion exchange resin and the treatment with the sulfonic acid type cation exchange resin are performed separately, it is preferable that the treatment with the sulfonic acid type cation exchange resin is performed first, followed by the treatment with the anion exchange resin. That is, for example, when a phenolic compound is passed through a sulfonic acid type cation exchange resin packed bed, polystyrene sulfonic acid or phenolsulfonic acid is eluted from the sulfonic acid type cation exchange resin and flows out to be contained in the phenolic compound. It is possible to adsorb and remove polystyrene sulfonic acid and phenol sulfonic acid by treating the eluted phenolic compound containing polystyrene sulfonic acid and phenol sulfonic acid with an anion exchange resin. Treatment of sulfonic acid or phenolsulfonic acid is not necessary.

  Thus, when using an anion exchange resin together, as processing temperature by anion exchange resin, it is 50-120 degreeC which is the processing temperature of the phenolic compound by the above-mentioned sulfonic acid type cation exchange resin, Especially 55-55. It is preferably 80 ° C., and since it is excellent in heat resistance against such temperature conditions, it is preferable to use a weakly basic anion exchange resin as the anion exchange resin.

  The amount of the anion exchange resin used is not particularly limited, but is preferably 50% by volume or less, for example, 1 to 30% by volume, particularly 1 to 10% by volume, based on the amount of the sulfonic acid cation exchange resin. .

[Distillation purification]
As described above, after treating the phenolic compound with the sulfonic acid type cation exchange resin, or the sulfonic acid type cation exchange resin and the anion exchange resin, the phenolic compound is purified by distillation according to a conventional method, Impurities that have become high-boiling compounds by high molecular weight by treatment with sulfonic acid type cation exchange resin, and impurities that have become high-boiling compounds by condensation to high molecular weight by treatment with anion exchange resin Thus, it is possible to efficiently distill and separate from the phenolic compound, and it is possible to obtain a highly purified purified phenolic compound from which impurities are highly removed.

  The phenolic compound purified according to the present invention is a high-purity phenolic compound in which impurities during the production of the phenolic compound are sufficiently reduced, coloring due to impurities is reduced, and bisphenol A such as bisphenol A and bisphenol A, etc. It is useful as a raw material for producing various derivatives represented by aromatic polycarbonate resins starting from phenols and starting from phenolic compounds, and for other uses.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In addition, the values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value. A range defined by a combination of values of the following examples or values of the examples may be used.

  In addition, the evaluation method of the physical property of the sulfonic acid type cation exchange resin used in the following Examples and Comparative Examples is as follows.

<Degree of crosslinking>
It calculated | required by the ratio (weight%) of the crosslinkable aromatic monomer with respect to the total weight of all the preparation polymerizable monomers.

<Average particle diameter (weight average particle diameter)>
The sieves having a sieve mesh diameter of 1180 μm, 850 μm, 710 μm, 600 μm, 425 μm, and 300 μm were stacked so that the sieve mesh diameter was decreased as it went downward. The stacked sieve was placed on a vat, and about 100 mL of cation exchange resin was put into the 1180 μm sieve stacked on the uppermost stage.
Water was gently poured onto the resin from a rubber tube connected to the demineralized water supply port, and the small particles were sieved downward.
The cation exchange resin remaining in the 1180 μm sieve was further screened for small particles by the following method. That is, water was filled to a depth of about 1/2 of another bat, and a 1180 μm sieve was repeatedly shaken by applying up and down and rotating motions in the bat to screen out small particles.
The small particles in this vat were returned to the next 850 μm sieve, and the cation exchange resin remaining on the 1180 μm sieve was collected in another vat. If the cation exchange resin is clogged in the sieve, place the sieve in the vat in reverse, closely contact the rubber tube connected to the demineralized water supply port, and flow the water strongly to exchange cations in the sieve. The resin was removed. The cation exchange resin taken out was transferred to a bat where the cation exchange resin remaining on the 1180 μm sieve was collected, and the total volume was measured with a graduated cylinder. This volume was defined as a (ml).
The cation exchange resin that passed through the 1180 μm sieve was subjected to the same operation for the 850 μm, 710 μm, 600 μm, 425 μm, and 300 μm sieves, respectively, and volume b (volume of the resin remaining on the 850 μm sieve) using a graduated cylinder ( mL), c (volume of resin remaining on 710 μm sieve) (mL), d (volume of resin remaining on 600 μm sieve) (mL), e (volume of resin remaining on 425 μm sieve) (ML), f (the volume of the resin remaining on the 300 μm sieve) (mL) was determined, and finally the volume of the resin that passed through the 300 μm sieve was measured with a graduated cylinder to obtain g (mL).

V = a + b + c + d + e + f + g,
a / V × 100 = a ′ (%)
b / V × 100 = b ′ (%)
c / V × 100 = c ′ (%)
d / V × 100 = d ′ (%)
e / V × 100 = e ′ (%)
f / V × 100 = f ′ (%)
g / V × 100 = g ′ (%)
Was calculated.

From the calculated a ′ to g ′, the cumulative residual amount (%) of each sieve was taken on one axis, and the diameter (mm) of the sieve mesh was taken on the other axis, and this was plotted on logarithmic probability paper. Take 3 points in descending order of residue, draw a line that satisfies these 3 points as much as possible, and determine the diameter (mm) of the sieve mesh corresponding to 50% of the accumulated residue from this line. The diameter.
(In addition, the calculation method of the said average particle diameter is well-known publicly described on page 140-142, for example, Mitsubishi Chemical Corporation ion exchange resin division "Diaion 1" revised 1st edition (October 31, 2007). (This is the calculation method.)

<Uniformity coefficient>
On the logarithmic probability paper, the cumulative residual amount (%) of each sieve of a ′ to g ′ calculated in the above average particle diameter measurement and the diameter (mm) of the corresponding sieve mesh are plotted. Three points were selected in the order of the most, and a straight line was drawn to satisfy these three points as much as possible. From this straight line, the diameter (mm) of the sieve mesh corresponding to 90% of the accumulated residue was obtained and used as the effective diameter. Next, the diameter (mm) of the sieve mesh corresponding to the residual cumulative amount of 40% was determined, and the uniformity coefficient was determined by the following equation.
Uniformity coefficient = [diameter of the mesh corresponding to the residual 40% (mm)] / [effective diameter (mm)]
(In addition, the calculation method of the said uniform coefficient is well-known publicly described on pages 140-142, for example, "Diaion 1" revised edition (October 31, 2007) issued by Mitsubishi Chemical Corporation ion exchange resin division. (This is a calculation method.)

<Modification rate>
In a 100 mL Erlenmeyer flask, 1 g of resin denatured with a thiol compound and dehydrated by centle was added and precisely weighed. 0.5 g of potassium iodide was added, then 1 mL of acetic acid was added with a pipette, 20 mL of demineralized water was further added, and the mixture was stirred with a stirrer. After 30 minutes, a solution containing the resin was appropriately determined with a 1/100 N potassium iodate solution. This was repeated three times, and the average value was defined as the amount of SH supported by the resin, that is, the modification rate of the thiol compound.

[Example 1]
<Preparation of thiol-modified sulfonic acid type cation exchange resin>
Particle size of 490 to 510 μm of sulfonic acid type cation exchange resin “Diaion (registered trademark) PK206H” (Mitsubishi Chemical Corporation) (porous type, degree of cross-linking 3.0%, exchange capacity 0.84 meq / mL-resin) Minamata classification was done in the range. The average particle diameter of the sulfonic acid cation exchange resin after classification was 500 μm, and the uniformity coefficient was 1.03. After classification, the sulfonic acid type cation exchange resin was weighed with a 10 ml graduated cylinder, dehydrated with a centrifugal separator, put into a petri dish, and dried with a vacuum dryer at 50 ° C. for 8 hours.

  A condenser, thermocouple, glass stirring rod, Teflon (registered trademark) stirring blade, and three-one motor were set in a 200 mL four-necked flask, and phenol (Kishida Chemical Co., Ltd.) heated and melted at 70 ° C. in this four-necked flask. Special reagent grade (same below) (80.50 g) and the above dry cation exchange resin are placed in a nitrogen stream (10 mL / min) and immersed in an oil bath heated to 70 ° C., and sulfonic acid at 70 ° C. for 2 hours. The type cation exchange resin was allowed to swell in a stationary state, and then, with stirring at 180 rpm, a phenol solution of 2- (2-pyridine) ethanethiol was added with an automatic pipetter and further swelled for 1 hour. The modification ratio of the obtained thiol-modified sulfonic acid type cation exchange resin with respect to all sulfonic acid groups was 10 mol%.

<Preparation of treated phenol>
In a 125 mL pressure bottle, acetol (hydroxyacetone) (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), mesityl oxide (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), 2-methylbenzofuran (reagent manufactured by Sigma-Aldrich Co.), acetophenone (reagent special grade manufactured by Kishida Chemical Co., Ltd.) ), Benzaldehyde (special grade manufactured by Kishida Chemical Co., Ltd.) and α-methylstyrene (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and phenol melted at 70 ° C. was added to make a uniform solution. The concentration of each component was adjusted to 1.0% by weight. This solution was further diluted with phenol to prepare a phenol to be treated having each component of 1000 ppm.

<Phenol purification (heavy ratio of impurities in phenol)>
To the thiol-modified sulfonic acid type cation exchange resin swollen with the above phenol, the above-mentioned phenol to be treated (9.5 g) was added with an auto pipetter to initiate the reaction.
Sixty minutes after the start of the reaction, 1 mL of the reaction solution was sampled and quenched in a 20 mL screw vial containing 5.0 mL of methanol in advance. This methanol dilution was subjected to GC (gas chromatograph) analysis under the following conditions to determine the concentration of each component.

(GC analysis conditions)
GC device: Agilent 6850 series Temperature rising condition: 50 ° C. → 10 ° C./min→300° C. (held for 10 minutes)
Analysis time: 35 minutes Analysis column: Agilent J & W GC column
HP-5 50m × 0.20mmID, 0.33μm
Carrier gas: He 40cm / S
Detector: FID
Vaporization chamber temperature: 200 ° C
Detector temperature: 250 ° C
Split ratio: 5/1
Injection volume: 1.00 μL (in methanol)

  The results are shown in Table 1B.

[Example 2]
In Example 1, as a sulfonic acid type cation exchange resin, a sulfonic acid type cation exchange resin “Diaion (registered trademark) PK208H” manufactured by Mitsubishi Chemical Corporation (porous type, degree of crosslinking: 4.0%, exchange capacity: 1) .12 meq / mL-resin) was used for elutriation classification in a particle size range of 490 to 510 μm. Dehydrated as it is, vacuum-dried, then modified with 2- (2-pyridine) ethanethiol in the same manner as in Example 1, and the same as in Example 1 using the resulting thiol-modified sulfonic acid type cation exchange resin. The phenol was purified and the results are shown in Table 1B.
When the average particle diameter and uniformity coefficient of “Diaion (registered trademark) PK208H” which was not categorized with water tank were measured, the average particle diameter was 500 μm and the uniformity coefficient was 1.03.

[Comparative Example 1]
In Example 1, as a sulfonic acid type cation exchange resin, “Diaion (registered trademark) PK228H” manufactured by Mitsubishi Chemical Corporation (porous type, degree of crosslinking: 14.0%, exchange capacity: 2.07 meq / mL-resin) The product was dehydrated and vacuum-dried without being classified into elutriates, and then swollen with phenol containing no thiol compound, and subjected to phenol purification in the same manner without modification with thiol compound.
The results are shown in Table 1B.
The average particle diameter and uniformity coefficient of “Diaion (registered trademark) PK228H” which was not classified into water tanks were measured. The average particle diameter was 750 μm and the uniformity coefficient was 1.5.

[Comparative Example 2]
<Manufacture of gel type sulfonic acid type cation exchange resin>
In Comparative Example 2, as shown below, a gel type having a degree of crosslinking of 6.4% and an exchange capacity of 1.84 meq / mL-resin by the same method as described in the examples of JP-A-2006-328290. A sulfonic acid type cation exchange resin was produced.

・ Reactor:
As a reactor for the polymerization reaction, a pressure resistant reactor made of stainless steel (hereinafter abbreviated as “SUS” as appropriate) equipped with a stirring blade, a pressure gauge, a nitrogen tube, and a thermometer was used.

・ Water phase:
As an aqueous phase, 2150 mL of an aqueous solution containing 30 mL of a 2 wt% aqueous polyvinyl alcohol solution and 10 mL of a 0.1 wt% methylene blue aqueous solution was prepared. While stirring the obtained aqueous phase, nitrogen gas was bubbled through a 10 μm SUS sintered filter for 1 hour. The dissolved oxygen concentration was 0.1 ppm or less.

・ Oil phase (monomer phase):
As raw material monomers, 497 g of styrene and 56.2 g of divinylbenzene (manufactured by Dow Chemical Co., 63% purity) are used, and water-containing BPO (benzoyl peroxide) (BPO concentration 75% by weight) 0.75 g is used as a polymerization initiator. Then, 0.55 g of PBZ (t-butyl perbenzoate) (0.1% by weight of both BPO and PBZ with respect to the total amount of monomers) was mixed and an oil phase (monomer phase) was prepared. While stirring the obtained oil phase, nitrogen gas was bubbled through a 10 μm SUS sintered filter for 1 hour to remove dissolved oxygen almost completely.

・ Polymerization reaction:
The gas phase in the reactor is purged with nitrogen by repeating the degassing operation of putting the above aqueous phase and oil phase into the above reactor, depressurizing at 1 kPa at room temperature, and then substituting with nitrogen gas three times. The reactor was sealed after almost completely removing oxygen in the gas phase. The suspension was stirred at 110 rpm for 30 minutes at 30 ° C. to obtain a suspension. After raising the temperature to 80 ° C. over 2 hours and holding at 80 ° C. for 4 hours (preliminary polymerization), raising the temperature to 120 ° C. over 2 hours and holding at 120 ° C. for further 4 hours (rear polymerization), The polymerization reaction was carried out in two stages. After completion of the reaction, the reactor was cooled to 50 ° C. or lower, and the resulting polymer was taken out of the reactor, washed with demineralized water, and dried at 50 ° C. for 8 hours using a vacuum dryer. The yield of the obtained polymer was 99.5%.

・ Introduction of sulfonic acid group:
200 g of the obtained polymer was put into a 2 L three-necked flask, 400 g of nitrobenzene was added, and the mixture was stirred at room temperature for 0.5 hour, then heated to 80 ° C. and further stirred for 3 hours to swell the polymer. After cooling to room temperature, 1400 g of 98% sulfuric acid was added and stirred. The temperature was raised to 100 ° C. over 4 hours, and the reaction was further continued at 100 ° C. for 4 hours. Thereafter, the reaction solution was cooled, and demineralized water was added dropwise over 15 hours while the internal temperature did not exceed 50 ° C. During this time, the reaction solution was extracted three times in the middle to remove sulfuric acid. Thereafter, the nitrobenzene and the aqueous phase were removed, and further, demineralized water was added and heated to distill away the remaining nitrobenzene. The obtained resin was washed with 10 BV of demineralized water to produce a sulfonic acid type cation exchange resin.

When the average particle size and uniformity coefficient of the produced gel-type sulfonic acid type cation exchange resin were measured, the average particle size was 750 μm and the uniformity coefficient was 1.5.
Phenol was purified in the same manner as in Example 1 except that this gel type sulfonic acid type cation exchange resin was used as the sulfonic acid type cation exchange resin, and the results are shown in Table 1B.

[Comparative Example 3]
In Example 1, as a sulfonic acid type cation exchange resin, “Diaion (registered trademark) SK104H” manufactured by Mitsubishi Chemical Corporation (gel type, cross-linking degree 4.0%, exchange capacity 1.25 meq / mL-resin) The product was dehydrated and vacuum-dried without being classified into elutriates, and then subjected to a modification treatment in the same manner as in Example 1 (however, the modification rate was 20 mol%), and was similarly subjected to purification of phenol.
The results are shown in Table 1B.
When the average particle diameter and uniformity coefficient of “Diaion (registered trademark) SK104H” which was not classified into water tanks were measured, the average particle diameter was 750 μm and the uniformity coefficient was 1.5.

[Comparative Examples 4 to 7]
In Comparative Example 3, the thiol compound cation exchange resin was modified in the same manner except that the thiol compound shown in Table 1A was used instead of 2- (2-pyridine) ethanethiol and the modification rate shown in Table 1A was used. Using the thiol-modified sulfonic acid cation exchange resin thus obtained, phenol was purified in the same manner as in Example 1, and the results are shown in Table 1B.

[Comparative Example 8]
In Example 1, as a sulfonic acid type cation exchange resin, “Diaion (registered trademark) RCP145H” manufactured by Mitsubishi Chemical Corporation (porous type, degree of crosslinking: 14.0%, exchange capacity: 0.87 meq / mL-resin) The phenol was purified in the same manner except that was used (however, the modification rate was 20 mol%).
The results are shown in Table 1B.
When the average particle diameter and uniformity coefficient of “Diaion (registered trademark) RCP145H” which was not categorized with water tank were measured, the average particle diameter was 750 μm and the uniformity coefficient was 1.5.

[Evaluation of results]
Tables 1A and B show that impurities in phenol can be efficiently removed by using a porous sulfonic acid cation exchange resin having a crosslinking degree of 6.0% or less.
On the other hand, the comparative examples 1 and 8 are porous, but the effect of removing impurities is poor because the degree of crosslinking is large. Since Comparative Examples 2 to 7 were gel type, the effect of removing impurities was poor, and the gel type sulfonic acid type cation exchange resin did not give sufficient results even when thiol modification was performed.

[Example 3]
<Catalyst load test>
To the same reactor as in Example 1, phenol (89.90 g) heated to 70 ° C. and dried sulfonic acid type cation exchange resin “Diaion (registered trademark) PK206H” manufactured by Mitsubishi Chemical Corporation were added. . It was attached to an oil bath heated to 100 ° C. and left to swell for 30 minutes, and then stirred at 180 rpm for 30 minutes. 1.0 g of each of four types of impurities, acetol, mesityl oxide, methylstyrene, and benzaldehyde, was weighed and added to a phenol solution to initiate the reaction. The reaction solution was sampled every 15 minutes, diluted with a 20% phenol / methanol solution, and GC analysis was performed to confirm the reduction rate of impurities. The results are shown in Table 2A.
Further, from the first hour after the start of the reaction, 2.0 g of the mixed solution containing the above four kinds of impurities is added every other hour for up to 6 hours, reacted at 100 ° C. for 8 hours, and then allowed to cool to room temperature. did. Although stored at room temperature until 12 hours later, the solution did not crystallize and remained a reddish brown solution.

<Evaluation of catalyst life>
Twelve hours after the reaction, the oil bath was heated to set the internal temperature to 70 ° C., and 9.3 g of a phenol solution of the mixture was added so that the concentrations of the four impurities were 1000 ppm. The reaction solution was sampled every hour, GC analysis was performed on the solution diluted with a 20% phenol / methanol solution, and the catalyst life was evaluated. The residual ratio of each component after 4 hours of reaction is shown in Table 2B.

[Comparative Example 9]
The same procedure as in Example 3 was performed except that the type of resin used was changed from “PK206H” to “Diaion (registered trademark) SK104H” manufactured by Mitsubishi Chemical Corporation. The results are shown in Table 2A and Table 2B.

[Evaluation of results]
Compared with the sulfonic acid type cation exchange resin of Comparative Example 9, the sulfonic acid type cation exchange resin of Example 3 has a higher impurity reduction rate and can maintain activity for a long period of time.

Claims (6)

In the method for producing a purified phenol compound, which is purified by contacting a phenol compound represented by the following formula (1) with a sulfonic acid cation exchange resin:
The sulfonic acid cation exchange resin is a porous cation exchange resin having an average particle size of 10 to 850 μm, a degree of crosslinking of 1.0% or more and 4.5 % or less,
A method for producing a purified phenolic compound, wherein a sulfonic acid group of the sulfonic acid type cation exchange resin and pyridine ethanethiol form an ionic bond.

(In the above formula (1), R ₁ and R ₂ may be the same or different from each other, and each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or a haloalkyl group having 1 to 3 carbon atoms.) Oite to claim 1, exchange capacity of the sulfonic acid type cation-exchange resin which corresponds to the neutral salt decomposition capacity of the sulfonic acid groups per resin 1mL is, it is 0.2~1.3meq / mL- resin A process for producing a purified phenolic compound characterized by The method for producing a purified phenol compound according to claim 1 or 2 , wherein the sulfonic acid cation exchange resin has a uniformity coefficient of 1.4 or less. The sulfonic acid group cation exchange resin according to any one of claims 1 to 3 , wherein a part of the sulfonic acid group of the sulfonic acid type cation exchange resin is modified with pyridine ethanethiol, and the modification rate is 1 to 40 mol%. A method for producing a purified phenolic compound. 5. The sulfonic acid type cation exchange resin is brought into contact with the phenolic compound before use for conditioning the phenolic compound represented by the formula (1) according to claim 1. A process for producing a purified phenolic compound characterized in that   The method for producing a purified phenol compound according to any one of claims 1 to 5, wherein the phenol compound is brought into contact with the sulfonic acid cation exchange resin and the anion exchange resin.