JP2006008634A - Method for producing bisphenols - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method, capable of obtaining a high purity bisphenol F without increasing the molar ratio of phenol/formaldehyde so much. <P>SOLUTION: This method for producing a bis(hydroxyphenyl)methane by performing the condensation reaction of the phenol with formaldehyde in the presence of an acid catalyst is provided by feeding at least one liquid in 2 kinds of liquids consisting of a first liquid containing hydroxybenzyl alcohol produced by performing the reaction of a phenol with a formaldehyde in the presence of a base catalyst and a second liquid containing an acid catalyst, into a mixing space through in a plurality of fine flowing passages having 1-500 μm width, and also 2 kinds of the liquids from passages crossing their central axes at one point, mixing and reacting under an acid condition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing bisphenol F useful as a resin raw material.

  Bisphenols produced by the reaction of monophenols and formaldehydes, such as bis (hydroxyphenyl) methane (hereinafter referred to as bisphenol F), have a lower viscosity and heat resistance than the so-called bis-A type epoxy resin made from bisphenol A. In addition to providing an excellent epoxy resin, it is also used as a curing agent for epoxy resins and a phenol resin modifier, and is attracting attention. Among them, for epoxy resin applications, further improvement in viscosity and heat resistance is strongly desired as needs are diversified.

  In general, bisphenol F is produced by a condensation reaction of phenol and formaldehyde using an acidic catalyst such as oxalic acid as a catalyst. Among the bisphenol F produced, 4,4'-bisphenol F, 2,4'-bisphenol F In addition to the three isomers (binuclear) of 2,2'-bisphenol F, various heavy substances are included, including trinuclear bodies that are further polycondensed with phenol after addition of formaldehyde. It is. Epoxy resins obtained by epoxidizing bisphenol F containing these heavy substances have a high viscosity and greatly impair the low viscosity characteristic of bisphenol F epoxy. It has also been reported that paints containing bisphenol F epoxy resins containing heavy materials are inferior in terms of coating corrosion resistance, chemical resistance, etc. compared to paints containing high purity bisphenol F epoxy resins as constituents. (Japanese Patent Laid-Open No. 2-166114).

  Therefore, in the production of bisphenol F, various methods for suppressing the formation of heavy substances have been studied. For example, currently used bisphenol F having a purity of 90 to 94% has a phenol / formaldehyde molar ratio of 30 to 40 which is 15 times or more of the theoretical molar ratio in the homogeneous reaction system using the oxalic acid catalyst. Therefore, it takes a long time and operation cost to distill and recover excess phenol after the reaction is completed, and the productivity of the kettle is very low at 10% or less.

  Patent Document 1 below describes a method for obtaining bisphenol F having a purity of 88% at a reaction temperature of 45 ° C. with a molar ratio of phenol / formaldehyde of about 5 using a large amount of 85% high-concentration phosphoric acid. ing. Patent Document 2 uses a large amount of an organic solvent such as toluene, a catalyst such as water and oxalic acid, a phenol / formaldehyde in a low molar ratio, a liquid phase mainly composed of toluene and the like, mainly water and oxalic acid and the like. A method of obtaining bisphenol F by reacting in a liquid-liquid heterogeneous system under stirring with a liquid phase to be obtained, and distilling and recovering an organic solvent such as toluene and phenol after the reaction is disclosed. Furthermore, in Patent Document 3, 50 to 80% phosphoric acid water is used as a catalyst, raw material aldehyde is added sequentially, and the produced bisphenol F is rapidly extracted into the phenol phase, thereby suppressing the heavy by-product. A method has been proposed. However, in any case, no method has been provided that satisfies both productivity and quality.

Japanese Patent Publication No. 3-72049 Japanese Patent Application Laid-Open No.6-135872 JP 09-67287 A JP 2002-346355 A Special Table 2002-512272

  By the way, although the micromixer which has two or more microchannels and a mixing space or a mixing area | region is known by the said patent documents 4-5 etc., there is nothing which teaches that this is suitable as a manufacturing apparatus of bisphenol F.

  An object of the present invention is to provide a production method capable of improving the purity of bisphenol F to be produced while having excellent productivity without increasing the phenol / formaldehyde molar ratio so much.

  As a result of intensive studies in view of the above circumstances, the present inventors have found that a first liquid containing hydroxybenzyl alcohol produced by reacting phenols and formaldehyde in the presence of a base catalyst and a second liquid containing an acid catalyst. When at least one of the two liquids is supplied to the mixing space from a plurality of micro flow channels having a width of 1 to 500 μm, and the central axis of the two liquid flow channels intersects at one point, hydroxybenzyl alcohol Has been found to be able to react quickly and efficiently to reduce the production ratio of heavy substances, thereby completing the present invention.

  That is, the present invention includes hydroxybenzyl alcohol produced by reacting phenols and formaldehyde in the presence of a base catalyst in a method for producing bis (hydroxyphenyl) methanes by condensing phenols and formaldehyde. Of the two liquids comprising the first liquid and the second liquid containing the acid catalyst, at least one liquid is from a plurality of micro flow channels with a width of 1 to 500 μm, and the two liquids are at one central point of the flow channel. This is a method for producing bis (hydroxyphenyl) methanes, characterized in that a mixed space is supplied from an intersecting flow path, mixed, and reacted under acidic conditions.

  Here, satisfying any one or more of the following requirements is a better manufacturing method. 1) The first liquid is a liquid containing hydroxybenzyl alcohol obtained by reacting at a molar ratio of phenols / formaldehydes of 2-30, and 2) the reaction temperature in the presence of a base catalyst is 40- The reaction temperature under acidic conditions at 100 ° C. is 50 to 170 ° C. 3) The reaction product in the presence of the base catalyst is continuously subjected to the reaction under acidic conditions with a rapid temperature change. 4) At least one flow path for supplying two liquids branches in the middle to form a plurality of flow paths, and is supplied to the mixing space. 5) The plurality of branched flow paths have the same cross-sectional shape. 6) The linear velocity when being supplied to the mixing space from a plurality of microchannels is 1 m / sec or more, or 7) The apparatus having the microchannels and the mixing space is a micromixer.

  The reaction apparatus is an apparatus that supplies the two kinds of flowing liquids independently to the mixing space, and the supply channel that supplies at least one kind of liquid includes a plurality of subchannels that supply the liquid to the mixing space. The supply channel and subchannel are formed so that all the central axes of the channels that supply the liquid to the mixing space intersect at one point if they do not branch. Thus, an apparatus having a structure in which uniform mixing is quickly performed is desirable. For example, a micromixer having such a structure is preferably exemplified.

Hereinafter, the reaction conditions of the present invention will be described in detail.
Reaction raw materials are phenols and formaldehydes. From this reaction raw material, hydroxybenzyl alcohol is produced using a base catalyst, and bisphenol F is produced from a liquid containing hydroxybenzyl alcohol using an acidic catalyst. Hereinafter, the reaction for generating hydroxybenzyl alcohol is sometimes referred to as a first reaction, and the reaction for generating bisphenol F is sometimes referred to as a second reaction.

  Phenols that generate bisphenol F are preferred as the phenols, but mono- and di-substituted phenols can also be used for the purpose of controlling heat resistance and other physical properties. Preferred examples of the substituted phenol include lower alkyl-substituted phenols such as cresol and xylenol.

Examples of formaldehydes include formaldehyde, paraformaldehyde, trioxane, and tetraoxane that generate formaldehyde in the reaction system and formaldehyde. Paraformaldehyde is preferred.
As described above, phenol and formaldehyde as used in the present invention may include derivatives thereof. However, in order to facilitate understanding, phenols and formaldehydes may be referred to as phenol and formaldehyde within a range not causing misunderstanding. Bis (hydroxyphenyl) methanes may be represented by bisphenol F.

  The basic catalyst used in the first reaction is more basic than phenol, such as metal hydroxides such as sodium hydroxide and potassium hydroxide, metal alkoxides such as sodium methoxide, sodium ethoxide and potassium tert-butoxy. A high degree of metal base is preferred. Of these, metal hydroxides such as sodium hydroxide and potassium hydroxide are preferred.

  The molar ratio of phenol / formaldehyde used for the first reaction is 2-30, preferably 5-15. When this molar ratio exceeds 30, the productivity is greatly reduced, which is not economical. The molar ratio 2 is a stoichiometric ratio, but in the range of 2 to 5, the conversion of formaldehyde in the base-catalyzed reaction does not end depending on conditions, and reacts with phenol in the subsequent acid-catalyzed reaction. The content (binuclear / binuclear or higher polynuclear) may be low. In the range of 5 to 15, a bisphenol having a high binuclear content can be more efficiently produced.

  In the first reaction, formaldehyde and phenol are reacted in the presence of a base catalyst. The raw material phenol can be used as a molten phenol solution as it is or in a solution state using various solvents. The solvent is not particularly limited as long as it dissolves phenol and the catalyst suitably, but aromatic hydrocarbons such as toluene and xylene, ethers such as 1,4-dioxane and diphenyl ether, and benzonitrile are preferable.

  The base catalyzed reaction which is the first reaction is 40 to 100 ° C, preferably 60 to 90 ° C. Above 100 ° C., formaldehyde reacts with two or more phenols to form bis or tris- (hydroxymethyl) -phenol, which in turn causes heavy products in the acid-catalyzed second reaction. On the other hand, if the temperature is lower than 40 ° C., the reaction does not proceed sufficiently and it takes a long time, but unreacted formaldehyde reacts with phenols in a second order in the second reaction to produce a heavy product.

  In the first reaction, it is preferable to react 90% or more of formaldehyde, preferably 99% or more. However, a large amount of phenol added excessively may remain unreacted. After completion of the first reaction, the produced hydroxybenzyl alcohol may be separated and concentrated, but it is convenient to use the solution for the second reaction with a solvent, unreacted phenol, catalyst and the like.

  In the second reaction, the first liquid containing hydroxybenzyl alcohol obtained in the first reaction and the second liquid containing an acid catalyst are reacted under acidic conditions. The first liquid is a liquid containing hydroxybenzyl alcohol, and can be a liquid obtained by concentrating or separating the hydroxybenzyl alcohol obtained in the first reaction or a liquid obtained by adding a solvent to the liquid. The reaction mixture containing the hydroxybenzyl alcohol obtained in the first reaction is advantageous. In addition, you may mix | blend a solvent, phenol, etc. with this reaction liquid mixture as needed. The second liquid is a liquid containing an acid catalyst, and if necessary, a solvent such as water or an organic solvent, phenol or the like may be blended.

  Examples of the acid catalyst include inorganic mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid, heteropolyacids such as phosphotungstic acid, phosphomolybdic acid and phosphomolybdotungstic acid, metal halide salts such as zinc chloride and aluminum chloride, trichloroacetic acid, Halogenated carboxylic acids such as dichloroacetic acid, aromatic sulfonic acids, formic acid, and oxalic acid can be mentioned, among which oxalic acid, inorganic mineral acids, and aromatic sulfonic acids are preferred. When the first liquid contains a base catalyst, the acid catalyst is used in an amount sufficient to neutralize the acid catalyst and make the whole acidic.

  In the second reaction, the first liquid containing hydroxybenzyl alcohol and the second liquid containing an acid catalyst are mixed through a plurality of microchannels, and the reaction is performed under acidic conditions. The temperature in this reaction is 50 to 170 ° C, preferably 80 to 140 ° C. Below 50 ° C., the reaction does not proceed sufficiently, and the reaction does not end in the mixing space. Further, when the temperature exceeds 170 ° C., the quality is deteriorated due to coloring of the product, and there is a concern that the product is blocked in the mixed space due to partial vaporization of the solvent and unreacted phenol. The reaction time is adjusted so that 90% or more, preferably 99% or more of the hydroxybenzyl alcohol is reacted.

  Here, it is desirable to supply the first liquid to the second reaction promptly. In particular, when the first liquid containing the base catalyst is heated to a temperature of 100 ° C. or higher before being mixed with the second liquid, hydroxybenzyl alcohol condenses with each other to form a crosslinked heavy product. To do. Therefore, when the first liquid is continuously charged into the second reaction apparatus, the first liquid is rapidly heated to the second reaction temperature, mixed with the second liquid, and quickly supplied to the second reaction. It is good. For this purpose, it is desirable to rapidly heat to the second reaction temperature via a micro heat exchanger having high heat exchange efficiency, for example, and send the solution to the mixing space where the second reaction occurs.

Next, a reaction apparatus used in the second reaction, preferably a micromixer will be described.
In the second reaction, it is important to perform rapid and uniform mixing and react the substrates all at once. Therefore, an apparatus that rapidly mixes the first liquid and the second liquid is used. In such an apparatus, at least one of the two liquids supplied as reaction raw materials is supplied to the mixing space from a plurality of micro flow channels having a width of 1 to 500 μm, and the central axes of the two liquid flow channels intersect at one point. Of structure.

  In other words, the supply channel that supplies at least one fluid has a plurality of subchannels that flow into the mixing space, and when these subchannels supply liquid to the mixing space and do not branch, 1 Two supply channels supply liquid to the mixing space. The supply channels and the central axes of the plurality of subchannels are formed so as to intersect at one point. The point where the central axes intersect is located in the mixing space. As used herein, “channel” refers to a flow path through which liquid flows, and “subchannel” refers to each flow path branched into a plurality of channels. Usually, a subchannel comprises a microchannel.

  The central axis of the supply channel or the subchannel means an axis (or a straight line) along the moving direction of the center of mass (or center of gravity) of the liquid flowing into the mixing space. Specifically, when the supply channel or subchannel of the liquid flowing into the mixing space is a cylinder or a rectangular tube, the center of gravity (the center of the circle or the circle) The axis passing through the diagonal line) and extending along the length of the cylinder corresponds to the central axis. In addition, intersecting at one point means intersecting on an extension line of the central axis, and may be a point having a certain area, not a mathematical point.

  According to the present invention, the productivity can be improved without increasing the molar ratio of phenol and formaldehyde, and the purity of bisphenol F produced can be improved. Moreover, when obtaining the same dinuclear content rate, the molar ratio of formaldehyde can be raised and productivity can be improved.

Further, the apparatus will be described more specifically with reference to the drawings.
FIG. 1 is a drawing schematically showing the flow and mixing of the raw material liquid. As indicated by the arrows, the two liquids A and B flow through the supply channel 12 and the supply channel 18, respectively, and then the liquid A is divided at the branch point 14 and passes through the subchannels 16 and 16 ′. Then, it is supplied to the mixing space 10. The liquid B is supplied to the mixing space 10 without being divided through the supply channel 18.

  As shown in the figure, the central axis of the liquid A flowing into the mixing space 10 via the subchannels 16 and 16 ', and the central axis of the liquid B flowing into the mixing space 10 via the supply channel 18 without being divided Is shown by a one-dot chain line. The illustrated embodiment shows the case where the channel and the subchannel are cylindrical or rectangular, and therefore, the central axis is drawn so as to pass through substantially the center of the channel and the subchannel, and the central axis intersects at the point 20. It shows how to do.

  Further, in FIG. 1, the mixed liquid discharge channel 26 starts after the mixed space 10 where the liquids A and B merge, and all these channels are arranged in substantially the same plane. At this time, the angles α and α ′ formed by the supply subchannels 16 and 16 ′ and the discharge channel 26 and the angles β and β ′ formed by the supply channel 18 and the supply subchannels 16 and 16 ′ are each greater than 0 ° and 180 °. Although values below 0 ° can be adopted, α and α ′, and β and β ′ are more preferably equal. Similarly, the angle formed by the supply channel 18 and the discharge channel 26 can take a value greater than 0 ° and 180 ° or less.

  The raw material liquid supplied from the channel and the subchannel is quickly and uniformly mixed in the mixing space to cause a reaction. The volume of the mixing air is adjusted so as to obtain a predetermined residence time. However, if the reaction is not sufficient, the reaction may continue in the subsequent discharge channel 26, and the number of the discharge channels 26 may be plural. There may be.

  The channel and the subchannel each have a semicircular shape, a rectangular shape, or other cross sections, but the subchannels through which the same liquid flows preferably have the same cross section. Furthermore, the subchannel preferably has the same or smaller cross section than the channel through which the liquid flows. The depth of the channel and the subchannel is preferably equal to or smaller than the width, and the flow path length is not limited.

  Here, the reaction of the two raw material liquids proceeds in the mixed space after merging, and the conditions such as the catalyst concentration and the reaction temperature are the conditions of the mixture in the mixed space such as the concentration of hydroxybenzyl alcohol and the concentration of unreacted phenol. Determined by state. Accordingly, the temperature, flow rate, and path before mixing of each liquid can take any value that satisfies a predetermined condition in the mixing space. However, it is supplied at a flow rate corresponding to the cross-sectional area of the channel supplied to the mixing space (conversely, the cross-sectional area of the channel is determined according to the flow rate of the supplied liquid), and the linear velocity is 1 m / sec or more. Is preferable, and more preferably 2 m / sec or more.

  In this way, in the present invention, since the central axes of the converging liquids collide and contact so that they intersect at a single point, these fluids are instantaneously divided (or refined) into smaller fluid masses by their kinetic energy. At the same time, the contact state of the fluid mass is improved. As a result, the contact interface area between the joining liquids increases rapidly, and mixing between these liquids is promoted, so that more rapid and uniform mixing is achieved. Therefore, by using such an apparatus, it becomes possible to control a high-speed sequential reaction, and the remarkable result can be said to be a method for producing bisphenols.

  After completion of the reaction, bisphenol having a high binuclear content can be easily obtained by removing the solvent, unreacted phenol, catalyst and the like by conventional methods (eg, distillation, extraction, etc.).

Next, the reactor used in the examples is shown in FIGS.
FIG. 2 is a perspective view showing a state where three parts constituting the apparatus 100 are disassembled. In the supply unit 102, the liquids A and B are supplied from the bores 112 and 114 that reach the annular channels 108 and 110 having a rectangular cross section. In the confluence 104, the liquids A and B flow from the sub-channels 124 and 126 divided into four toward the center 128 through the through-bore 116 and 118 arranged at equal intervals in the circumferential direction of the annular channel. To do. Needless to say, the central axis of the subchannel 124 and the central axis of the subchannel 126 intersect at the center 128, and the joined liquid C is discharged to the outside of the apparatus via the bore 130.

  FIG. 3 shows another reaction apparatus, but is a perspective view showing an exploded state of three parts constituting the apparatus 100 as in FIG. 3 and the description thereof, the same reference numerals as those in FIG. 2 have the same meaning. In the reaction apparatus of FIG. 3, the liquid B can be introduced from the center of the supply unit 102. The liquid A is supplied from the bores 112 and 114 that reach the annular channels 108 and 110 having a rectangular cross section, and the liquid B is supplied from the channel 132 that passes through the center of the supply unit 102. In the confluence 104, the liquid A flows from the sub-channels 124 and 126 divided into eight toward the center 128 through the through-bore 116 and 118 arranged at equal intervals in the circumferential direction of the two annular channels. In contrast, the liquid B flows into the center 128 via the channel 134 without being divided. Needless to say, the central axis of the subchannels 124 and 126 and the central axis of the channel 134 intersect at the center 128, and the joined liquid C is discharged to the outside of the apparatus via the bore 130.

  In this way, in the present invention, since the central axes of the converging liquids collide and contact so that they intersect at one point, these fluids are instantaneously divided (or refined) into smaller fluid masses by their kinetic energy. At the same time, the contact state of the fluid mass is improved, and rapid and uniform mixing is achieved. This makes it possible to control the high-speed sequential reaction, and is considered to improve the selectivity of bisphenol F.

  After completion of the reaction, bisphenol having a high binuclear content can be easily obtained by removing the solvent, unreacted phenol, catalyst and the like by conventional methods (eg, distillation, extraction, etc.).

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. The analysis was performed using a high performance liquid chromatograph. Further,% is% by weight unless otherwise specified.

The material of the device was stainless steel, and the specifications of each channel, subchannel and bore were as follows:
Cross-sectional shape, width, depth, diameter of annular channel 108: rectangular cross-section, 1.5mm, 1.5mm, 25mm
Cross-sectional shape, width, depth, diameter of annular channel 110: rectangular cross-section, 1.5mm, 1.5mm, 20mm
Bore 112 diameter, length 1.5mm, 10mm (circular cross section)
Bore 114 diameter, length 1.5mm, 10mm (circular cross section)
Bore 132 diameter, length 1.5mm, 10mm (circular cross section)
Bore 116 diameter, length 0.5mm, 4mm (circular cross section)
Bore 118 diameter, length 0.5mm, 4mm (circular cross section)
Bore 134 diameter, length 0.5mm, 4mm (circular cross section)
Microchannel 124 cross-sectional shape, width, depth, length: rectangular cross-section, 200μm, 200μm, 12.5mm
Microchannel 126 cross-sectional shape, width, depth, length: rectangular cross-section, 200μm, 200μm, 10mm
Bore 130 diameter and length: 1mm, 10mm (circular cross section)

Example 1
To a 200 ml eggplant flask, 80 g (0.850 mol) of phenol and 3.6 g (0.11 mol) of 94% paraformaldehyde were added and heated and stirred in a 90 ° C. oil bath to dissolve paraformaldehyde. To this was added 1 ml (0.002 mol) of a 2N aqueous sodium hydroxide solution, and the mixture was stirred for 10 minutes to complete the reaction and obtain liquid A. Analysis showed that the conversion of formaldehyde was 99.5% and the yields of o-hydroxybenzyl alcohol and p-hydroxybenzyl alcohol were 72.0% and 27.1%, respectively. In the same manner, 3.42 g (0.018 mol) of paratoluenesulfonic acid monohydrate was added to 80 g (0.85 mol) of phenol, and heated and stirred in a water bath at 80 ° C. to dissolve paratoluenesulfonic acid monohydrate. Was designated as B liquid.
Immerse the device shown in Fig. 2 with a preheated part in which a 50cm stainless steel tube (outer diameter 1.6mm, inner diameter 1.0mm) is spirally wound on the upstream side of each inlet of liquid A and liquid B. The raw material liquids A and B were both flowed at 9.0 ml / min. A 30 cm Teflon (registered trademark) tube (outer diameter 1.6 mm, inner diameter 1.0 mm) equipped at the rear end of the mixer was immersed in an oil bath to form a reaction part. The reaction temperature was 110 ° C. The product was rapidly cooled to stop the reaction and then analyzed. The formaldehyde conversion and binuclear content are shown in Table 1.

Example 2
To a 300 ml eggplant flask, 175.5 g (1.865 mol) of phenol and 4.24 g (0.133 mol) of 94% paraformaldehyde were added and stirred in an oil bath at 90 ° C. to dissolve paraformaldehyde. To this, 3.6 ml (0.007 mol) of 2N aqueous sodium hydroxide solution was added and stirred for 10 minutes to complete the reaction, and liquid A was obtained. As a result of the analysis, the formaldehyde conversion rate was 99.8%, and the yields of o-hydroxybenzyl alcohol and p-hydroxybenzyl alcohol were 72.2% and 27.2%, respectively.
To a 50 ml eggplant flask, add 12.5 g (0.133 mol) of phenol and 5.22 g (0.027 mol) of paratoluenesulfonic acid monohydrate, and heat and stir in an 80 ° C water bath to dissolve paratoluenesulfonic acid monohydrate. The resulting solution was designated as solution B.
The reaction was carried out in the same manner as in Example 1 except that the liquid A and liquid B were used and flowed at 14.0 ml / min and 1.0 ml / min, respectively.

Example 3
To a 300 ml eggplant flask, 175.5 g (1.865 mol) of phenol and 4.24 g (0.13 mol) of 94% paraformaldehyde were added and stirred in an oil bath at 90 ° C. to dissolve paraformaldehyde. To this, 3.6 ml (0.007 mol) of 2N aqueous sodium hydroxide solution was added and stirred for 10 minutes to complete the reaction, and liquid A was obtained. As a result of the analysis, the formaldehyde conversion rate was 99.8%, and the yields of o-hydroxybenzyl alcohol and p-hydroxybenzyl alcohol were 72.2% and 27.2%, respectively.
Add 12.5 g (0.13 mol) of phenol and 5.22 g (0.027 mol) of p-toluenesulfonic acid monohydrate to a 50 ml eggplant flask and heat and stir in an 80 ° C water bath to dissolve p-toluenesulfonic acid monohydrate. The resulting solution was designated as solution B.
Using the apparatus shown in FIG. 3, the reaction was carried out in the same manner as in Example 1 except that the liquid A and the liquid B were flowed at 14.0 ml / min and 1.0 ml / min, respectively.

Comparative Example 1
A 200 ml baffled separable flask was charged with 120 g (1.275 mol) of phenol and 2.71 g (0.085 mol) of 94% paraformaldehyde, heated in an oil bath, and stirred with a turbine blade (rotation speed: 600 rpm). The internal temperature was 90 ° C. After paraformaldehyde was completely dissolved, 0.75 ml (0.0015 mol) of 2N aqueous sodium hydroxide solution was added, and stirring was continued for another 10 minutes to complete the first reaction. Analysis showed that the conversion of formaldehyde was 99.5% and the yields of o-hydroxybenzyl alcohol and p-hydroxybenzyl alcohol were 72.0% and 27.1%, respectively. Subsequently, 2.57 g (0.0135 mol) of paratoluenesulfonic acid monohydrate was added, and heating and stirring were continued for 30 minutes to complete the second reaction, and the contents were analyzed.

Comparative Example 2
The same reaction as in Example 1 was carried out except that the PEEK T-shaped channel mixer shown in FIG. 4 having a channel width of 800 μm was used instead of the apparatus shown in FIG.
The analysis results are summarized in Table 1.

Schematic diagram of mixing style Exploded perspective view of reactor Exploded perspective view of another reactor Schematic diagram of a conventional mixer

Explanation of symbols

100: reactor, 102: feed section, 108 and 110: annular channel, 112 and 114: bore, 104: junction, 116, 118: through bore, 124 and 126: subchannel, 128: crossing center, 130: discharge Bore

Claims (8)

  In the method for producing bis (hydroxyphenyl) methane by condensing phenols and formaldehyde, a first liquid containing hydroxybenzyl alcohol produced by reacting phenols and formaldehyde in the presence of a base catalyst and an acid catalyst Among the two liquids comprising the second liquid containing at least one liquid, at least one liquid is mixed from a plurality of micro flow channels having a width of 1 to 500 μm, and the two liquids are mixed from a flow channel whose central axis intersects at one point. A process for producing bis (hydroxyphenyl) methanes, characterized in that it is supplied to a space, mixed, and reacted under acidic conditions.   The method for producing bis (hydroxyphenyl) methanes according to claim 1, wherein the first liquid is a liquid containing hydroxybenzyl alcohol obtained by reacting at a molar ratio of phenols / formaldehydes of 2 to 30.   The process for producing bis (hydroxyphenyl) methanes according to claim 1 or 2, wherein the reaction temperature in the presence of a base catalyst is 40 to 100 ° C, and the reaction temperature under acidic conditions is 50 to 170 ° C.   The bis (hydroxyphenyl) methane according to any one of claims 1 to 3, wherein the reaction product in the presence of a base catalyst is continuously subjected to a reaction under acidic conditions with a rapid temperature change. Manufacturing method.   5. The bis (hydroxyphenyl) methanes according to claim 1, wherein at least one flow path for supplying the two liquids is branched in the middle to form a plurality of flow paths and is supplied to the mixing space. Production method.   The method for producing bis (hydroxyphenyl) methanes according to claim 5, wherein the plurality of branched flow paths have the same cross-sectional shape.   The method for producing bis (hydroxyphenyl) methanes according to claim 1, wherein a linear velocity when being supplied to the mixing space from a plurality of microchannels is 1 m / sec or more. The method for producing bis (hydroxyphenyl) methanes according to any one of claims 1 to 7, wherein the apparatus having a microchannel and a mixing space is a micromixer.

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