JPH10225638A - Catalyst for producing bisphenol, its preparation and production of bisphenol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of bisphenol from ketones and phenols by using an industrially advantageous heterogeneous catalyst with a high conversion rate and selectively rate. SOLUTION: In a reaction of the ketones and phenols, an org. high molecular siloxane having a sulfonic acid group and a mercapto group in which a silica matrix is formed by hydrolyzing at least one kind selected from a group consisting of an org. sulfonic acid group-containing silane compd. capable of forming high molecular siloxane matrix and an org. sulfonic acid group- containing low molecular siloxane and a mercapto group-containing silane compd. capable of forming the high molecular siloxane matrix, then gelling the obtained mixed sol by subjecting to dehydration and condensation is used as the catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to bisphenols obtained by the dehydration condensation reaction of phenols and ketones, in particular, to bisphenols obtained by the dehydration condensation reaction of phenol and acetone.
2-bis (4'-oxyphenyl) propane (hereinafter abbreviated as bisphenol A) and 4,4 '-(1-phenylethylidene) bisphenol (hereinafter abbreviated as bisphenol AP) by a dehydration condensation reaction between phenol and acetophenone. ), A method for preparing the same, and a method for producing bisphenol.

[0002] Bisphenol A and bisphenol AP are industrially extremely useful compounds such as polycarbonate, polyester, epoxy resin, and raw materials for thermal paper developer. In particular, bisphenol A used for polycarbonate resin is required to be colorless and high in purity.

[0003]

2. Description of the Related Art Bisphenol A is usually produced by a dehydration condensation reaction between two molecules of phenol and one molecule of acetone in the presence of an acid catalyst such as hydrochloric acid. When, for example, hydrochloric acid is used as the homogeneous catalyst, it is possible to react while adducting phenol and bisphenol A by crystallization by operating at a low temperature. Bisphenol A can be produced with '-selectivity. However, a homogeneous catalyst such as hydrochloric acid requires a step of removing or neutralizing the catalyst in the reaction mixture, and the operation becomes complicated. In addition to this, the acid is uniformly dissolved in the reaction solution, causing corrosion of the equipment, etc.
Therefore, it is necessary to use a corrosion-resistant material for the reaction device and the like, which causes environmental and economic problems. For this reason, the production of bisphenol A using a heterogeneous solid catalyst has been industrially carried out.

As the solid heterogeneous catalyst, zeolite, a partially neutralized and insolubilized heteropolyacid salt, a strongly acidic cation exchange resin and the like are known. However, these solid heterogeneous catalysts have low activity and selectivity of both catalysts. As a method for overcoming the low performance of these solid acid catalysts, it has been known that by adding a sulfur-containing compound as a co-catalyst to a reaction system together with an acid catalyst, catalytic activity and reaction selectivity are improved.

[0005] Thiol compounds such as alkyl mercaptans and benzyl mercaptans have long been known as sulfur-containing compounds having an effect of addition. These compounds are homogeneously dissolved in the reaction system, and improve the activity of the acid catalyst and provide high P, P′-selectivity of bisphenol A. Is difficult to separate, which causes problems in the purification of the product. Therefore, a method of immobilizing the thiol compound and avoiding contamination with the product has been studied. For example, in Japanese Patent Publication No. 37-14721, a catalyst in which a mercaptoalkyl alcohol is esterified with a part of an acidic group of a strongly acidic cation exchange resin, and a mercapto compound is immobilized on the cation exchange resin by an ester bond,
In 19953, a catalyst in which a strongly acidic cation exchange resin was partially neutralized with a mercaptoalkylamine and immobilized, and in JP-A-52-19189, a strongly acidic cation exchange resin was partially neutralized with a cyclic mercaptoamine and immobilized by ionic bonding. Catalysts, such as those in which a mercapto amino acid is immobilized by ionic bonding with a cation exchange resin, are known from British Patent No. 1539186. However, catalysts in which a mercapto compound is immobilized on these ion-exchange resins have low heat resistance of the ion-exchange resin itself and tend to be deteriorated. Further, immobilization of the mercapto compound exemplified above is thermally unstable and decomposes and releases. Cheap. As a result, there are the same problems as the above-mentioned disadvantages of the homogeneous acid catalyst and the uniform mercapto compound. Furthermore, the above-mentioned immobilization is due to a reaction with an acid group which is effective as a reaction catalyst, and has a drawback accompanied by a decrease in the amount of acid.

As a method for overcoming these disadvantages, Japanese Patent Application Laid-Open No. 8-208545 proposes an organic polymer siloxane having a sulfonic acid group and a mercapto group. These organic high molecular siloxane catalysts are thermally stable as compared with the above strongly acidic cation exchange resin, and the mercapto compound is also immobilized by siloxane bonds directly in the siloxane matrix without crushing sulfonic acid groups. Therefore, the immobilization is effective and stable.

[0007] Bisphenol AP is usually produced by a dehydration condensation reaction between two molecules of phenol and one molecule of acetophenone in the presence of an acid catalyst such as hydrochloric acid and a sulfur-containing compound. When, for example, hydrochloric acid is used as a homogeneous catalyst, the reactivity of acetophenone is much lower than that of acetone, so that coexistence of a sulfur-containing compound serving as a cocatalyst is an essential condition. As a known method for producing bisphenol AP from acetophenone and phenol, for example, a method of obtaining bisphenol AP with a yield of 86% by a reaction at 75 ° C. for 3 days using hydrogen chloride and methyl mercaptan as catalysts (an Italian patent) 655536), hydrogen chloride and zinc chloride as catalysts at 60 ° C.
A method of obtaining acetophenone conversion 92%, bisphenol AP selectivity 92%, bisphenol AP yield 84.6% by reaction for 2 days (JP-A-61-33136), using hydrogen chloride, zinc chloride and butyl mercaptan as catalysts A method of obtaining an acetophenone conversion rate of 96.5% and a bisphenol AP yield of 87.6% by a reaction at 50 ° C. for 6 hours (JP-A-2-196746), a method using a heteropoly acid and butyl mercaptan as catalysts at 100 ° C. A method of obtaining an acetophenone conversion rate of 88.3% and a bisphenol AP yield of 81.7% by reaction for a time
No. 45039).

However, like bisphenol A, a homogeneous catalyst such as hydrochloric acid requires a step of removing or neutralizing the catalyst in the reaction mixture, and the operation becomes complicated. In addition, the uniform dissolution of the acid in the reaction solution causes corrosion of equipment, etc., and therefore, corrosion-resistant materials must be used for the reaction equipment, etc., causing environmental and economic problems. Therefore, in the case of bisphenol AP, production with a solid heterogeneous catalyst is industrially desirable. However, as described above, there is no report of using a solid heterogeneous catalyst because the reactivity of acetophenone is significantly lower than that of acetone.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing bisphenols by a dehydration condensation reaction between phenols and ketones, wherein an acid component, a mercapto compound and the like are mixed into the product bisphenols. The present invention provides a highly active and highly selective catalyst without decomposing and liberating an acid and a mercapto compound even in a high-temperature reaction, and provides a highly efficient and economical method for producing bisphenols using this catalyst. It is to be.

[0010]

Means for Solving the Problems The present inventors have found that bisphenols, especially bisphenol A, and phenol and acetophenone by dehydration condensation of phenols and ketones in the presence of an acid catalyst by the dehydration condensation of phenols and ketones. Bisphenol A by the dehydration condensation reaction of
In producing P, attention was paid to the advantages of solid acid catalysts, the effectiveness of mercapto compounds and the effect of immobilization of mercapto compounds, and the problem of separation and purification of conventional mercapto compounds in a homogeneous system, in immobilization of mercapto compounds. Overcoming the problem of instability, and further considering the excellent catalytic action of the organic polymer siloxane having a sulfonic acid group and a mercapto group, as a result of intensive studies aimed at improving the catalytic action performance, In producing bisphenols by a dehydration condensation reaction with ketones, at least one selected from the group consisting of organic sulfonic acid group-containing silane compounds and organic sulfonic acid group-containing siloxane oligomers capable of forming a polymeric siloxane matrix as a catalyst And mercapto group-containing silanization capable of forming a polymeric siloxane matrix Of the mixture, or a mixture of these mixtures and a silane compound capable of forming a silica matrix which is a high-molecular siloxane, and then gelling the resulting mixed sol by dehydration condensation to form a silica matrix. By using the formed organic polymer siloxane having sulfonic acid groups and mercapto groups, sulfonic acid groups and mercapto groups can be uniformly and widely dispersed and efficiently immobilized. The present invention was found to be an extremely active catalyst in which elimination of components and cocatalyst components was suppressed, and the present invention was completed.

That is, the present invention relates to 1) at least one selected from the group consisting of an organic sulfonic acid group-containing silane compound and an organic sulfonic acid group-containing low molecular weight siloxane capable of forming a polymer siloxane matrix, A mercapto group-containing silane compound capable of forming a matrix; or 2) at least one selected from the group consisting of an organic sulfonic acid group-containing silane compound and an organic sulfonic acid group-containing low-molecular siloxane capable of forming a polymeric siloxane matrix When the mercapto group-containing silane compound capable of forming a polymeric siloxane matrix of the general _{formula: R a n SiX (4-} n) ( wherein n is 0 or 1 to 3 of an integer, R _a is the number of carbon atoms X is a hydrocarbon group or a fluorine-containing hydrocarbon group of 1 or more and 20 or less, and X is a chlorine atom, a bromine atom, an iodine atom At least one selected from the group consisting of a hydroxyl group and an alkoxy group, and Si represents a silicon atom), and hydrolyze at least one silane compound represented by the following formula: This is a method for preparing a bisphenol-producing catalyst, which is characterized in that an organic polymer siloxane having a sulfonic acid group and a mercapto group is formed into a silica matrix by gelation by condensation.

The present invention also relates to 1) at least one selected from the group consisting of an organic sulfonic acid group-containing silane compound and an organic sulfonic acid group-containing low molecular weight siloxane capable of forming a high molecular siloxane matrix, and a high molecular siloxane matrix. And / or 2) at least one selected from the group consisting of an organic sulfonic acid group-containing silane compound and an organic sulfonic acid group-containing low molecular siloxane that can form a high-molecular siloxane matrix. , and a mercapto group-containing silane compound capable of forming a polymeric siloxane matrix of the general _{formula: R a n SiX (4-} n) ( wherein n is 0 or 1 to 3 of an integer, R _a is C 1 -C X is a hydrocarbon group or a fluorine-containing hydrocarbon group of 20 or less, and X is a chlorine atom, a bromine atom, an iodine atom, At least one selected from the group consisting of an acid group and an alkoxy group, wherein Si represents a silicon atom), and hydrolyzing at least one of the silane compounds represented by the following formula: An object of the present invention is to provide a bisphenol-producing catalyst prepared by a method for forming an organic polymer siloxane having a sulfonic acid group and a mercapto group into a silica matrix by gelation by dehydration condensation.

Further, the present invention provides a process for producing a bisphenol, which comprises reacting a phenol with a ketone in the presence of an organic high molecular siloxane catalyst having a sulfonic acid group and a mercapto group forming the silica matrix. Is the way.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The phenol used in the present invention is a compound (phenol) in which a hydroxy group is directly substituted and bonded to a benzene ring, and substituted phenols having a substituent other than the hydroxy group can also be used. At this time, the substituents other than the hydroxy group are phenols substituted by at most four substituents, preferably phenols having two or less substituents, more preferably one or less.

When the number of substituents other than the hydroxy group is large, the reaction hardly proceeds due to factors such as stericity. When the number of the substituents other than the hydroxy group is 5, the condensation reaction with acetone substantially does not proceed. Does not progress. Here, in the case of phenols having a substituent on the benzene ring other than the hydroxy group, the substituent is not particularly limited, and any substituent can be used as long as it is a substituent that can be generally substituted on the benzene ring. Although there is no problem, specific examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-
Saturated aliphatic hydrocarbon groups such as butyl group, sec-butyl group and tert-butyl group; alicyclic hydrocarbon groups such as cyclopentyl group and cyclohexyl group; and hydrocarbons such as aromatic hydrocarbon groups such as phenyl group and tolyl group. Examples include a hydrogen group, a methoxy group, an ethoxy group, an alkoxy group such as a phenoxy group, a nitro group, an amino group, and a halogen atom. When a plurality of (specifically, 2 or more and 4 or less) benzene rings are substituted with these substituents, these groups may be the same or different.

Further, specific examples of these phenols include unsubstituted phenol, o-, p- and m-
Cresol, o-, p- and m-ethylphenol, o
-, P- and mn-propylphenol, o-, p-
And mi-propylphenol, o-, p- and m-
n-butylphenol, o-, p- and m-sec-butylphenol, o-, p- and m-tert-butylphenol, 2,4-xylenol, 2,6-xylenol, 2,6-di-tert-butylphenol and the like Alkyl-substituted phenols, alicyclic hydrocarbon-substituted phenols such as p-cyclohexylphenol, o- and p-
Aromatic-substituted phenols such as phenylphenol, o- and p-tolylphenols, alkoxy-substituted phenols such as o- and p-anisole, o- and p-ethoxyphenol, o- and p-phenoxyphenol,
Examples include nitrophenols, aminophenols, and chlorophenols. Of course, the present invention is not limited to only these phenols. In the present invention, at least one of these phenols is used.

The ketones used in the present invention are represented by the general formula: R '-(C = O) -R "(wherein R' and R" are each a hydrogen atom or a hydrocarbon having 1 to 10 carbon atoms. And these groups may be the same or different groups, and these groups may have a substituent such as a halogen atom.
-Is a carbonyl group). Specific examples include aldehydes such as formaldehyde and acetaldehyde, alkyl ketones such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-i-butyl ketone and diethyl ketone, cyclohexanone, 2-methylcyclohexanone, and 3-methylcyclohexanone. And the like, aromatic ketones such as acetophenone and benzophenone, and halogen-substituted ketones such as 1,3-dichloroacetone. Of course, the present invention is not limited to only these ketones. In the present invention, at least one of these ketones is used.
Use seeds.

In the present invention, a method is preferred in which the phenol is phenol, the ketone is acetone or acetophenone, and the bisphenol is bisphenol A and bisphenol AP. Further, the purity of these phenols and ketones used in the present invention is not particularly limited, even if it is industrial purity,
Reagent purity can be used. It is of course possible to use highly purified and highly purified products. Moreover,
It is also possible to use the reaction mixture diluted with a medium inert to the reaction, for example, a saturated hydrocarbon.

The catalyst used in the present invention is an organic polymer siloxane having a sulfonic acid group and a mercapto group (SH group) forming a silica matrix. More specifically, at least one selected from the group consisting of an organic sulfonic acid group-containing silane compound and an organic sulfonic acid group-containing low molecular siloxane capable of forming a polymer siloxane matrix, and a mercapto group capable of forming a polymer siloxane matrix A mixture with at least one selected from the group consisting of the contained silane compounds, if necessary, was subjected to a treatment such as hydrolysis to form a mixed sol and further gelled by dehydration condensation to form a silica matrix obtained. It is an organic polymer siloxane having a sulfonic acid group and a mercapto group. At this time, when preparing the mixed sol,
A general formula together with a mixture of at least one selected from the group consisting of the organic sulfonic acid group-containing silane compound and the organic sulfonic acid group-containing low molecular weight siloxane and at least one selected from the group consisting of the mercapto group-containing silane compounds. _{: R a n SiX (4-} n) ( wherein n is 0 or 1 to 3 of an integer, R _a is a hydrocarbon group or a fluorine-containing hydrocarbon group having 1 to 20 carbon atoms, X is Chlorine atom,
At least one selected from the group consisting of a bromine atom, an iodine atom, a hydroxyl group, and an alkoxy group, and Si represents a silicon atom), and sol-gelation and gelation are performed. An organic polymer siloxane having a sulfonic acid group and a mercapto group, which forms a silica matrix obtained by the above, may be used. In some cases, the latter preparation method is a preferable catalyst from the viewpoint of the stability of the silica matrix and the like.

The organic sulfonic acid group-containing silane compound capable of forming a high molecular siloxane matrix used in the present invention has an organic sulfonic acid group directly bonded to a silicon atom, and can be used alone or in ethyl silicate, It is a silane compound which can be solidified by a usual sol-gel reaction as a mixture of silane compounds such as silicon tetrachloride to form a gel-like substance. The organic sulfonic acid group-containing low molecular weight siloxane is a siloxane compound in which two or more molecules of the above organic sulfonic acid group-containing silane compound form a siloxane bond by hydrolysis. The low-molecular siloxane referred to here is a siloxane compound that gels even when siloxane bonds are formed and does not solidify. Usually, two or more molecules of the above-mentioned organic sulfonic acid group-containing silane compound
It is a siloxane formed by several tens of molecules. Also, silica sol before gelation is included. Preferably, the organic sulfonic acid group-containing silane compound is a siloxane formed with 10 molecules or less, but is not particularly limited in the present invention, and may be a siloxane that maintains a uniform state or a sol state in a solvent. I don't mind.

[0021] Specifically, as an organic sulfonic acid group-containing silane compound capable of forming a polymeric siloxane matrix have the general _{formula: R b n SiX (4-} n) (n in the formula is 1 to 3 integer , R _b is a hydrocarbon group having 1 to 15 carbon atoms having at least one sulfonic acid group, and X
Is at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group and an alkoxy group,
Si represents a silicon atom).

The organic sulfonic acid group-containing low molecular weight siloxane is defined as an organic sulfonic acid group-containing silane compound represented by the general formula: R _{b n} SiX _(4-n) in which each Si—X bond is a Si—oxygen bond. To form a Si—O—Si— bond (siloxane bond) and is soluble in water or an organic solvent. For example, when formed from two molecules of the silane compound, the general formula: (X _{(3-n ')} ) ( _Rb ) _n 'S
i-O-Si ( _Rb ) _{n '} (X _(3-n') ) (wherein n 'is an integer of 1 or more and 2 or less, and _Rb is a carbon atom having at least one or more sulfonic acid group. X is at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group and an alkoxy group, and Si represents a silicon atom. Siloxane. In the present invention, at least one of these silane compounds and siloxane compounds is used.

In the present invention, the organic sulfonic acid group-containing silane compound capable of forming the siloxane matrix and the method for preparing an organic sulfonic acid group-containing low molecular weight siloxane formed from these silane compounds are not particularly limited in the present invention. Any method can be used as long as the above silane compound or siloxane is obtained, but it can be prepared, for example, by the following method.

The organic high molecular siloxane containing an organic sulfonic acid group is hydrolyzed, for example, by contact with water in the presence of an acid to dissolve the solid to form an aqueous solution. According to this method, in an aqueous solution, for example, if the organic sulfonic acid group is an organic sulfonic acid group represented by R _b in the above general formula, the general formula: R _{b n} Si (OH) _(4-n) (where n is 1 Above 3
A silane compound represented by the following integer, wherein R _b is a hydrocarbon group having 1 to 15 carbon atoms having at least one sulfonic acid group, OH is a hydroxyl group, and Si represents a silicon atom. Dissolves as Of course, from the group consisting of a silane compound represented by the general formula: R _{b n} Si (OH) _(4-n) and a water-soluble organic sulfonic acid group-containing low-molecular siloxane compound condensed with the silane compound depending on acidic conditions and the like. It is obtained as at least one selected aqueous solution. The obtained aqueous solution is used for preparing the catalyst of the present invention after concentrating and removing water, if necessary.

The general formula: R_c nSix_(4-n)(In the formula
n is an integer of 1 or more and 3 or less;_c Is 1 or more and 1 carbon
X is a chlorine atom, a bromine atom,
Select from the group consisting of iodine atom, hydroxyl group and alkoxy group
Si is a silicon atom.
By sulfonating the silane compound represented by
Preparation of organic sulfonic acid group-containing silane compounds
Can also be. In addition, in this method, no solvent or solvent
SO in the presence_ThreeCarbon and water of hydrocarbon group
SO between elementary bonds_ThreeAnd insert at least one
A silane compound having a phonic acid group can be obtained. Must
If necessary, after isolation and purification by distillation or the like, the present invention
Used in the preparation of catalysts in R_cAs an alkyl
Group, aromatic group, etc., and the aromatic group is a phenyl group
There is.

In the present invention, at least one selected from the group consisting of an organic sulfonic acid group-containing silane compound and an organic sulfonic acid group-containing low molecular siloxane capable of forming a high molecular siloxane matrix obtained by the above-mentioned method, A mixture with at least one selected from the group consisting of mercapto group-containing silane compounds capable of forming a molecular siloxane matrix, or a mixture of these with a general formula:
_{R a n SiX (4-n} ) ( wherein n is 0 or 1 to 3 of an integer, R _a is a hydrocarbon group or a fluorine-containing hydrocarbon group having 1 to 20 carbon atoms, X is chlorine At least one selected from the group consisting of an atom, a bromine atom, an iodine atom, a hydroxyl group and an alkoxy group, and Si represents a silicon atom). By gelation of the mixed sol obtained by dehydration condensation by dehydration, an organic polymer siloxane having a sulfonic acid group and a mercapto group forming a silica matrix can be prepared.

Examples of _Ra include an alkyl group, an aromatic group, a fluorinated alkyl group and a fluorinated aromatic group.
The organic sulfonic acid group includes an alkylsulfonic acid group and an aromatic sulfonic acid group. The aromatic sulfonic acid group includes a phenylsulfonic acid group.

As the silane compound containing a mercapto group,
General _{formula: R d n SiX (4-} n) ( wherein n is 1 to 3 an integer, R _d is at least 1 having 1 to 15 carbon atoms
X is a hydrocarbon group having at least one mercapto (SH) group as a substituent, X is at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group and an alkoxy group, and Si is a silicon atom Represents a silane compound).

R _d represents a mercaptomethyl group, a 2-mercaptoethyl group, a 3-mercapto-n-propyl group, a 4-mercapto-n-butyl group, a p-mercaptophenyl group and a p-mercaptomethylphenyl group. At least one selected from the group consisting of:

Here, the mixed gelation in the present invention will be described. The mixed gelation in the present invention is sufficiently achieved by a usual mixed sol-gel reaction. Specific examples of the mixed gelation method that is easy to carry out include a silane compound having an organic sulfonic acid group or an organic sulfonic acid group-containing low-molecular-weight siloxane as an acid component of a catalyst and a mercapto component as a mercapto component as a co-catalyst. the group-containing silane compound, a solid acid amount of the solid catalyst of interest were charged amount calculated from the mercapto amount, the general formula as component to further stabilize the silica _{matrix: R a n SiX (4- n} ) ( wherein n is 0 or an integer of 1 to 3, _Ra is a hydrocarbon group having 1 to 20 carbon atoms or a fluorinated hydrocarbon group, and X is a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group and an alkoxy group. At least one selected from the group consisting of
Is mixed with at least one silane compound represented by the following formula (Si represents a silicon atom), and if necessary, a uniform mixed solution is prepared using a solvent such as ethanol. After adding half the amount of water to the hydrolyzable groups, heat and stir,
Concentrate under acidic conditions. The obtained high viscosity liquid is generally called silica sol. Also at this time,
The dispersibility of a specific component in a silica matrix can also be changed by, for example, previously forming a component or more components into a sol and then forming a sol with the remaining components.

To the above-mentioned sol, an excess amount of water, aqueous ammonia, etc. with respect to the amount of hydrolyzable groups are added, and the mixture is gelled under basic conditions. At this time, if necessary, the mixture may be heated and stirred to ripen it for a long time. In carrying out the gelation, the gelation may be carried out by diluting in a medium such as an alcohol or an aliphatic saturated hydrocarbon (hexane, heptane, etc.) which is inert to the sol.

The obtained gel can be isolated by filtration or distilling off the solvent. Since the sulfonic acid of this gel is of the ammonium salt type or the like, it must be returned to the acid form by acid treatment in order to use it as a solid acid catalyst. In the present invention, the amount of sulfonic acid and the amount of mercapto at the time of charging are not particularly limited, but are preferably milligram equivalent (meq / g: mmol of functional group per 1 g of solid catalyst).
It is recommended that the number is 0.05 to 5, preferably 0.3 to 3 milligram equivalents. Of course, the present invention is not limited to only these ranges.

Further, X in each of the above general formulas represents at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom and an alkoxy group. A group that makes it possible to create molecular siloxane bonds. Specifically, as an alkoxy group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-
Examples thereof include an alkyl alkoxy group such as a butoxy group, a sec-butoxy group and a t-butoxy group, and an aromatic alkoxy group such as a phenoxy group and a naphthoxy group. The present invention is not limited only to these alkoxy groups, and may be a mixture of these substituents.

The amounts (quantity ratio) of the phenols and ketones used as raw materials are not particularly limited, but are preferably in the range of 0.1 to 100 in terms of the phenols / ketone molar ratio, and more preferably 0.5 to 100. It is encouraged to practice in the range of 50. If the amount of phenols is too small, it is difficult to achieve a high conversion of the raw material ketone, and if the amount of phenols is too large, it is possible to achieve a high conversion of ketones, but the phenols may be more than necessary. This is because the use of phenols causes the reactor to be excessively large and requires a large amount of phenols to be circulated, which prevents efficient production.

The reaction temperature is not particularly limited in the present invention, but is preferably in the range of 0 to 300 ° C, more preferably 30 to 200 ° C. If the reaction temperature is too low, an extremely long reaction time is required to achieve a high conversion of the raw materials, in other words, the reaction rate is extremely reduced, and the productivity of the reaction product is reduced. On the other hand, if the reaction temperature is extremely high, undesired side reactions and the like proceed, and the increase in by-products and the stability of the starting materials, such as phenols and ketones, and the bisphenols as the products, are also unfavorable. , Resulting in lower reaction selectivity and not economical.

The reaction can be carried out under any of reduced pressure, increased pressure and normal pressure. From the viewpoint of reaction efficiency (reaction efficiency per unit volume), it is not preferable to perform the reaction at a pressure that is too low. A normally preferred working pressure range is 0.1 to 200 atm, more preferably 0.5 to 200 atm.
~ 100 atm. Of course, the invention is not limited to these pressure ranges.

In carrying out the present invention, the amount of the catalyst to be used is not particularly limited. For example, when the reaction is carried out in a batch system, preferably, the amount of the catalyst is 0.001% by weight based on the phenol as a raw material. It is recommended to carry out in a range of from about 200%, more preferably from 0.1 to 50%. Using too small amounts of organic polymeric siloxane catalysts with organic sulfonic acids and mercapto groups,
This is because the reaction speed is substantially lowered to cause a problem in efficiency, and if used in an excessively large amount, the stirring efficiency of the reaction solution or the like may be lowered and a trouble may be caused.

In carrying out the present invention, it is also possible to add a solvent or gas inert to the catalyst and the reaction reagent into the reaction system and dilute the reaction system. Specifically, methane, ethane, propane, butane, hexane,
Aliphatic hydrocarbons such as cyclohexane, inert gases such as nitrogen, argon and helium, and in some cases hydrogen can also be used as a diluent.

In carrying out the present invention, the method can be carried out in any of a batch system, a semi-batch system, and a continuous flow system. The reaction can be carried out in any of a liquid phase, a gas phase and a gas-liquid mixed phase using an organic polymer siloxane having an organic sulfonic acid group and a mercapto group as a solid catalyst. Preferably, it is recommended to carry out a liquid phase reaction from the viewpoint of reaction efficiency. Various methods such as a fixed bed, a fluidized bed, a suspension bed, and a fixed bed with a fixed shelf are employed as a method for filling the organic high molecular siloxane having an organic sulfonic acid group and a mercapto group. Absent.

The reaction time (residence time or catalyst contact time in a flow reaction) is not particularly limited.
It is usually 0.1 second to 30 hours, preferably 0.5 second to 15 hours. After the reaction, the reaction product is filtered from the catalyst or the like,
It can be separated and recovered by a separation method such as extraction and distillation. Bisphenols, which are the target products, are separated and separated from the recovered product, and a normal separation and purification method such as a sequential processing method such as solvent extraction, distillation, alkali treatment, or acid treatment, or an operation in which these are appropriately combined. Can be separated and purified to obtain. Further, the unreacted raw material can be recovered and recycled to the reaction system again.

In the case of a batch reaction, the catalyst recovered by separating the reaction product after the reaction can be used again as it is, or after regenerating part or all of the catalyst, and repeatedly. When the reaction is carried out in a fixed-bed or fluidized-bed flow reaction system, the reaction is suspended by suspending the reaction if a part or all of the catalyst is deactivated or reduced in activity, and then the catalyst is regenerated and subjected to the reaction. Alternatively, a part thereof can be continuously or intermittently extracted, regenerated, recycled to the reactor, and reused. Further, new catalyst can be supplied to the reactor intermittently. When the reaction is carried out in a moving bed type flow reaction, the catalyst can be separated and recovered in the same manner as in the batch reaction, and if necessary, regenerated and used.

[0042]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to only these examples. (A) Production of Acid Component-Containing Raw Material Aqueous Solution 200 ml of methylene chloride was placed in a two-necked 500 ml round bottom flask equipped with a dropping funnel, and liquid S was added thereto.
46.80 g (0.585 mol) of O ₃ was dissolved. The flask was cooled with ice and 124.02 g (0.585 mol) of trichlorophenylsilane was added dropwise over 30 minutes under nitrogen, and then the ice bath was removed and the mixture was stirred at room temperature for several hours. After removing the dropping funnel, use an oil bath at 120 ° C.
For several hours under normal pressure to distill off methylene chloride and unreacted SO ₃ . After cooling, cool on ice and add 200 g of water for 30 minutes.
Then, the mixture was refluxed for several hours while bubbling nitrogen through to remove generated hydrogen chloride. The obtained reaction solution was distilled off under normal pressure, and then heated at 100 ° C. under reduced pressure for several hours to dryness. 31.59 g of water (1.75 g) was added to this solid.
(5 mol) was completely dissolved. 114.9 g of an aqueous solution of phenylsulfonic acid group-containing hydroxysilane containing impurities such as phenylhydroxysilane was used as an aqueous solution of an acid component-containing raw material for preparing a catalyst.

(B) Production of an Ethanol Solution Containing an Acid Component 200 ml of methylene chloride was placed in a two-necked 500 ml round-bottomed flask equipped with a dropping funnel.
46.80 g (0.585 mol) of O ₃ was dissolved. The flask was cooled with ice and 124.02 g (0.585 mol) of trichlorophenylsilane was added dropwise over 30 minutes under nitrogen, and then the ice bath was removed and the mixture was stirred at room temperature for several hours. After removing the dropping funnel, use an oil bath at 120 ° C.
For several hours under normal pressure to distill off methylene chloride and unreacted SO ₃ . After cooling, dry ethanol 16 at room temperature
1.50 g was added dropwise over 30 minutes, and then refluxed for several hours while bubbling nitrogen through to remove generated hydrogen chloride. 238.60 g of an ethanol solution of phenylsulfonic acid group-containing ethoxysilane containing impurities such as unreacted phenylethoxysilane and the like was used as an acid component-containing raw material ethanol solution for catalyst preparation.

Example 1 In a two-necked 500 ml round bottom flask equipped with a stir bar, 12.52 g of the above aqueous solution containing an acid component, 35.50 g (170.67 mmol) of tetraethoxysilane, and 6.72 g of mercaptopropyltrimethoxysilane. (34.
28 mmol) and 30 ml of ethanol were added and mixed. To this, 7.53 g (0.418 mol) of water was added dropwise over 30 minutes. It was then heated and stirred at 80 ° C. for several hours. This was allowed to cool, 30 ml of ethanol and 20 ml of n-hexane were added and mixed. Further, a mixture of 15 ml of 28% ammonia water and 75 ml of water was added dropwise,
Stirred at room temperature for 4 hours. This was distilled off under reduced pressure using an evaporator to obtain a white solid. Next, 200 ml of 2N hydrochloric acid was added, and the mixture was stirred at room temperature for 1 hour to return to a proton type. After being thoroughly washed with a large amount of pure water, it was dried under reduced pressure to obtain 29.00 g of an organic polymer siloxane catalyst having a sulfonic acid and a mercapto group (referred to as catalyst 1). It was 0.80 meq / g as a result of measuring the solid acid amount of this catalyst. From this solid acid amount, the total content of sulfonic acid in the acid component-containing raw material aqueous solution was 23.17 mmol,
The yield of sulfonation of phenylsilane with SO ₃ was calculated to be 46.5%.

Example 2 Into a two-necked 500 ml round bottom flask equipped with a stirring rod, 26.00 g of the above-mentioned acid component-containing raw material ethanol solution and 35.50 g of tetraethoxysilane (170.67 mmol)
l), mercaptopropyltrimethoxysilane 6.72
g (34.28 mmol) and 30 ml of ethanol were added and mixed. 7.53g of water (0.418mo
l) was added dropwise over 30 minutes. Then it is heated, 8
Stirred at 0 ° C. for several hours. This is left to cool and ethanol 30
ml and 20 ml of n-hexane were added and mixed. Further, a mixture of 15 ml of 28% aqueous ammonia and 75 ml of water was added dropwise, and the mixture was stirred at room temperature for 4 hours. This was distilled off under reduced pressure using an evaporator to obtain a white solid. Next, 200 ml of 2N hydrochloric acid was added, and the mixture was stirred at room temperature for 1 hour to return to a proton type. After being thoroughly washed with a large amount of pure water, it was dried under reduced pressure to obtain 30.00 g of an organic polymer siloxane catalyst having a sulfonic acid and a mercapto group (referred to as catalyst 2). As a result of measuring the amount of solid acid of the present catalyst, 1.01 meq /
g. From this solid acid amount, the total content of sulfonic acid in the above-mentioned acid component-containing raw material ethanol solution was 30.24 mm
It was found that the yield of sulfonation of phenylsilane with SO ₃ was 47.4%.

Example 3 Into a two-necked 500 ml round bottom flask equipped with a stirring rod, 26.00 g of the above-mentioned acid component-containing raw material ethanol solution and 17.75 g of tetraethoxysilane (85.34 mmol)
l), 16.39 g of ethyltriethoxysilane (85.
34 mmol) 6.72 g (34.28 mmol) of mercaptopropyltrimethoxysilane, 30 m of ethanol
1 and mixed. 7.53 g of water (0.418
mol) was added dropwise over 30 minutes. It was then heated and stirred at 80 ° C. for several hours. This was allowed to cool, 30 ml of ethanol and 20 ml of n-hexane were added and mixed.
Further, a mixture of 15 ml of 28% aqueous ammonia and 75 ml of water was added dropwise, and the mixture was stirred at room temperature for 4 hours. This was distilled off under reduced pressure using an evaporator to obtain a white solid. Then 2N
Hydrochloric acid (200 ml) was added and the mixture was stirred at room temperature for 1 hour to return to the proton form. After thoroughly washing with a large amount of pure water, drying is performed under reduced pressure, and an organic polymer siloxane catalyst having a sulfonic acid, an ethyl group and a mercapto group (referred to as catalyst 3) 4
1.79 g were obtained. As a result of measuring the solid acid amount of this catalyst, it was 0.79 meq / g.

Example 4 In a two-necked 500 ml round bottom flask equipped with a stirring rod, 26.00 g of the above-mentioned acid component-containing raw material ethanol solution and 17.75 g of tetraethoxysilane (85.34 mmol)
l), 16.39 g of ethyltriethoxysilane (85.
34 mmol) 6.72 g (34.28 mmol) of mercaptopropyltrimethoxysilane, 30 m of ethanol
1 and mixed. 7.53 g of water (0.418
mol) was added dropwise over 30 minutes. It was then heated and stirred at 80 ° C. for several hours. This was allowed to cool, 30 ml of ethanol and 20 ml of n-hexane were added and mixed.
Further, a mixture of 15 ml of 28% aqueous ammonia and 75 ml of water was added dropwise, and the mixture was stirred at room temperature for 4 hours.
For several days and aged well. This was distilled off under reduced pressure using an evaporator to obtain a white solid. Then 2N hydrochloric acid 2
After adding 00 ml, the mixture was stirred at room temperature for 1 hour and returned to the proton type. After washing well with a large amount of pure water, dry under reduced pressure,
Organic polymer siloxane catalyst having sulfonic acid, ethyl group and mercapto group (referred to as catalyst 4) 41.80
g was obtained. 0.77 m as a result of measuring the solid acid content of the catalyst
eq / g.

Example 5 Into a two-necked 500 ml round bottom flask equipped with a stirring rod, 26.00 g of the above-mentioned acid component-containing ethanol solution and 16.39 g of ethyltriethoxysilane (85.34 mmol)
l), 30 ml of ethanol was added and mixed. To this, 3.77 g (0.21 mol) of water was added dropwise over 30 minutes. The mixture was further stirred at room temperature for 1 hour, hydrolyzed first, and then 17.75 g of tetraethoxysilane (85.34 m
mol), mercaptopropyltrimethoxysilane6.
72 g (34.28 mmol) were added, and water 3.7 was added thereto.
7 g (0.21 mol) was added dropwise over 30 minutes. It was then heated and stirred at 80 ° C. for several hours. This was allowed to cool, 30 ml of ethanol and 20 ml of n-hexane were added and mixed. Further, a mixture of 15 ml of 28% aqueous ammonia and 75 ml of water was added dropwise, and the mixture was stirred at room temperature for 4 hours, further stirred at 80 ° C. for several days, and aged sufficiently. This was distilled off under reduced pressure using an evaporator to obtain a white solid. Next, 200 ml of 2N hydrochloric acid was added, and the mixture was stirred at room temperature for 1 hour.
Returned to the proton form. After washing well with a large amount of pure water,
It was dried under reduced pressure to obtain 41.79 g of an organic polymer siloxane catalyst having sulfonic acid, an ethyl group and a mercapto group (referred to as catalyst 5). It was 0.80 meq / g as a result of measuring the solid acid amount of this catalyst.

Example 6 In a two-necked 500 ml round bottom flask equipped with a stirring rod, 26.00 g of the above-mentioned acid component-containing ethanol solution and 16.39 g of ethyltriethoxysilane (85.34 mmol)
l), 30 ml of ethanol was added and mixed. To this, 3.77 g (0.21 mol) of water was added dropwise over 30 minutes. After further stirring at 80 ° C. for several hours, the mixture was allowed to cool, and 17.75 g (85.34 mmol) of tetraethoxysilane was added.
6.72 g of mercaptopropyltrimethoxysilane (3
4.28 mmol) and 3.77 g of water (0.
21 mol) was added dropwise over 30 minutes. It was then heated and stirred at 80 ° C. for several hours. This was allowed to cool, 30 ml of ethanol and 20 ml of n-hexane were added and mixed. Further, a mixture of 15 ml of 28% aqueous ammonia and 75 ml of water was added dropwise, and the mixture was stirred at room temperature for 4 hours.
The mixture was stirred at 0 ° C. for several days and aged well. This was distilled off under reduced pressure using an evaporator to obtain a white solid. Next, 200 ml of 2N hydrochloric acid was added, and the mixture was stirred at room temperature for 1 hour to return to a proton type. After thoroughly washing with a large amount of pure water, drying under reduced pressure, an organic polymer siloxane catalyst having a sulfonic acid, an ethyl group and a mercapto group (referred to as catalyst 6) 41.
79 g were obtained. As a result of measuring the solid acid content of the catalyst, 0.7
It was 8 meq / g.

Example 7 291.6 g of tetraethoxysilane (1.402 mol) was placed in a two-necked 1000 ml round bottom flask equipped with a stirring rod.
l), 144.68 g of phenyltriethoxysilane
(0.600 mol) and 200 ml of ethanol,
Stir at room temperature for 1 hour and mix well. 0.01N
Was added dropwise over 1 hour. Then, the mixture was stirred at an internal temperature of 78 ° C. for 20 hours in an open system and concentrated. This was allowed to cool to room temperature, and ethanol 120 ml, n-hexane 18
0 ml was added, and the mixture was stirred at room temperature for 1 hour and mixed well. A mixture of 100 ml of 28% aqueous ammonia and 540 ml of water was added dropwise over 1 hour. The mixture was further stirred at room temperature for 4 hours. The obtained white suspension was filtered, and the white matter was washed with a large amount of pure water and then dried in a hot air drier at 100 ° C. for one day. The organic polymer siloxane having a phenyl group in the silica matrix thus obtained is 146.7.
0 g is placed in a 2000 ml round bottom flask and concentrated sulfuric acid 14
Then, the mixture was heated and stirred at 80 ° C. for 6 hours to sulfonate. After the reaction, the reaction solution was allowed to cool to room temperature, and 4000 ml of water was carefully added for dilution. This was filtered, and the obtained white matter was washed with a large amount of pure water. 100 ℃ in hot air dryer
For 1 day. Organic polymer siloxane 14 having phenylsulfonic acid groups in the obtained silica matrix
As a result of measuring the amount of 4.0 g of solid acid, 0.60 meq /
g.

143.0 g of the above organic polymer siloxane having a phenylsulfonic acid group (solid acid amount: 0.60 m
eq / g) was placed in a 1500 ml round bottom flask, and 1000 ml of pure water was added. The mixture was refluxed for 24 hours, allowed to cool, and filtered. The weight of the filtered white matter was 130.81.
g, the solid acid amount was reduced to 0.48 meq / g. The obtained filtrate was concentrated to obtain 25.59 g of a colorless transparent liquid. When calculated from the decrease in the amount of solid acid, 2
This means that 3.01 mmol of the low-molecular-weight siloxane having a phenylsulfonic acid group is dissolved.

In a two-necked 500 ml round bottom flask equipped with a stirring rod, 6.40 g of the above-mentioned aqueous solution containing a phenylsulfonic acid group and 12.13 g of tetraethoxysilane.
(58.32 mmol), 4.63 g (23.50 mmol) of mercaptopropyltrimethoxysilane, and 10 ml of ethanol were added and mixed. Then heat it,
Stirred at 80 ° C. for several hours. Allow it to cool and add ethanol 1
5 ml and n-hexane 5 ml were added and mixed. Further, a mixture of 5 ml of 28% aqueous ammonia and 25 ml of water was added dropwise, and the mixture was stirred at room temperature for 4 hours. This was distilled off under reduced pressure using an evaporator to obtain a white solid. Then 2N hydrochloric acid 2
After adding 00 ml, the mixture was stirred at room temperature for 1 hour and returned to the proton type. After washing well with a large amount of pure water, dry under reduced pressure,
8.01 g of a polymer siloxane catalyst having a sulfonic acid and a mercapto group (referred to as catalyst 7) was obtained. As a result of measuring the amount of solid acid of this catalyst, it was 0.70 meq / g.

Examples 8 to 14 3.80 g (65.4) of acetone was placed in a 70 ml pressure-resistant reactor.
3mmol), 33.00 g of phenol (350.65)
mmol) and 2.00 g of any of catalysts 1 to 7 were charged, and the inside of the pressure-resistant reactor was pressurized to 5 kg / cm ² gauge pressure with nitrogen gas, followed by heating and stirring at 100 ° C. for 2 hours to carry out a reaction. After completion of the reaction, the reaction solution was cooled to room temperature. After releasing the pressure, the reaction solution was taken out and analyzed and quantified by liquid chromatography. As a result, as shown in Table 1, bisphenol A was produced in good yield.

Example 15 The reaction was carried out under the same conditions as in Example 8 except that the amount of acetone charged was 1.90 g. As a result, as shown in Table 1, bisphenol A was produced in a high yield based on acetone.

Example 16 The reaction was carried out under the same conditions as in Example 8 except that the reaction temperature was 120 ° C. and the reaction time was 1 hour. Table 1 shows the results
As shown in Table 2, bisphenol A was produced in high yield.

Example 17 After the reaction, the catalyst 4 used in Example 11 was taken out by filtration, and the raw materials were again charged and reacted under the same conditions. The results indicated that bisphenol A was formed as shown in Table 1, and the catalyst did not deteriorate by use.

[0057]

[Table 1] Table 1 収率 Product yield (based on charged acetone) %) {Catalyst p, p'-BPA o, p'-BPA COD} ────────────────────────── Example 8 165.0% 2.4% 0.1% Example 9 265.0% 2.4% 0.1% Example 10 3 70.0% 2.3% 0.1% Example 11 4 70.1% 2.5% 0.1% Example 12 5 73.4% 2. 4% 0.2% Example 13 6 72.7% 2.3% 0.1% Example 14 7 45.0% 2.4% 0.2% Example 15 1 92.0% 3.5% 0.3% Example 16 1 75.4% 3.9% 0.1% Example 17 4 69.2% 2.5% 0 1% ────────────────────────────────────p, p'-BPA: 2,2-bis (4'-oxyphenyl) propane o, p'-BPA: 2- (2'-oxyphenyl) -2- (4'-oxyphenyl) propane (isomer) COD: 2,2,4-trimethyl-4 -(4'-oxyphenyl) chroman (reaction by-product)

Example 18 In a two-necked 500 ml round bottom flask equipped with a stirring rod, 12.52 g of the above aqueous solution containing an acid component, 17.75 g (85.34 mmol) of tetraethoxysilane, and 16.73 g of mercaptopropyltrimethoxysilane. (85.
34 mmol) and 30 ml of ethanol were added and mixed. To this, 7.53 g (0.418 mol) of water was added dropwise over 30 minutes. It was then heated and stirred at 80 ° C. for several hours. This was allowed to cool, 30 ml of ethanol and 20 ml of n-hexane were added and mixed. Further, a mixture of 15 ml of 28% ammonia water and 75 ml of water was added dropwise,
Stirred at room temperature for 4 hours. This was distilled off under reduced pressure using an evaporator to obtain a white solid. Next, 200 ml of 2N hydrochloric acid was added, and the mixture was stirred at room temperature for 1 hour to return to a proton type. After being thoroughly washed with a large amount of pure water, it was dried under reduced pressure to obtain 29.50 g of an organic polymer siloxane catalyst having a sulfonic acid and a mercapto group (referred to as catalyst 8). It was 0.77 meq / g as a result of measuring the solid acid amount of this catalyst.

Example 19 In a 70 ml pressure-resistant reactor, 7.80 g of acetophenone (6
5.00 mmol), 33.00 g of phenol (35
0.65 mmol), 2.00 g of Catalyst 1 was charged, and 10
The mixture was heated and stirred at 0 ° C. for 3 hours to carry out a reaction. After completion of the reaction, the reaction solution was cooled to room temperature. After releasing the pressure, the reaction solution was taken out and analyzed and quantified by liquid chromatography. As a result, as shown in Table 2, bisphenol AP was produced in good yield.

Example 20 7.80 g of acetophenone (6.
5.00 mmol), 33.00 g of phenol (35
0.65 mmol), 2.00 g of catalyst 8, and 10
The mixture was heated and stirred at 0 ° C. for 3 hours to carry out a reaction. After completion of the reaction, the reaction solution was cooled to room temperature. After releasing the pressure, the reaction solution was taken out and analyzed and quantified by liquid chromatography. As shown in Table 2, as the amount of mercapto was increased, bisphenol AP was produced in a very good yield.

Comparative Example 1 7.80 g of acetophenone (6
5.00 mmol), 33.00 g of phenol (35
0.65 mmol), and phosphotungstic acid (H ₃ PW ₁₂ O ₄₀ ) heated at 350 ° C. for 3 hours to remove water of crystallization.
Then, 0.12 g of mercaptopropionic acid was added, and the mixture was heated and stirred at 100 ° C. for 3 hours to carry out a reaction. After completion of the reaction, the reaction solution was cooled to room temperature. After releasing the pressure, the reaction solution was taken out and analyzed and quantified by liquid chromatography. The results are shown in Table 2.

[0062]

[Table 2] Table 2 収率 Product yield (based on acetophenone charged) %) 触媒 Catalyst acetophenone conversion rate Bisphenol AP ─────────────────────── Example 19 1 38.0% 35.0% Example 20 8 65.0% 57.1% Comparative Example 1 40.0% 36.4% ──────────────────────────────────

[0063]

According to the present invention, the following effects can be obtained. (1) Bisphenols can be produced with good yield and selectivity by a dehydration condensation reaction between ketones and phenols. (2) Bisphenol A, which is industrially important, can be produced with remarkably superior safety, process and economy. (3) Bisphenol AP, which is industrially important,
It can be produced with significant process and economic advantages. As described above, the present invention can provide a method for producing bisphenol which is industrially remarkably excellent.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hirofumi Ino 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside of Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Shinobu Aoki 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical (72) Inventor Takashi Terashima 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Shuichi Tokumoto 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. 72) Inventor Kazuaki Matsui 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside of Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Kazuo Takamura 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Toatsu Chemical Co., Ltd.

Claims (20)

[Claims] 1. A polymer siloxane matrix is formed with at least one selected from the group consisting of an organic sulfonic acid group-containing silane compound and an organic sulfonic acid group-containing low molecular siloxane capable of forming a polymer siloxane matrix. And / or 2) at least one selected from the group consisting of an organic sulfonic acid group-containing silane compound and an organic sulfonic acid group-containing low molecular siloxane capable of forming a polymeric siloxane matrix, and a mercapto group-containing silane compound capable of forming a siloxane matrix of the general formula: R _{a n} Si
X _(4-n) (where n is 0 or an integer of 1 or more and 3 or less, _Ra is a hydrocarbon group having 1 or more and 20 or less carbon atoms or a fluorinated hydrocarbon group, and X is a chlorine atom or a bromine. At least one selected from the group consisting of an atom, an iodine atom, a hydroxyl group and an alkoxy group, and Si represents a silicon atom.)
An organic polymer having a sulfonic acid group and a mercapto group, which forms a silica matrix by hydrolyzing at least one silane compound represented by the following formula, and then gelling by subjecting the obtained mixed sol to dehydration condensation. A method for preparing a catalyst for producing bisphenol, characterized by using siloxane. 2. The organic sulfonic acid group-containing low molecular siloxane is a water-soluble organic sulfonic acid group-containing low molecular siloxane obtained by hydrolysis of an organic sulfonic acid group-containing organic high molecular siloxane. the method of. 3. An organic sulfonic acid group-containing silane compound capable of forming a polymer siloxane matrix has a general formula: R
_{b n} SiX _(4-n) (where n is an integer of 1 or more and 3 or less,
R _b is a hydrocarbon group having 1 or more and 15 or less carbon atoms having at least one sulfonic acid group, and X is at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group and an alkoxy group. in it, Si is a silane compound represented by represents a silicon atom), an organic sulfonic acid group-containing low molecular weight siloxanes general formula: R _{b n} SiX
_(4-n) a siloxane compound containing an organic sulfonic acid group that is soluble in water or an organic solvent, wherein two or more molecules of the silane compound are substituted with at least one of X in each molecule to form a siloxane bond. Item 7. The method according to Item 1. 4. The method according to claim 1, wherein the hydrocarbon group is an alkyl group. 5. The method according to claim 1, wherein the hydrocarbon group is an aromatic group.
The described method. 6. The method according to claim 1, wherein the fluorinated hydrocarbon group is a fluorinated alkyl group. 7. The method according to claim 1, wherein the fluorinated hydrocarbon group is a fluorinated aromatic group. 8. The method according to claim 1, wherein the organic sulfonic acid group is an alkyl sulfonic acid group. 9. The method according to claim 1, wherein the organic sulfonic acid group is an aromatic sulfonic acid group. 10. The method according to claim 9, wherein the aromatic sulfonic acid group is a phenylsulfonic acid group. 11. The organic sulfonic acid group-containing silane compound has the general _{formula: R c n SiX (4-} n) ( wherein n is 1 to 3 an integer, R _c is a 1 to 15 carbon atoms X is a hydrocarbon group, and X is at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group and an alkoxy group, and Si represents a silicon atom. The method according to claim 1, which is obtained by performing 12. The sulfonation is carried out according to the general formula: R _{c n} SiX
_{(4-n) (n} in the formula is 1 to 3 an integer, R _c Is a hydrocarbon group having 1 to 15 carbon atoms, X is at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group and an alkoxy group, and Si represents a silicon atom). The method according to claim 11, which is carried out by bringing the represented silane compound into contact with SO _{3 in the} absence or presence of a solvent. 13. The method according to claim 11, wherein R _c is an aromatic group. 14. The method according to claim 13, wherein the aromatic group is a phenyl group. 15. Mercapto group-containing silane compound has the general _{formula: R d n SiX (4-} n) ( wherein n is 1 to 3 an integer, R _d is at least 1 having 1 to 15 carbon atoms X is a hydrocarbon group having at least one mercapto (SH) group as a substituent, and X is at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group and an alkoxy group.
The method according to claim 1, wherein the compound is a silane compound represented by the following formula: 16. R _d is mercaptomethyl group, 2-mercaptoethyl group, 3-mercapto -n- propyl, 4
The method according to claim 15, which is at least one member selected from the group consisting of -mercapto-n-butyl group, p-mercaptophenyl group and p-mercaptomethylphenyl group. 17. A catalyst for producing bisphenol prepared by the method according to claim 1. Description: 18. In the presence of the catalyst according to claim 17,
A method for producing bisphenol, comprising reacting a phenol with a ketone. 19. The method according to claim 18, wherein the phenol is phenol, the ketone is acetone, and the bisphenol is bisphenol A. 20. The phenol is phenol, the ketone is acetophenone, and the bisphenol is 4,
19. The method according to claim 18, which is 4 '-(1-phenylethylidene) bisphenol.