WO2012108385A1 - Method for producing bisphenol compound - Google Patents

Abstract

The present invention provides a method for producing a bisphenol compound by reacting a phenol compound and a carbonyl compound in the presence of a cation exchanger having a strongly acidic group and 2-(2-mercaptoethyl)pyridine, the production method being characterized in that the concentration of water in the reaction raw material that contains the phenol compound and the carbonyl compound is 0.05 to 0.5 wt.%.

Description

Method for producing bisphenol compound

The present invention relates to a method for producing a bisphenol compound. More specifically, in a method for producing a bisphenol compound from a phenol compound and a carbonyl compound in the presence of a cation exchanger having a strong acid group and 2- (2-mercaptoethyl) pyridine, the reaction raw material contains water at a specific concentration. The present invention relates to a method for producing a bisphenol compound.

A bisphenol compound is generally produced by a condensation reaction between a phenol compound and a carbonyl compound in the presence of an acidic catalyst. As the acidic catalyst, a mineral acid such as hydrochloric acid is also used, but industrially, a cation exchange resin having an acidic group such as sulfonic acid is widely used from the viewpoint of corrosion of the apparatus by the catalyst and cost. In addition, for the purpose of improving the conversion rate, selectivity, etc., a compound containing a thiol group or a protected thiol group (hereinafter sometimes abbreviated as “thiol compound”) may be allowed to react with a catalyst. Are known.

The co-catalyst thiol compound coexists with the catalyst as follows: (1) a method in which the thiol compound is added to the reaction raw material and supplied; and (2) a functional group capable of binding to a sulfonic acid group such as an amino group. There is a method in which a sulfonic acid group of a sulfonic acid type cation exchange resin is modified with a thiol compound (for example, aminoalkanethiol compound, pyridinealkanethiol compound, etc.) contained.

The method of modifying the sulfonic acid type cation exchange resin with the thiol compound of (2) does not mix the thiol compound into the reaction product, and therefore the method of adding the thiol compound of (1) to the reaction raw material. Are better. Various compounds such as aminoalkanethiol compounds and pyridinealkanethiol compounds are known as thiol compounds that can be used to modify the sulfonic acid type cation exchange resin.

In the above method for producing a bisphenol compound, regarding the influence of the amount of water present in the reaction system, the concentration of water contained in the reaction raw material is 0.2% by weight or more in the presence of a strongly acidic cation exchange resin catalyst. Then, since the conversion rate of the carbonyl compound which is a raw material falls, it is disclosed that it is unpreferable (refer patent document 1). In this document, it is described that it is preferable that water does not exist in the reaction system, and when the concentration is changed, the influence on impurities other than the produced bisphenol compound is not studied at all.

Regarding the relationship between the presence of water in the reaction system and impurities other than the produced bisphenol compound in the above bisphenol compound production method, the reaction is carried out in the presence of a strongly acidic ion exchange resin catalyst modified with an alkyl-SH group such as cysteamine. It has been disclosed that adding 0.6 to 5% by weight of water to the raw material improves the selectivity of bisphenol compounds and reduces the generation of chroman and indanes (see Patent Document 2). In the method, impurities are reduced, but since the amount of water added is large, there is a problem that the reaction activity is remarkably lowered. In this method, since the reaction activity is remarkably reduced, it is necessary to increase the amount of catalyst in order to ensure an equivalent amount of production, and it is necessary to increase the number of reactors or increase the size of the reactor. This is industrially disadvantageous.

As a method for producing a bisphenol compound in which the same amount of water is present in the reaction system, the amount of water in the reaction raw material is adjusted by adjusting the amount of water in the presence of a strongly acidic ion exchange resin catalyst modified with a 4-pyridylethyl mercaptan compound. It is disclosed that the selectivity of '-bisphenol A is controlled (see Patent Document 3). Further, it is disclosed that the amount of water present in the reaction system is preferably 1 to 5% by weight of the feed solution. However, when such water is added to the reaction system, there is a problem that the reaction activity is remarkably lowered, and further, this document does not discuss any by-products generated during the production of the bisphenol compound.

JP 2009-196929 A JP-A-6-172241 US Pat. No. 7,132,575 JP 2010-189380 A

An object of the present invention is to solve the above-mentioned problems, and reacting a phenol compound and a carbonyl compound in the presence of a cation exchanger having a strong acid group and 2- (2-mercaptoethyl) pyridine. In the method for producing a bisphenol compound, the object is to provide an industrially advantageous method capable of efficiently producing the desired bisphenol compound with high selectivity while suppressing the formation of by-products. is there.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a strong acid cation exchange resin and 2- (2-mercaptoethyl) pyridine as a cocatalyst for the strong acid cation exchange resin catalyst. It has been discovered that the presence of 0.05 to 0.5% by weight of water in the raw material improves the selectivity of the target bisphenol compound and reduces the amount of indane compound produced as a by-product. The strong acid cation exchange resin catalyst modified with 2- (2-mercaptoethyl) pyridine used for the synthesis of bisphenol compound is a strong acid cation exchange resin catalyst modified with 4- (2-mercaptoethyl) pyridine. Compared to the above, it is said that the initial activity is almost equal or inferior, but it is known to produce a bisphenol compound with high selectivity while maintaining a high conversion rate over a long period of time (patent) (Ref. 4). When the present inventors produce a bisphenol compound using a strong acid cation exchange resin catalyst modified with 2- (2-mercaptoethyl) pyridine, the water concentration in the reaction raw material is determined by converting the acetone conversion rate. The present inventors have found that a bisphenol compound can be produced with high selectivity by increasing a minute amount such that the concentration does not reach a greatly decreasing concentration. The present invention has been made based on these findings.

That is, the present invention provides the following.
[1] A method for producing a bisphenol compound in which a phenol compound and a carbonyl compound are reacted in the presence of a cation exchanger having a strong acid group and 2- (2-mercaptoethyl) pyridine, the phenol compound and the carbonyl compound A process for producing a bisphenol compound, characterized in that the concentration of water in the reaction raw material containing 0.05 to 0.05% by weight.
[2] In the cation exchanger having a strong acid group and the 2- (2-mercaptoethyl) pyridine, at least a part of the strong acid group of the cation exchanger having a strong acid group is 2- (2-mercaptoethyl). The method for producing a bisphenol compound according to [1], wherein the bisphenol compound is present as a modified strong acid type cation exchanger protected by pyridine.
[3] The modified strong acid cation exchanger according to [2], wherein 3 to 30% of the strong acid group is protected by 2- (2-mercaptoethyl) pyridine. A method for producing a bisphenol compound.
[4] The cation exchanger having a strong acid group and the modified strong acid cation exchanger having a particle size of 30 to 650 μm account for 50% or more of the total [1] to [3 ] The manufacturing method of the bisphenol compound in any one of.
[5] The method for producing a bisphenol compound according to any one of [1] to [4], wherein the amount of the phenol compound relative to the carbonyl compound in the reaction raw material is 10 to 40 times in molar ratio.
[6] A phenol compound and a carbonyl compound are reacted at a temperature of 50 to 90 ° C. in the presence of the cation exchanger having a strong acid group and / or a modified strong acid cation exchanger. ]-The manufacturing method of the bisphenol compound in any one of [5].
[7] The method for a bisphenol compound according to any one of [1] to [6], wherein the bisphenol compound is bisphenol A.

According to the method of the present invention, when a phenol compound and a carbonyl compound are reacted in the presence of a cation exchanger having a strong acid group and 2- (2-mercaptoethyl) pyridine, 0.05 wt. By the presence of ˜0.5% by weight, the production of by-products such as indane compounds can be suppressed. The indane compound here refers to p-isopropenylphenol cyclic dimer and isomers thereof. As a result, a bisphenol compound can be continuously produced stably at a high conversion rate and high selectivity over a long period of time, which is extremely advantageous industrially. Compared to the case where the same reaction is carried out in the presence of a cation exchanger having a strong acid group modified with 2- (4-mercaptoethyl) pyridine, which is a conventional technique, the production of by-products can be suppressed with a small amount of water. It has the effect.

It is a figure which shows the superposition | polymerization apparatus used for the manufacturing method of a gel type bead. It is a figure which shows the nozzle member installed in a droplet manufacturing apparatus. Using 2- (2-mercaptoethyl) pyridine-modified strong acidic cation exchange resin catalyst and 4- (2-mercaptoethyl) pyridine-modified strong acidic cation exchange resin catalyst, the water content in the initial phenol solution was 0.3. It is a graph which shows the relationship of the indane compound selectivity when it is made to react by%. 6 is a graph showing the relationship between the water content in the initial phenol solution and the acetone conversion when the reaction is carried out using a 2- (2-mercaptoethyl) pyridine-modified strong acidic cation exchange resin catalyst. Relationship between water content in initial phenol solution and total selectivity of bisphenol and 2,4 'isomer when reacted with 2- (2-mercaptoethyl) pyridine modified strongly acidic cation exchange resin catalyst It is a graph which shows. 3 is a graph showing the relationship between the water content in the initial phenol solution and the indane compound selectivity when the 2- (2-mercaptoethyl) pyridine-modified strong acidic cation exchange resin catalyst is used for the reaction.

The description of the constituent requirements described below is an example (representative example) of an embodiment of the present invention, and is not specified by these contents.
The present invention relates to a process for producing a bisphenol compound in which a phenol compound and a carbonyl compound are reacted in the presence of a cation exchanger having a strong acid group and 2- (2-mercaptoethyl) pyridine. A method for producing a bisphenol compound, characterized in that the concentration of water in the reaction raw material containing the compound is 0.05 to 0.5% by weight (hereinafter sometimes referred to as “the production method of the present invention”) .

In the production method of the present invention, the bisphenol compound is produced by a condensation reaction between a phenol compound and a carbonyl compound. A phenol compound means a compound having phenol as a partial structure. In the condensation reaction between a phenol compound and a carbonyl compound, it is understood that the strong ortho-para orientation of the phenolic hydroxyl group, in particular the para orientation, is used. Therefore, the phenol compound used is a substituent at the ortho or para position. Those without are preferred. Among them, the bisphenol compound which is a condensation reaction product is generally preferably a 4,4′-bisphenol compound from the viewpoint of its use, and from this point, a phenol compound having no substituent at the para position is preferable.

When the phenol compound has a substituent, the substituent does not inhibit the ortho-para orientation of the phenolic hydroxyl group, and the use of the resulting bisphenol compound as long as it does not sterically hinder the condensation position of the carbonyl compound. It may be arbitrary depending on the physical properties. Typical examples of the substituent include a lower alkyl group having 1 to 4 carbon atoms. Moreover, the compound of the same substitution position can be used also about the phenol compound which substituted halogen atoms, such as a fluorine atom, a chlorine atom, and a bromine atom, instead of this substituent. The number of substituents may be one or more.

Specific examples of the phenol compound include phenol (unsubstituted phenol), o-cresol, m-cresol, 2,5-xylenol, 2,6-xylenol, 2,3,6-trimethylphenol, Examples include 2,6-di-tert-butylphenol, o-chlorophenol, m-chlorophenol, 2,5-dichlorophenol, and 2,6-dichlorophenol. Of these, phenol is particularly preferred. Although the manufacturing method of the said phenol compound has a well-known method used normally, the phenol compound collect | recovered within the bisphenol manufacturing process explained in full detail behind can also be used.

The above-mentioned phenolic compound (excluding the phenolic compound recovered within the bisphenol production process described later) can be used as it is as long as it has a high purity, but generally it is preferably used after purification. The method for purifying the phenol compound is not particularly limited. For example, the phenol compound is reacted with an acidic catalyst such as a general cation exchanger having a strong acid group at 40 to 110 ° C. and contained in the phenol compound. For example, a method of removing heavy components by distilling after the impurities to be heavy are distilled. Usually, the purified phenol compound is used as it is, but when water is contained in the phenol compound, it is generally preferable to use it after removing the water. Although there is no restriction | limiting in particular as the method of removing the water | moisture content in a phenol compound, For example, the method of distilling the phenol compound containing a water | moisture content in presence of an azeotropic agent, and isolate | separating a phenol compound and a water | moisture content etc. is mentioned. The phenol compound thus obtained is used as a reaction raw material by supplying it to the reactor.

The carbonyl compound used in the production method of the present invention is not particularly limited, and specific examples include ketones having about 3 to 10 carbon atoms such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, and acetophenone, And aldehydes having about 1 to 6 carbon atoms such as formaldehyde, acetaldehyde, propionaldehyde and butyraldehyde. Of these, acetone is preferred.

When phenol is used as the phenol compound and acetone is used as the carbonyl compound, bisphenol A useful as a raw material for polycarbonate resin and the like can be obtained, which is particularly preferable.
Examples of the method for producing the carbonyl compound include known methods that are generally used, and a carbonyl compound recovered in a bisphenol production process, which will be described in detail later, can also be used.

The molar ratio of the phenol compound and carbonyl compound used as a raw material for the condensation reaction is usually 10 to 40 mol, preferably 12 to 25 mol, with respect to 1 mol of the carbonyl compound. When there is too little usage-amount of a phenol compound, there exists a tendency for a by-product to increase. On the other hand, if the amount is too large, there is almost no change in the effect. Rather, the amount of the phenol compound to be recovered and reused tends to increase, which tends to be uneconomical.

In the production method of the present invention, a cation exchanger having a strong acid group or a cation exchanger having a strong acid group obtained by modifying a part of the strong acid group with 2- (2-mercaptoethyl) pyridine is used as the acidic catalyst.
The cation exchanger having a strong acid group subjected to this modification is obtained by introducing a strong acid group such as a sulfonic acid group into a commonly used cation exchanger.
The exchange capacity (amount of strong acid group) as the cation exchanger having a strong acid group is usually 0.5 meq / mL or more, preferably 1.0 meq / mL or more per unit volume of the resin in the water state. On the other hand, it is usually 3.0 meq / mL or less, preferably 2.0 meq / mL or less. In the case of a dry resin, it is usually 1.0 meq / g or more per unit weight, preferably 2.0 meq / g or more, and usually 6.0 meq / g or less, preferably 5.5 meq / g or less. is there. In the wet state in which the adhering water is removed from the water-containing resin, it is usually 0.5 meq / g or more, preferably 1.0 meq / g or more, while usually 3.0 meq / g or less, preferably 2.0 meq / g. It is as follows. If this exchange capacity is too low, the catalytic activity is insufficient, and a cation exchanger having an excessively high exchange capacity is difficult to produce.

The exchange capacity of the cation exchanger having a strong acid group is, for example, “Diaion, Ion Exchange Resin / Synthetic Adsorbent Manual 1” (Mitsubishi Chemical Corporation, revised 4th edition, issued on October 31, 2007, 133). ˜Page 135) or a method according to this method.
The main form of the cation exchanger having a strong acid group used here includes a gel type and a porous type (porous type, high porous type, or macroporous type), and the bisphenol compound of the present invention. From the viewpoint of production cost, a gel type is preferable. In addition, a porous type (a porous type, a high porous type, or a macroporous type) is also preferable from the viewpoint of ensuring substance diffusibility, resin durability, and strength. The gel type includes a simple gel type copolymer and an expanded network type gel copolymer, both of which can be used. On the other hand, the porous type is a porous copolymer, which can be used with any surface area, porosity, average pore diameter and the like.

As a method for preparing a cation exchanger having a gel-type or porous-type strong acid group, a conventionally known method can be used. For example, “Technology and Application of Ion Exchange Resin” (issued by Organo Corporation, revised edition, Showa) (May 16, 1981, pages 13 to 21).
The size of the cation exchanger having a strong acid group used in the production method of the present invention (hereinafter sometimes referred to as “catalyst beads”) and the modified strong acid cation exchanger described below has an average particle size of Usually, it exists in the range of 0.2 mm or more and 2.0 mm or less, and a particle size distribution uniformity is 1.6 or less normally, Preferably it is 1.5 or less. Further, particularly preferably, the catalyst beads used in the present invention and the modified strong acid cation exchanger described below are 50% or more of the whole, preferably 60% or more, more preferably 80% or more, most preferably 90% or more has a particle size of 30 to 650 μm.

The catalyst beads may be produced by any method as long as the catalyst beads having the size described above can be produced. The following is a copolymerization reaction of a polymerizable monomer containing a styrene monomer and a crosslinkable monomer. The gel type catalyst beads obtained in the above will be described in detail as an example.
The styrenic monomer that is a raw material for the gel-type catalyst beads is a monomer having an arbitrary substituent in a range that does not impair the function as an ion exchange resin on styrene or a benzene ring of styrene or a vinyl group of styrene, Polymers such as polyesters, polycarbonates, polyamides, polyolefins, poly (meth) acrylic acid esters, polyethers, polystyrenes, and macromonomers in which the ends of oligomers have a styryl structure may also be used. Here, “(meth) acryl” means “acryl” and “methacryl”. The same applies to “(meth) acryloyl” described later.

The styrene monomer is preferably a monomer represented by the following formula (1).

(In the formula, X ₁ , X ₂ and X ₃ are each a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, a halogen atom, an alkylsilyloxy group, a nitro group or a nitrile group, and Y is a hydrogen atom. Amino group, alkylamino group, alkyl group, alkenyl group, alkynyl group, halogen atom, haloalkyl group, aryl group such as phenyl group and naphthyl group, aralkyl group such as benzyl group, alkoxyalkyl group, nitro group, alkanoyl group, Aroyl group such as benzoyl group, alkoxycarbonyl group, allylalkoxycarbonyl group, alkoxy group, haloalkoxy group, allyloxy group, aralkyloxy group, alkoxyalkyloxy group, alkanoyloxy group, alkoxycarbonyloxy group, aralkyloxycarbonyloxy group, Or Alkyl .N showing an aryloxy group is an integer from 1 to 5, X _1, X _2, X ₃ is a plurality of Y when may be the same or different from each other, and n is 2 or more are identical or different May be.)
Specific examples of the styrene monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, fluorostyrene, chlorostyrene, bromo Vinyl groups such as styrene such as styrene in which the benzene ring is substituted with an alkyl group having 1 to 4 carbon atoms or a halogen atom, α-methylstyrene, α-fluorostyrene, β-fluorostyrene, etc. have 1 to 4 carbon atoms. And styrene substituted with an alkyl group or a halogen atom. Of these, styrene is most preferable as the styrene monomer. Moreover, these styrene-type monomers may be used individually by 1 type, and 2 or more types may be mixed and used for them.

The crosslinkable monomer is a compound having two or more carbon-carbon double bonds copolymerizable with the styrene monomer in the molecule. Specifically, polyvinylbenzene such as divinylbenzene and trivinylbenzene, divinyltoluene and the like Two or more benzene rings such as alkyldivinylbenzene, bis (vinylphenyl), bis (vinylphenyl) methane, bis (vinylphenyl) ethane, bis (vinylphenyl) propane, and bis (4-vinylphenyl) sulfone Or the aromatic divinyl compound which has a structure couple | bonded through coupling groups, such as an alkylene group and a styrylene group, is mentioned. Polymers such as polyester, polycarbonate, polyamide, polyolefin, poly (meth) acrylic ester, polyether, polystyrene, etc. Polymeric carbon-carbon double bonds such as styryl structure at both ends of the oligomer and (meth) acrylic structure It may be a macromonomer having Among these, divinylbenzene is preferable as the crosslinkable monomer. Depending on the divinylbenzene, ethylvinylbenzene (ethylstyrene) may be produced as a by-product when it is produced, and this divinylbenzene may be used in the present invention. can do.
These crosslinkable monomers may be used individually by 1 type, and 2 or more types may be mixed and used for them.

The polymerizable monomer for producing the gel-type catalyst beads includes the styrenic monomer and the crosslinkable monomer, but additionally contains other monomers that can be polymerized therewith as necessary. Also good. Specific examples of such polymerizable monomers (hereinafter sometimes referred to as “third monomers”) include polycyclic aromatic skeletons such as naphthalene, anthracene, and phenanthrene, such as vinylnaphthalene and vinylanthracene. Vinyl monomers; (meth) acrylic acid esters such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate; diene hydrocarbon compounds such as butadiene and isoprene; α-olefins such as 1-pentene and 1-hexene ; (Meth) acrylonitrile and the like. These may be used alone or in combination of two or more.

In addition, by using such a third monomer, an effect such as an increase in oxidation resistance can be obtained. In this case, the amount used is usually 50 mol% or less with respect to the styrene monomer, preferably It is 20 mol% or less, and particularly preferably 10 mol% or less. If the amount of the third monomer used is too large, the amount of strong acid groups per unit weight that can be introduced into the resulting copolymer decreases, and the desired catalytic activity may not be obtained.

The degree of crosslinking of the gel-type beads, which are a copolymer obtained by polymerizing a polymerizable monomer containing a styrene monomer and a crosslinking monomer, is preferably 1% or more, more preferably 2% or more, and preferably 8% or less. 5% or less is more preferable. The degree of cross-linking here refers to the concentration of the cross-linkable monomer in the polymerizable monomer to be subjected to polymerization on the weight basis, and is the same as the definition used in this field.

If the degree of crosslinking is too small, it will be difficult to maintain the strength of the resulting catalyst beads and modified strong acid type cation exchanger, and when used as a catalyst, the phenolic compound or phenolic compound and water will be used before use. Swelling or shrinking when conditioning by contacting with a liquid mixture or the like causes crushing of catalyst beads and modified strong acid type cation exchanger, etc., which is not preferable. On the other hand, if the degree of crosslinking is too large, the resulting catalyst beads and modified strong acid type cation exchanger will not easily swell, so that diffusion resistance in the catalyst beads and modified strong acid type cation exchanger will easily occur, and catalytic activity will be increased. This is not preferable because it causes a significant decrease in.

The copolymerization reaction of a polymerizable monomer containing a styrene monomer and a crosslinkable monomer can be performed based on a known technique using a radical polymerization initiator. As the radical polymerization initiator, one or more of benzoyl peroxide, lauroyl peroxide, t-butyl hydroperoxide, azobisisobutyronitrile and the like are used. Usually, the weight of the polymerizable monomer (total monomer) Weight) to 0.05 wt% or more and 5 wt% or less.

The polymerization mode is not particularly limited, and can be carried out in various modes such as solution polymerization, emulsion polymerization, suspension polymerization, etc. In order to keep the uniformity coefficient and average particle size described below within a specified range, a sieve is used. It is also possible to classify by. And in this invention, the well-known method of obtaining the spherical copolymer of a uniform particle size is applied suitably. For example, prior to polymerization, a method is known in which an oil-in-water dispersion in which monomer-containing droplets of uniform particle size are dispersed in a separate apparatus is prepared, and this dispersion is charged into a polymerization vessel and polymerized. As a method for producing an oil-in-water dispersion with a uniform particle size, a nozzle plate having an upwardly formed ejection hole is provided at the bottom of a water-filled container, and the monomer-containing liquid is supplied into the water through this ejection hole. By doing so, a method of dispersing the monomer-containing droplets in water (for example, see Japanese Patent Application Laid-Open No. 2003-252908 and Japanese Patent No. 3899786) can be used. This method is employed in the embodiments described later.

The polymerization temperature in the copolymerization reaction is usually room temperature (about 18 to 25 ° C.) or higher, preferably 40 ° C. or higher, more preferably 70 ° C. or higher, usually 250 ° C. or lower, preferably 150 ° C. or lower, more preferably. Is 140 ° C. or lower. If the polymerization temperature is too high, depolymerization occurs at the same time, and the degree of polymerization completion is reduced. If the polymerization temperature is too low, the degree of polymerization completion will be insufficient. The polymerization atmosphere can be carried out under air or an inert gas, and nitrogen, carbon dioxide, argon or the like can be used as the inert gas.

The method for introducing strong acid groups into the gel-type beads, which are copolymers obtained by the above copolymerization reaction, is not particularly limited, and can be performed according to a conventional method. The strong acid group is preferably a sulfonic acid group, and the method of introducing a sulfonic acid group (sulfonation) is, for example, in the absence of an organic solvent, or benzene, toluene, xylene, nitrobenzene, chlorobenzene, tetrachloromethane. In the presence of an organic solvent such as dichloroethane, trichloroethylene or propylene dichloride, the gel-type beads as a copolymer are reacted with a sulfonating agent such as sulfuric acid, chlorosulfonic acid or fuming sulfuric acid. Here, as for an organic solvent and a sulfonating agent, all may be used individually by 1 type, and 2 or more types may be mixed and used for them. The reaction temperature at this time is usually about 0 to 150 ° C., and is appropriately selected according to the sulfonating agent and the organic solvent to be used.

The cation exchanger having a strong acid group is obtained by separating the gel-type beads into which the strong acid group has been introduced by washing, isolation or the like according to a conventional method.
In the production method of the present invention, when the catalyst is used in a fixed bed flow system, the catalyst beads contained therein or the modified strong acid type cation exchanger described below has a particle size of 30 to 600 μm. Those that occupy 50% or more are preferably used.

When the catalyst beads or the modified strong acid cation exchanger described below has a particle size of 30 to 650 μm is 50% or more of the total, excellent performance in terms of catalyst activity and desired bisphenol compound selectivity Is obtained. On the other hand, if the catalyst beads or the modified strong acid type cation exchanger described below has a particle size of 30 to 650 μm is less than 50% of the total, the catalyst activity is lowered due to diffusion resistance in the catalyst particles. At the same time, the sequential reaction within the catalyst particles causes a decrease in selectivity.

When the average particle diameter of the catalyst beads used in the production method of the present invention or the modified strong acid cation exchanger described below is smaller than 100 μm, it is necessary to remarkably increase the supply pressure of the raw material to the catalyst layer. Since the force applied to the catalyst increases and the catalyst particles are easily worn and refined, the life of the catalyst packed layer is shortened. In addition, when the raw material supply pressure is increased, the amount of energy consumption is increased and the economic efficiency of the process is deteriorated. Therefore, the average particle size is preferably 100 μm or more, and the pressure in the catalyst packed bed when used in the fixed bed flow system Since the loss can be suppressed to a low level, the average particle size is more preferably 300 μm or more.

Further, when the particle size uniformity coefficient of the catalyst beads or the modified strong acid cation exchanger described below is 1.10 or less, the pressure loss in the catalyst packed bed when used in a fixed bed flow system is low. Can be suppressed. Therefore, when using it on a fixed bed, it is preferable that the uniformity coefficient is 1.05 or less because the same effect is further improved. On the other hand, if the uniformity coefficient is greater than 1.10, it is necessary to remarkably increase the supply pressure of the raw material to the catalyst layer, the force applied to the catalyst particles is increased, and the catalyst particles are likely to be worn and refined. The life of the catalyst packed bed is shortened. Further, when the raw material supply pressure is increased, the energy consumption is increased correspondingly, and the economic efficiency of the process is deteriorated.

The average particle size and the particle size distribution uniformity referred to in this specification for the resin are expressed by the following formulas described in Diaion Manual 1 (Mitsubishi Chemical Corporation, 4th edition, 2007, pages 140 to 142). It is defined by the calculated value.
Average particle diameter = diameter corresponding to 50% of the cumulative volume of resin Uniformity coefficient = diameter corresponding to the cumulative volume on the large particle side corresponding to 40% / diameter corresponding to the cumulative volume on the large particle side corresponding to 90% It can also be used as the value of the sieving method by converting the measured value obtained by using a method other than the centrifugal sedimentation method, Coulter method, image analysis method, laser diffraction scattering method and the like.

In the production method of the present invention, the reaction is carried out in the presence of the catalyst beads and the co-catalyst 2- (2-mercaptoethyl) pyridine. Here, 2- (2-mercaptoethyl) pyridine is a compound in which the 2-position of the pyridine ring is substituted with a mercaptoethyl group.
The 2- (2-mercaptoethyl) pyridine is represented by a commercially available product or a method described in JP-A No. 2002-003475, JP-A No. 2002-220373, JP-A No. 2005-170820, and the like. Any of those produced according to known methods may be used.

In the production method of the present invention, the catalyst beads and the co-catalyst 2- (2-mercaptoethyl) pyridine may be present individually in the reaction system, or at least a part of the catalyst beads is 2 It is also preferable to use a compound protected by-(2-mercaptoethyl) pyridine (sometimes referred to as “modified strong acid type cation exchanger” in the present specification) in the reaction system.

A method for protecting the strong acid group of the catalyst beads with 2- (2-mercaptoethyl) pyridine is a known method, for example, according to a method disclosed in JP-A-11-246458, water, alcohol, A solution in which 2- (2-mercaptoethyl) pyridine is dissolved in a solvent such as ketone, ether and phenol, or 2- (2-mercaptoethyl) pyridine not diluted with the solvent is directly dispersed in the solvent. It is performed by a method of mixing and stirring by a method such as dropping to the catalyst beads. By this method, a part of the strong acid group of the cation exchanger having a strong acid group reacts (neutralizes) with the thiol compound and is denatured by ionic bonding.
As the modified strong acid type cation exchanger, one in which 3 to 30%, preferably 3 to 20%, of the strong acid group is protected with 2- (2-mercaptoethyl) pyridine is used.

In the present invention, the catalyst beads and the modified strong acid type cation exchanger become an obstacle to the reaction when moisture remains in the resin, and the present invention adjusts the moisture concentration in the reaction raw material. Since it is characteristic to carry out, it is preferable to remove the water | moisture content in an ion exchange resin by making it contact with the phenol compound which is a raw material before using for reaction. In addition, it is desirable to remove moisture in the phenol compound as a raw material before the reaction. Examples of the method for removing water include azeotropic distillation as described in the method for producing a phenol compound. By such treatment, the induction period at the start of the reaction is shortened and can be used for the reaction promptly.

In the production method of the present invention, the catalyst beads and 2- (2-mercaptoethyl) pyridine or the modified strong acid cation exchanger are charged into a reactor, and a phenol compound and a carbonyl compound are supplied to the reactor. These are reacted to produce a bisphenol compound. In the present invention, the phenol compound and the carbonyl compound may be reacted in the modified strong acid type cation exchanger or in a reactor packed with the catalyst beads and 2- (2-mercaptoethyl) pyridine as an acidic catalyst. Is not particularly limited as long as it is a method in which the reaction is carried out by supplying the carbonyl compound continuously or batchwise, for example, any of fixed bed flow method, fluidized bed method, continuous stirring method and batch method Good.

In addition, when the reaction between the phenol compound and the carbonyl compound is performed in a fixed bed flow system, a cation exchanger having a strong acid group filled with a screen or the like provided at least in either the upper part or the lower part of the apparatus, if necessary, or The modified strong acid cation exchanger may be allowed to flow only through the reaction solution without flowing out of the apparatus. The reaction solution may flow from the upper part to the lower part of the apparatus (down flow type) or may flow from the lower part to the upper part of the apparatus (up flow type).

In the present invention, a phenol compound and a carbonyl compound are continuously or batchwise supplied to a reactor packed with a modified strong acid cation exchanger or the catalyst beads and 2- (2-mercaptoethyl) pyridine as an acidic catalyst. To produce a bisphenol compound. As a reaction system, a batch system is also known, but by reacting continuously, a bisphenol compound can be produced more efficiently than when the reaction is performed in a batch system.

The phenol compound and the carbonyl compound may be supplied separately to the reactor, or may be mixed and supplied. The mixing ratio of the phenol compound and the carbonyl compound is as described above.
In the production method of the present invention, the concentration of water in all the reaction raw materials is adjusted to 0.05 to 0.5% by weight. The concentration of the water is more preferably 0.1 to 0.3% by weight, and most preferably 0.15 to 0.25% by weight. In order to allow such a concentration of water to be present in the reaction system, a method of adding an appropriate amount of water using a raw material not containing water is preferable. In addition, it is desirable to remove moisture in the phenol compound as a raw material before the reaction. Examples of the method for removing water include azeotropic distillation as described in the method for producing a phenol compound. Even when a raw material containing water is used, water can be added and used so that the water concentration of the raw material becomes the above concentration.

The reaction temperature is usually performed at a temperature at which the reaction solution can exist in a liquid state without solidifying. When the phenol compound is phenol, it is preferably 40 ° C. or higher, 50 ° C. or higher, more preferably 60 ° C. or higher. The higher the reaction temperature, the more advantageous the reaction rate, but the maximum temperature in the reactor is preferably 120 from the viewpoint of the heat resistance temperature of the cation exchanger having a strong acid group or the modified strong acid type cation exchanger. It is desirable to carry out the reaction under the conditions of not higher than 100 ° C., more preferably not higher than 100 ° C., still more preferably not higher than 90 ° C. When the reaction temperature increases, the strong acid group such as a sulfonic acid group is eliminated due to partial decomposition even at a temperature lower than the heat resistance temperature of the cation exchanger having the strong acid group or the modified strong acid cation exchanger. From such a viewpoint, the lowest possible temperature is preferable, but if the temperature is too low, the produced bisphenol compound may solidify.

Although the reaction time varies depending on conditions such as the amount of catalyst used, reaction temperature, etc., in the method of performing the reaction continuously, it is usually based on LHSV (liquid hydrated catalyst beads or modified strong acid type cation exchange resin as a standard. - hourly space velocity) is performed in 0.05 ~ 20 hr ^-1, preferably at LHSV0.2 ~ 10hr ^-1. In the batch reaction, the reaction is performed in about 0.1 to 20 hours.
In addition to a large excess of phenol, the reaction solution produced by the above method contains unreacted raw materials, impurities generated during the reaction, etc., so the target bisphenol compound is extracted from these solutions. It is necessary to take it out. The method for separating and purifying the bisphenol compound as the target substance from the reaction mixture is not particularly limited, and is performed according to a known method. The case where the target substance is bisphenol A will be described below as an example.

Subsequent to the above reaction, the reaction mixture obtained by the reaction is separated into a component containing bisphenol A and phenol and a low-boiling component containing water, unreacted acetone, etc. produced as a by-product in the reaction (hereinafter referred to as this). Sometimes referred to as “low boiling point component separation step”). The low boiling point component separation step is preferably performed by a method of separating the low boiling point component by distillation under reduced pressure, and the low boiling point component may contain phenol or the like. The component containing bisphenol A and phenol can adjust the concentration of bisphenol A to a desired concentration by removing phenol by distillation or adding phenol as necessary.
The phenol compound such as phenol recovered by the distillation or the like can be recycled and used as a raw material for the bisphenol compound production method.

As a liquid containing a phenol compound to be recycled, a phenol solution obtained by separating a target bisphenol compound from a reaction product liquid (a method of solidifying a bisphenol compound described below by crystallization and solid-liquid separation in a solid-liquid separation step) When the bisphenol compound is separated by this, this liquid is generally called “mother liquor”, but there are other methods such as distillation, which are not limited thereto. Can be used. The phenol compound purified as described above should be used as a cleaning solution for the crystals obtained in the solid-liquid separation step described below, and recycled to the reactor together with the mother liquor in a desired manner depending on the process. You can also.

At that time, it is preferable to separate the whole amount or a part thereof and remove impurities such as heavy components after treatment with an acid or alkali catalyst, or recover the bisphenol compound and use it as a raw material for the bisphenol compound. When the phenol compound recovered in the process is recycled and used as a washing liquid for the crystals obtained in the solid-liquid separation step, it is generally preferable to use it after purification.
In small scales such as laboratories, high-purity phenolic compounds purified as phenolic compounds used as raw materials are also used, but in industrial scales, phenolic compounds recovered in the process are usually recycled and used. It is advantageous to do so.

In the recycling of the phenol compound, the phenol compound is phenol, and a solution containing at least one of bisphenol A, 2,4′-isomer, and p-isopropylphenol is supplied to the reactor as a recycling liquid containing phenol. When used, the amount is usually 0.3 to 20 parts by weight of bisphenol A per 100 parts by weight of phenol. In addition, the 2,4'-isomer is usually 0.3 to 10 parts by weight with respect to 100 parts by weight of phenol. Further, p-isopropylphenol is usually 0.1 to 1.0 part by weight per 100 parts by weight of phenol. The total amount of bisphenol A, 2,4'-isomer and p-isopropylphenol is usually 1 to 35 parts by weight per 100 parts by weight of phenol.

On the other hand, when other unknown substances coexist in the recycling liquid containing phenol, the amount is usually 0.3 to 10 parts by weight with respect to 100 parts by weight of phenol. . The total amount of bisphenol A, 2,4'-isomer, p-isopropylphenol, and other structurally unknown substances is usually 1 to 45 parts by weight based on 100 parts by weight of phenol.

If the concentration of these compounds with respect to phenol is to be lower than this lower limit, an additional purification step is required, which is not preferable. If these compounds are contained in excess of the upper limit with respect to phenol, bisphenol A, 2,4′-isomer, and adduct of bisphenol A and phenol precipitate as crystals in the reaction system, and the operation is continued. May become difficult. Moreover, when manufacturing bisphenol A as a product, refinement | purification may become difficult.

The low boiling point component obtained in the low boiling point component separation step separates and recovers unreacted acetone by the acetone circulation step, and circulates the collected acetone (hereinafter sometimes referred to as recovered acetone) to the reaction step. Can do.
The recovered acetone contains a trace amount of lower alcohol as an impurity. The lower alcohol means an alcohol having 1 to 8 carbon atoms, and is typically methanol. The methanol concentration in the total acetone including unreacted acetone and recovered acetone supplied to the reaction step is desirably 1,000 ppm or less, preferably 500 ppm or less, more preferably 300 ppm or less.

Since methanol contained in the recovered acetone does not participate in the reaction, it accumulates in the separated and recovered acetone. Accumulated methanol degrades the modified strong acid cation exchanger and shortens the catalyst life, so it is desirable to keep the methanol concentration low by distillation or the like.
Subsequently, the reaction mixture obtained by the reaction through the low boiling point component separation step is subjected to a crystallization step for obtaining a slurry containing crystals of an adduct of bisphenol A and phenol. The concentration of bisphenol A, which is a component containing bisphenol A and phenol used in the crystallization step, is preferably 10 to 40% from the viewpoint of ease of handling of the resulting slurry. As a crystallization method, a method of directly cooling a component containing bisphenol A and phenol, a method of cooling by mixing other solvent such as water and evaporating the solvent, and further removing phenol and concentrating. In order to obtain an adduct having a desired purity, crystallization may be performed once or twice or more.

The slurry obtained in the crystallization step is subjected to solid-liquid separation into adduct crystals and mother liquor by vacuum filtration, pressure filtration, centrifugal filtration, etc., and the adduct crystals of bisphenol A and phenol are recovered ( Hereinafter, this may be referred to as a “solid-liquid separation step”). In the crystallization step, bisphenol A crystals can also be obtained directly by crystallization.
After melting the adduct crystals obtained in the solid-liquid separation step by means of flash distillation, thin film distillation, steam stripping or the like, high purity molten bisphenol A is obtained. The removed phenol is purified as desired, and can be used for reaction, washing of crystals of the adduct obtained in the solid-liquid separation step, and the like.

The obtained high purity molten bisphenol A is solidified in the granulation step. A method of obtaining small spherical bisphenol A prills by injecting molten bisphenol A from a nozzle and bringing it into contact with a cooling gas is simple and preferred. In addition, it is also possible to obtain only bisphenol A by crystallization from the adduct crystal obtained in the solid-liquid separation step, without passing through the dephenol step.

Also, for the purpose of preventing accumulation of impurities in the system, at least a part of the mother liquor separated in the solid-liquid separation step can be treated in the impurity treatment step. For example, it is economical to mix an alkali or acid, heat and then distill to separate light and heavy components, and use the light component for the reaction after recombination treatment with an acid catalyst or the like. However, it is preferable. Here, by purging the heavy component out of the system, accumulation of impurities can be prevented and the purity of the product can be improved. The recovery rate of bisphenol A can also be improved by crystallization after isomerization of at least a part of the mother liquor using an acid catalyst. The 2,4-isomer contained in the mother liquor can be recovered as bisphenol A by a method such as isomerization, but impurities such as indane compounds are difficult to recover as bisphenol A once produced. Can only be removed by purging. By reducing the generation of impurities such as indane by the method of the present invention, it is possible to improve the recovery rate of bisphenol A, and it is possible to reduce the heavy component purged out of the system. Is advantageous.

Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to the following examples. In the following, “part” means “part by weight”.
[Example 1]
(1) Production of copolymer (gel-type beads) Using a droplet production apparatus and a polymerization reaction apparatus with an underwater speaker attached as a vibration apparatus shown in FIG. Hereinafter, it may be referred to as “copolymer”).
The droplet manufacturing apparatus 1 includes a droplet manufacturing tank 3 that holds an aqueous medium 2 that forms a continuous phase, a hydrophobic liquid storage tank 5 that holds a hydrophobic liquid 4 that is immiscible with the aqueous medium 2, and a hydrophobic liquid storage tank. And a hydrophobic liquid supply pipe 6 for supplying the hydrophobic liquid 4 stored in 5 to the droplet production tank 3. In addition, the droplet manufacturing apparatus 1 is in contact with the aqueous medium 2 and includes a nozzle member 7 having an ejection hole 11 for ejecting the hydrophobic liquid 4 supplied from the hydrophobic liquid supply pipe 6, and the inside of the droplet manufacturing tank 3. An underwater speaker (underwater acoustic device) 8 which is a vibration means for mechanically vibrating the aqueous medium 2, an aqueous medium storage tank 9 for storing the aqueous medium 2, and the aqueous medium 2 stored in the aqueous medium storage tank 9. And an aqueous medium supply pipe 10 for supplying the liquid to the droplet production tank 3. Here, reference numeral 12 denotes a hydrophobic liquid ejection storage tank, and reference numerals 13 and 14 denote a supply pump for the hydrophobic liquid and the aqueous medium, respectively.

As the nozzle member 7, as shown in FIG. 2, a circular plate having an outer diameter of 100 mm and 345 ejection holes 11 having a diameter of 0.125 mm arranged in an annular shape was used.
Further, the polymerization reaction device 16 in FIG. 1 is a polymerization in which the droplet 15 in the droplet production tank 3 of the droplet production device 1 is transferred together with the aqueous medium 2 and the polymerization reaction is performed without coalescing and crushing the droplet 15. It has a reaction tank 17 and a hydrophobic liquid droplet transfer pipe 18 that transfers the liquid droplet 15 from the droplet production tank 3 together with the aqueous medium 2 to the polymerization reaction tank 17 without fusing and crushing.

In the droplet manufacturing apparatus 1, the droplet is transferred from the hydrophobic liquid storage tank 5 through the hydrophobic liquid supply pipe 6 to the aqueous medium 2 that is held in the droplet manufacturing tank 3 to form a continuous phase. The hydrophobic liquid 4 can be ejected from the ejection holes 11 provided in the nozzle member 7 to form an ejection flow of the hydrophobic liquid 4. At that time, the aqueous medium 2 side is vibrated by, for example, an underwater speaker 8 to break the jet flow into droplets 15 of a hydrophobic liquid having a uniform particle diameter, and the aqueous medium storage tank 9 A flow of the aqueous medium 2 can be formed in the droplet production tank 3 by supplying the aqueous medium 2 stored in the droplet production tank 3 by the supply pump 14. The droplet 15 of the hydrophobic liquid thus made can be moved.

That is, a hydrophobic liquid ejection storage tank 12 exists in the lower part inside the droplet production tank 3, and a nozzle having an ejection hole 11 that opens toward the aqueous medium 2 and ejects the hydrophobic liquid 4 in the upper part thereof. A member 7 is attached. For this reason, the hydrophobic liquid 4 supplied by the supply pump 13 from the hydrophobic liquid storage tank 5 through the hydrophobic liquid supply pipe 6 is stored in the liquid discharge storage tank 12, and the ejection holes provided in the nozzle member 7. 11 is ejected straight upward. As shown in FIG. 2, a plurality of ejection holes 11 for the hydrophobic liquid 4 are arranged in the nozzle member 7 at a predetermined interval. The diameter of the ejection hole 11 is set according to a desired droplet size.
Since the droplet production tank 3 is connected to the polymerization reaction tank 17 by a droplet transfer pipe 18, droplet production formed by supplying the aqueous medium 2 from the aqueous medium storage tank 9 into the droplet production tank 3. Due to the flow of the aqueous medium 2 in the tank 3, the hydrophobic liquid droplets 15 produced in the droplet production tank 3 are continuously transferred to the polymerization reaction tank 17 together with the aqueous medium 2 and used for the polymerization reaction. .

In this example, first, as the aqueous medium 2, an aqueous solution containing 0.05% by weight of polyvinyl alcohol was filled from the aqueous medium storage tank 9 into the droplet production tank 3 and the polymerization reaction tank 17. The polyvinyl alcohol aqueous solution was heated to 40 ° C. and held until the polymerization reaction started. On the other hand, 96 parts of styrene containing benzoyl peroxide as a polymerization initiator, 4 parts of a polymerizable monomer mixed liquid consisting of divinylbenzene, and a flow rate of 1 from the ejection hole 11 of the nozzle member 7 from the hydrophobic liquid storage tank 5 as a hydrophobic liquid. It was ejected into the droplet production tank 3 at a rate of .54 mL / min / hole. At that time, vibration of 1400 Hz was applied to the jet stream from the underwater speaker 8 in order to break up the jet stream of the polymerizable monomer mixed liquid into droplets 15 having a uniform particle size. The average particle size of the droplets 15 of the polymerizable monomer mixture obtained at this time was 0.32 mm, and the uniformity coefficient was 1.01. The average particle size and uniformity coefficient of the droplet 15 were calculated by taking an enlarged photograph of the droplet and obtaining the particle size distribution by an image analysis method.

The generated droplets 15 were transferred to the polymerization reaction tank 17 along with the flow of the aqueous medium 2. Next, the mixture is polymerized by heating at 75 ° C. for 8 hours while stirring at a rotation speed that does not coalesce or crush the droplets 15 in the polymerization reaction tank 17 (crosslinking degree 4%). It was.
The obtained copolymer slurry was subjected to solid-liquid separation using a centrifuge, and recovered without containing a polyvinyl alcohol aqueous solution. The obtained copolymer was spherical particles having an average particle diameter of 0.29 mm and a uniformity coefficient of 1.02.

The average particle size and uniformity coefficient of this copolymer are “Diaion, Ion Exchange Resin / Synthetic Adsorbent Manual 1” (Mitsubishi Chemical Corporation, 4th revised edition, published on October 31, 2007, pages 140 to 141). ) Was calculated from the particle size distribution measured by the sieving method described in the following formula.
Average particle diameter = diameter corresponding to 50% of the cumulative volume of resin Uniformity coefficient = diameter corresponding to the cumulative volume on the large particle side corresponding to 40% / diameter corresponding to the cumulative volume on the large particle side corresponding to 90%

(2) Production of gel-type catalyst beads 180 g of the copolymer obtained in (1) above is placed in a 1 L four-necked flask, 198 g of nitrobenzene is added, and the mixture is heated and stirred at 70 ° C. for 1.5 hours. The polymer was swollen. After cooling, 324 g of nitrobenzene, 360 g of 98% by weight sulfuric acid and 189 g of fuming sulfuric acid were added, the temperature was raised to 70 ° C., heated for 4 hours, then heated to 105 ° C. and held for 3 hours. After the reaction, a large amount of water was added to dilute and remove the sulfuric acid in the flask, and then demineralized water was added and heated and stirred to distill off nitrobenzene. The obtained resin was washed with demineralized water to obtain gel type catalyst beads (hereinafter sometimes referred to as “strongly acidic cation exchange resin”).

The exchange capacity, average particle size, uniformity coefficient, and catalyst bead content with a particle size of 30 to 650 μm were determined for the strongly acidic cation exchange resin obtained, and the results are shown in Table 1. The content of catalyst beads having a particle size of 30 to 650 μm was calculated from the particle size distribution obtained by the sieving method as in the case of the copolymer.

(3) Preparation of 2- (2-mercaptoethyl) pyridine-modified strong acid type cation exchange resin In a 200 mL four-necked flask equipped with a nitrogen gas introduction tube, the wet strong acid cation exchange resin produced above About 40 mL of 20.0 g-wet, 60 ° C. demineralized water was added to wash the strongly acidic cation exchange resin. The washing solution was discarded by decantation, and about 40 mL of 60 ° C. demineralized water was introduced again. This washing operation was repeated three times. Next, after discarding the washing solution, about 40 mL of demineralized water was added, and the inside of the flask was replaced with nitrogen. Thereto was added 0.74 g (5.32 mmol) of 2- (2-mercaptoethyl) pyridine as a modifying agent (co-catalyst) at a time under stirring, and the mixture was further stirred at room temperature for 2 hours for modification treatment. went. After the treatment, the resulting modified cation exchange resin was washed with demineralized water to obtain a 2- (2-mercaptoethyl) pyridine-modified strong acidic cation exchange resin catalyst (modification rate: 17.2%).

The modification rate is determined by the amount of the strongly acidic cation exchange resin used for modification, the amount of the modifier (2- (2-mercaptoethyl) pyridine) added, and the sulfone in the strongly acidic cation exchange resin determined by titration. It calculated | required according to the following formula from the quantity of the acid group. Here, the amount of the sulfonic acid group in the strongly acidic cation exchange resin corresponds to the exchange capacity.
Modification rate (%) = [(number of moles of added cocatalyst (mmol)) / [(amount of sulfonic acid group in gel-type strongly acidic cation exchange resin (meq / g-wet state) × used for modification) Weight of gel-type strongly acidic cation exchange resin (g-wet state)]] × 100

(4) Production of bisphenol compound 3.0 g of 2- (2-mercaptoethyl) pyridine-modified strong acid cation exchange resin (hereinafter sometimes referred to as “catalyst”) prepared in (3) above. The sample was weighed and repeatedly washed with about 100 mL of phenol at 70 ° C. until the water content of the cleaning liquid became 0.1 wt% or less. Subsequently, phenol was added to the flask so as to be 120.0 g, and the water concentration in the reaction raw material was adjusted to 0.3 wt%, and nitrogen was introduced. Thereafter, 7.4 g of acetone was added all at once at a liquid temperature in the flask of 70 ° C. and a stirring rotational speed of 250 rpm, and the reaction was started. The amount of phenol relative to acetone was 10 times in molar ratio.

The reaction solution was collected 5 hours after the start of the reaction. Moreover, each composition density | concentration in a reaction liquid was quantified on the conditions described below by the high performance liquid chromatography and Karl Fischer moisture meter. The acetone conversion was obtained from the following formula. The selectivity of each product was calculated by calculating the (per product amount) / (total product amount excluding moisture and phenol) from the results of high performance liquid chromatography by the area percentage method. And the selectivity of the indane compound (p-isopropenylphenol cyclic dimer and its isomer) were determined. The results are shown in Table 2.

High-performance liquid chromatography: “LC-10A” manufactured by Shimadzu Corporation
Column: Waters Sun Fire ™ C18 5 μm,
4.6φ × 250mm
Detector: UV 280nm
Eluent: A solution 90% acetonitrile aqueous solution B solution 0.59 mol / L 0.5% sodium dihydrogen phosphate aqueous solution containing phosphoric acid aqueous solution Acetone conversion (%) = [[(number of moles of acetone in 1 kg of raw material)-( Mole of acetone in 1 kg of product liquid)] / (number of moles of acetone in 1 kg of raw material liquid)] × 100

[Example 2]
In the production of (4) bisphenol compound in Example 1, the reaction was carried out in the same manner as in Example 1 except that the water content in the reaction raw material was changed to 0.2% by weight. Rate, the total selectivity of bisphenol A and the 2,4 ′ isomer, and the selectivity of the indane compound. The results are shown in Table 2.

[Example 3]
In the production of the bisphenol compound of Example 1 (4), the water content in the reaction raw material was changed to 0.2% by weight, and the amount of phenol with respect to acetone was 13 times in molar ratio, which was the same as Example 1. In the same manner as in Example 1, the acetone conversion rate, the total selectivity of bisphenol A and the 2,4 ′ isomer, and the selectivity of the indane compound were determined. The results are shown in Table 2.

[Comparative Example 1]
In the production of the bisphenol compound of Example 1 (4), the reaction was carried out in the same manner as in Example 1 except that the water content in the reaction raw material was changed to 0.02% by weight. Rate, the total selectivity of bisphenol A and the 2,4 ′ isomer, and the selectivity of the indane compound. The results are shown in Table 2.

[Comparative Example 2]
In the production of the bisphenol compound of Example 1 (4), the reaction was carried out in the same manner as in Example 1 except that the water content in the reaction raw material was changed to 1.0% by weight. Rate, the total selectivity of bisphenol A and the 2,4 ′ isomer, and the selectivity of the indane compound. The results are shown in Table 2.

As is apparent from Table 2, as a result of using a sulfonic acid type cation exchange resin modified with 2- (2-mercaptoethyl) pyridine as an acidic catalyst, the selectivity of bisphenol A is the reaction rate in the bisphenol A production reaction. It was found that the water concentration in the raw material was particularly high at 0.2% by weight or more.

[Reference Example 1]
(1) Synthesis of 4- (2-mercaptoethyl) pyridine A nitrogen gas inlet tube, a thermometer, a Dimroth condenser, and a dropping funnel were attached to a 300 mL four-necked flask, and 102.9 g (0. 315 mol) and 11.42 g (0.15 mol) of thiourea were charged. After heating to 70 ° C. with stirring in a nitrogen atmosphere, 12.62 g (0.12 mol) of 4-vinylpyridine was added dropwise from the dropping funnel over about 1 hour while maintaining the reaction temperature of 70 ° C. The reaction was continued for 5 hours while maintaining the temperature. After cooling the reaction solution to room temperature, 30 ml of toluene was added.

Furthermore, under stirring, 45.74 g of 28 wt% aqueous ammonia (0.75 mol as ammonia) was added dropwise to the reaction solution over about 2 hours, taking care not to raise the liquid temperature. After completion of dropping, the temperature was raised to 40 ° C. and stirred for 3 hours. After the stirring was stopped, the reaction solution was transferred to a separatory funnel and separated into two phases. The upper phase (toluene phase) was taken out, and the lower phase (aqueous phase) was further extracted twice with 30 ml of toluene.

Next, toluene was distilled off by a rotary evaporator under the conditions of a bath temperature of 50 ° C. and a pressure of 12.5 to 1.1 kPa. The residue obtained here was distilled and purified using a thin film evaporator under conditions of a wall surface temperature of 130 ° C. and a pressure of 0.6 kPa. As a result, 15.6 g of 4- (2-mercaptoethyl) pyridine having a purity of 95.2% was obtained. Obtained. The yield based on the charged 4-vinylpyridine was 88.9%.

(2) Preparation of 4- (2-mercaptoethyl) pyridine-modified strong acid cation exchange resin In the preparation of 2- (2-mercaptoethyl) pyridine-modified strong acid cation exchange resin in Example 1, (3) The copolymer and gel type were prepared in the same manner as in Example 1 except that 4- (2-mercaptoethyl) pyridine obtained above was used instead of 2- (2-mercaptoethyl) pyridine as a catalyst. Catalyst beads were produced, and 4- (2-mercaptoethyl) pyridine-modified strong acid cation exchange resin (modified rate 15.8%) was prepared. The physical property measurement results of the resin are shown in Table 1.

(3) Production of bisphenol compound In Example 1, instead of 2- (2-mercaptoethyl) pyridine-modified strong acid type cation exchange resin, 4- (2-mercaptoethyl) pyridine-modified strong acid type cation obtained above was used. Using an ion exchange resin, the reaction is carried out in the same manner as in Example 1. As in Example 1, the acetone conversion, the total selectivity of bisphenol A and the 2,4 ′ isomer, and the selectivity of the indane compound are determined. Asked. The results are shown in Table 3 and FIG. As is apparent from FIG. 3, in the bisphenol A production reaction, the catalyst modified with 2- (2-mercaptoethyl) pyridine is more indane compound than the catalyst modified with 4- (2-mercaptoethyl) pyridine. The selectivity was low, and from Table 2, it was found that the water concentration in the reaction raw material was 0.2% by weight or more, and in particular, the effect of suppressing the formation of indane compounds was high.

[Example 4]
2- (2-Mercaptoethyl) pyridine-modified strongly acidic cation exchange resin catalyst (modified rate: 17.2%) 7 prepared in the same manner as in Example 1 using the gel-type catalyst beads produced in Example 1 5 mL was packed in a stainless steel column having an inner diameter of 1 cm and a total length of 44 cm. Phenol at 60 ° C. was passed through the top of the reactor filled with the catalyst at 26 mL / hr for 24 hours to completely replace the water in the catalyst with phenol, and then a mixture of 11 phenol / acetone (molar ratio) ( Acetone (4.4% by weight, phenol 76.9% by weight, 4,4′-bisphenol A 9.7% by weight, water 0.3% by weight, other substances 8.7% by weight) at 73 ° C. The reaction was carried out by continuously flowing in the down flow from the upper part of the reactor in hr. The reaction solution is collected from the lower part of the reactor and analyzed by gas chromatography under the following conditions. From the analysis value, acetone conversion, total selectivity of bisphenol A and 2,4 ′ isomer, and Selectivity was calculated. The results are shown in FIGS.

<Acetone conversion (%)>
Gas chromatography: “GC-14B” manufactured by SHIMADZU
Column: “DB-WAX 15 m × 0.53 mm × 1.0 μm” manufactured by Agilent Technologies
Detector: TCD
Carrier gas: He
Conversion rate of acetone (%) = [[(number of moles of acetone in 1 kg of raw material) − (number of moles of acetone in 1 kg of product liquid)] / (number of moles of acetone in 1 kg of raw material liquid)] × 100
<Total selectivity of bisphenol A and 2,4 ′ isomer (%), indane compound selectivity (%)>
Gas chromatography: “GC-2014” manufactured by SHIMADZU
Column: “INERT CAP 1 15 m × 0.25 mm × 1.5 μm” manufactured by GL Sciences Inc.
Detector: FID
Carrier gas: Nitrogen Silylating agent: N, O-Bis (trimethylsilyl) trifluoroacetamide (manufactured by GL Sciences Inc.)
Total selectivity of bisphenol A and 2,4 ′ isomer (%) = [(moles of bisphenol A in 1 kg of product liquid + moles of 2,4 ′ isomer) − (moles of bisphenol A in 1 kg of raw material liquid) +2,4 ′ isomer moles)] / [(acetone moles in 1 kg of raw material liquid) − (acetone moles in 1 kg of product liquid)] × 100
Indan selectivity (%) = [(mole number of indane compound in 1 kg of product liquid) − (mole number of indane compound in 1 kg of raw material liquid)] × 2 / [(mole number of acetone in 1 kg of raw material liquid) − (product liquid Mole of acetone in 1 kg)] × 100

[Example 5]
In the same manner as in Example 1 except that a gel type strongly acidic cation exchange resin (trade name: Diaion (registered trademark) SK104) manufactured by Mitsubishi Chemical Corporation was used as the gel type catalyst beads. 7.5 mL of the prepared 2- (2-mercaptoethyl) pyridine-modified strong acidic cation exchange resin catalyst (modification rate 15.8%) was packed in a stainless steel column having an inner diameter of 1 cm and a total length of 44 cm. Phenol at 60 ° C. was passed through the top of the reactor filled with the catalyst at 26 mL / hr for 24 hours to completely replace the water in the catalyst with phenol, and then a mixture of 11 phenol / acetone (molar ratio) ( Acetone 4.5 wt%, phenol 78.5 wt%, 4,4'-bisphenol A 9.4 wt%, water 0.09 wt%, other substances 7.5 wt%) The reaction was carried out by continuously flowing in the down flow from the upper part of the reactor in hr. The reaction solution was collected from the lower part of the reactor and analyzed by gas chromatography under the same conditions as in Example 4. Similarly, acetone conversion, total selectivity of bisphenol A and 2,4 ′ isomer, and indane Compound selectivity (%) was calculated. The results are shown in FIGS.

[Example 6]
2- (2-mercaptoethyl) pyridine-modified strongly acidic cation exchange resin catalyst (modified rate 16%) 3 g-wet prepared in the same manner as in Example 1 using the gel-type catalyst beads produced in Example 1 The state was filled in a glass column with a jacket having an inner diameter of 1 cm and a total length of 10 cm, and hot water at 70 ° C. was circulated through the jacket part. Phenol at 70 ° C. was passed through the top of the reactor filled with the catalyst at 1.5 mL / min for 1.5 hours to completely replace the moisture in the catalyst with phenol, and then phenol with a water content of 0.43% by weight. / Acetone mixed solution (phenol / acetone molar ratio 13) was continuously passed through the upper part of the reactor at 70 mL with a flow rate of 3 mL / min. The reaction solution was collected from the lower part of the reactor and analyzed by gas chromatography under the same conditions as in Example 4. Similarly, acetone conversion, total selectivity of bisphenol A and 2,4 ′ isomer, and indane Compound selectivity (%) was calculated. The results are shown in Table 4.

[Example 7]
In Example 6, the reaction was conducted in the same manner as in Example 6 except that a phenol / acetone mixed solution (phenol / acetone molar ratio 13) having a water content of 0.07% by weight was used. The total selectivity of bisphenol A and the 2,4 ′ isomer and the selectivity (%) of the indane compound were calculated. The results are shown in Table 4.

[Comparative Example 3]
In Example 6, the reaction was carried out in the same manner as in Example 6 except that a phenol / acetone mixed solution (phenol / acetone molar ratio 13) having a water content of 0.03% by weight was used. The total selectivity of bisphenol A and the 2,4 ′ isomer and the selectivity (%) of the indane compound were calculated. The results are shown in Table 4.

[Reference Example 2]
Using the gel-type catalyst beads used in Example 5, a 4- (2-mercaptoethyl) pyridine-modified strongly acidic cation exchange resin catalyst (modification rate 15%) prepared in the same manner as in Example 5, In Example 6, the reaction was performed in the same manner as in Example 6 except that a phenol / acetone mixed solution (phenol / acetone molar ratio 13) having a water content of 0.06% by weight was used. The total selectivity of bisphenol A and the 2,4 ′ isomer and the selectivity (%) of the indane compound were calculated. The results are shown in Table 4.

[Example 8]
Using the gel-type catalyst beads produced in Example 1, a 2- (2-mercaptoethyl) pyridine-modified strong acidic cation exchange resin catalyst (modification rate 5%) prepared in the same manner as in Example 1, In Example 6, the reaction was carried out in the same manner as in Example 6 except that a phenol / acetone mixed solution (phenol / acetone molar ratio of 13) having a water content of 0.05% by weight was used. The total selectivity of bisphenol A and the 2,4 ′ isomer and the selectivity (%) of the indane compound were calculated. The results are shown in Table 4. As is apparent from Table 4, when a 2- (2-mercaptoethyl) pyridine-modified strongly acidic cation exchange resin catalyst having a 5% modification rate was used, the modification rate was 16% (Example 6). The indane compound selectivity was found to be unchanged.

[Example 9]
In Example 6, the reaction was conducted in the same manner as in Example 6 except that a phenol / acetone mixed solution (phenol / acetone molar ratio 25) having a water content of 0.05% by weight was used. The total selectivity of bisphenol A and the 2,4 ′ isomer and the selectivity (%) of the indane compound were calculated. The results are shown in Table 5.

[Reference Example 5]
In Example 6, the reaction was carried out in the same manner as in Example 6 except that a phenol / acetone mixed solution (phenol / acetone molar ratio 7) having a water content of 0.07% by weight was used. The total selectivity of bisphenol A and the 2,4 ′ isomer and the selectivity (%) of the indane compound were calculated. The results are shown in Table 5. As is apparent from Table 5, it was found that when the phenol / acetone ratio was 10 or less, the acetone conversion rate was lowered and the selectivity of the indane compound was also raised.

[Example 10]
In Example 6, 75 ° C. warm water was passed through the jacket portion, and a phenol / acetone mixed solution (phenol / acetone molar ratio 13) having a water content of 0.43% by weight was added from the top of the reactor at 75 ° C. at 3 mL / min. The reaction was carried out in the same manner as in Example 6 except that the reaction was carried out continuously by downflow. As in Example 6, the conversion of acetone and the sum of bisphenol A and 2,4 ′ isomer were obtained. And the selectivity (%) of the indane compound were calculated. The results are shown in Table 6.

[Example 11]
In Example 6, 80 ° C. warm water was circulated through the jacket portion, and a phenol / acetone mixed solution (phenol / acetone molar ratio 13) having a water content of 0.43% by weight was added from the top of the reactor at 80 ° C. at 3 mL / min. The reaction was carried out in the same manner as in Example 6 except that the reaction was carried out continuously by downflow. As in Example 6, the conversion of acetone and the sum of bisphenol A and 2,4 ′ isomer were obtained. And the selectivity (%) of the indane compound were calculated. The results are shown in Table 6. As is clear from Table 6, it was found that even when the reaction temperature was 75 ° C. and 80 ° C., the selectivity of the indane compound was not affected as compared with the case of reaction at 70 ° C.

DESCRIPTION OF SYMBOLS 1 Droplet production apparatus 2 Aqueous medium 3 Droplet production tank 4 Hydrophobic liquid 5 Hydrophobic liquid storage tank 6 Hydrophobic liquid supply pipe 7 Nozzle member 8 Underwater speaker 9 Aqueous medium storage tank 10 Aqueous medium supply pipe 11 Ejection hole 12 Hydrophobic liquid Jet storage tank 13, 14 Supply pump 15 Droplet 16 Polymerization reactor 17 Polymerization reactor 18 Droplet transfer pipe

Claims (7)

1. A process for producing a bisphenol compound comprising reacting a phenol compound and a carbonyl compound in the presence of a cation exchanger having a strong acid group and 2- (2-mercaptoethyl) pyridine, the reaction comprising the phenol compound and the carbonyl compound A method for producing a bisphenol compound, wherein the concentration of water in the raw material is 0.05 to 0.5% by weight.
2. The cation exchanger having the strong acid group and the 2- (2-mercaptoethyl) pyridine are protected by at least part of the strong acid group of the cation exchanger having the strong acid group by 2- (2-mercaptoethyl) pyridine. The method for producing a bisphenol compound according to claim 1, wherein the method is present as a modified strong acid cation exchanger.
3. 3. The bisphenol compound according to claim 2, wherein the modified strong acid type cation exchanger is such that 3 to 30% of the strong acid group is protected by 2- (2-mercaptoethyl) pyridine. Production method.
4. 4. The cation exchanger having a strong acid group and a modified strong acid cation exchanger having a particle size of 30 to 650 μm are 50% or more of the total, respectively. The manufacturing method of the bisphenol compound as described in claim | item.
5. The method for producing a bisphenol compound according to any one of claims 1 to 4, wherein the amount of the phenol compound relative to the carbonyl compound in the reaction raw material is 10 to 40 times in molar ratio.
6. 6. The phenol compound and the carbonyl compound are reacted at a temperature of 50 to 90 ° C. in the presence of the cation exchanger having a strong acid group and / or a modified strong acid cation exchanger. The manufacturing method of the bisphenol compound in any one of.
7. The method of a bisphenol compound according to any one of claims 1 to 6, wherein the bisphenol compound is bisphenol A.

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