JPH08208545A - Production of bisphnol a - Google Patents

Abstract

PURPOSE: To obtain the subject compound useful as a raw material, etc., for polycarbonate resins, etc., in high conversion rate and selectivity by reacting phenol with acetone in the presence of an organic polymeric siloxane having a hydrocarbon group containing mercapto group and an acid. CONSTITUTION: Phenol is reacted with acetone in the presence of an organic polymeric siloxane having a hydrocarbon group containing mercapto group (preferably mercapto, 2-mercaptoethyl, 3-mercapto-n-propyl, p-mercaptophenyl or p-mercaptomethylphenyl group) and an acid to afford the objective compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing 2,2-bis (4'-oxyphenyl) propane (hereinafter abbreviated as bisphenol A) by a dehydration condensation reaction of phenol and acetone. Bisphenol A is an industrially extremely useful compound such as a raw material for polycarbonate, polyester, epoxy resin, and a developer for thermal paper.
In particular, bisphenol A used for polycarbonate resin is required to be colorless and highly pure.

[0002]

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 hydrochloric acid, for example, is used as the homogeneous catalyst, it can be reacted at a low temperature by crystallization of the adduct of bisphenol A with bisphenol A. Therefore, a high conversion rate of acetone and a high p, Bisphenol A can be produced with p'-selectivity. However, a homogeneous acid catalyst such as hydrochloric acid requires a step of removing or neutralizing the catalyst in the reaction mixture, which makes the operation complicated. In addition to this, the acid is uniformly dissolved in the reaction solution, which causes corrosion of the apparatus and the like. Therefore, a corrosion-resistant material must be used for the reaction apparatus, which is economically problematic. From this,
The production of bisphenol A using a solid heterogeneous catalyst has become industrially practiced.

Known solid heterogeneous catalysts are zeolites, partially neutralized and insolubilized heteropolyacid salts, strongly acidic cation exchange resins and the like. However, these solid heterogeneous catalysts have low catalyst activity and selectivity. As a method for overcoming the poor performance of these solid catalysts, it is known that the catalyst activity and reaction selectivity are improved by adding a sulfur-containing compound as a cocatalyst together with an acid catalyst to the reaction system.

As a sulfur-containing compound which has an effect of addition, thiol compounds such as alkyl mercaptan and benzyl mercaptan have long been known. These compounds are homogeneously dissolved in the reaction system and improve the activity of the acid catalyst and bring about high p, p'-selectivity of bisphenol A. Is difficult to separate, causing problems in product purification. Therefore, a method of immobilizing the thiol compound and avoiding contamination with the product is being investigated. For example, in JP-B-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, JP-B-46-
In 19953, a catalyst in which a strong acid cation exchange resin was partially neutralized with mercaptoalkylamine to immobilize it, and in JP-A-52-19189, a strong acid cation exchange resin was partially neutralized with cyclic mercaptoamine and fixed by ionic bond. In addition, a catalyst obtained by immobilizing a mercaptoamino acid with a cation exchange resin by an ionic bond is known in British Patent No. 1539186. However, the catalyst in which the mercapto compound is immobilized on these ion-exchange resins is low in heat resistance of the ion-exchange resin itself and easily deteriorates, and further, the above-exemplified mercapto compound is thermally unstable and decomposes and decomposes. It's easy to do. As a result, there are the same problems as the drawbacks of the homogeneous acid catalyst and the homogeneous mercapto compound as described above. Furthermore, the above-mentioned immobilization is due to the reaction with an acid group which is effective as a reaction catalyst, and has the drawback that the amount of acid is reduced.

[0005]

DISCLOSURE OF THE INVENTION In producing bisphenol A by dehydration condensation reaction of phenol and acetone in the presence of an acid catalyst, the present inventors have investigated the activity and selectivity of the reaction using a mercapto compound as a cocatalyst. Focusing on the improvement effect, as a result of diligent studies to overcome the problems of conventional separation and purification of mercapto compound in a homogeneous system, the problem of instability in immobilization of mercapto compound, etc., in the presence of an acid catalyst of phenol and acetone. When bisphenol A is produced by the dehydration condensation reaction in step 1, a mercapto compound added as a co-catalyst is added to the reaction system as an organic polymer siloxane in which an organic mercaptan compound is immobilized in a silica matrix, so that it is thermally stable. The elimination of mercapto groups is suppressed even under high temperature reaction conditions, and the reaction activity of the catalyst is increased. It was found that the selectivity is remarkably improved, and in addition to the process advantages of the heterogeneous acid catalyst, both the acid group represented by the sulfonic acid group and the mercapto group-containing hydrocarbon group are contained in the silica matrix. It was found that the co-catalyst and the acid catalyst are simultaneously immobilized by using the immobilized organic polymer siloxane, and the heterogeneous catalyst is highly active, highly selective and thermally stable. Arrived

In the present invention, an organic polymer siloxane having a mercapto group is used as a cocatalyst together with an acid catalyst so that the mercapto group in the reaction product system can be obtained even if the dehydration condensation reaction is carried out under high temperature conditions. It is possible to produce bisphenol A while maintaining the performance for a long period of time without any mixing of the above, and in addition, without lowering its cocatalyst effect.

Further, by using an organic polymer siloxane having both a sulfonic acid group and a mercapto group-containing hydrocarbon group as a catalyst, a stable heterogeneous catalyst without desorption of an acid catalyst and a cocatalyst component can be obtained. Bisphenol A can be produced by a highly economical method, which has advantages such as dehydration condensation reaction without deteriorating the activity of the catalyst and facilitating separation of the catalyst component.

That is, an object of the present invention is to provide a method for producing bisphenol A by dehydration condensation reaction of phenol and acetone in the presence of an acid catalyst, without adding a mercapto compound or the like to the product bisphenol A and It is an object of the present invention to provide a method for producing bisphenol A with high activity and high selectivity, in which a mercapto compound is not decomposed or released even at a high temperature reaction. Furthermore, it is also an object of the present invention to provide an industrially extremely effective novel solid catalyst that is highly efficient by immobilizing the acid catalyst in the reaction simultaneously with the mercapto group, and that can easily separate and recover the catalyst. is there.

[0009]

The present invention is a method for producing bisphenol A by a dehydration condensation reaction of phenol and acetone, wherein the reaction is carried out in the presence of an organic polymer siloxane having a mercapto group-containing hydrocarbon group and an acid. A method for producing bisphenol A characterized by the above.
Furthermore, bisphenol A is characterized in that an acid is also reacted in the presence of an organic polymer siloxane having a mercapto group-containing hydrocarbon group and a sulfonic acid group which are simultaneously immobilized.
Is also a manufacturing method of.

The present invention also has the general formula: X _n Si (R ₁ ).
_4-n (In the formula, n is an integer of 1 or more and 3 or less, X is at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom and an alkoxy group, and R ₁ is a mercapto group. A hydrocarbon group having at least one (SH group) and having 1 to 20 carbon atoms, a hydrocarbon group having an aromatic group having 6 to 20 carbon atoms, and a carbon number of 1 to 15 having at least one halogen atom. Alkyl group, at least one carbon, and having 2 or more carbon atoms having a carbon unsaturated bond 1
5 or less olefinic hydrocarbon groups and at least 1
Is at least one kind of hydrocarbon group selected from the group consisting of hydrocarbon groups having 2 to 15 carbon atoms and having 1 epoxy group, and Si represents a silicon atom. The organic polymer siloxane obtained by hydrolyzing at least one of the silane compounds represented by) is subjected to a sulfonation treatment to sulfonate the hydrocarbon group (R ₁ ) to obtain an organic polymer siloxane having a sulfonic acid group. After that, the general formula: X _n Si (R ₂ ) _4-n (where n is an integer of 1 or more and 3 or less, X is a chlorine atom,
At least one selected from the group consisting of a bromine atom, an iodine atom and an alkoxy group, R ₂ is a hydrocarbon group having 1 to 20 carbon atoms and at least one mercapto group (SH group), and Si is Represents a silicon atom. The present invention provides an organopolymer siloxane having a mercapto group-containing hydrocarbon group and a sulfonic acid group, which is obtained by silylation with at least one silane compound represented by the formula (1) and then hydrolysis.

[0011]

The present invention also uses silica gel of the general formula: X
_n Si (R ₁ ) _4-n (wherein, n is an integer of 1 or more and 3 or less, X is at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom and an alkoxy group, R
₁ is a hydrocarbon group having at least one mercapto group (SH group) and having 1 to 20 carbon atoms, and 6 to 20 carbon atoms
The following hydrocarbon group having an aromatic group, an alkyl group having at least one halogen atom and having 1 to 15 carbon atoms, at least one carbon, and an olefin having 2 to 15 carbon atoms having a carbon unsaturated bond 2 or more carbon atoms having a hydrocarbon group and at least one epoxy group of 15
At least one selected from the group consisting of the following hydrocarbon groups
Is a hydrocarbon group of the species, where Si represents a silicon atom. ) Is silylated with at least one silane compound and then hydrolyzed to obtain an organic polymer siloxane, which is subjected to a sulfonation treatment to give an organic polymer siloxane having a sulfonic acid group, and then further represented by the general formula: X _n Si (R ₂ )
_4-n (wherein n is an integer of 1 or more and 3 or less, X is at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom and an alkoxy group, and R ₂ is a mercapto group (SH 1 or more and 20 or more carbon atoms having at least one group
It is the following hydrocarbon group, and Si represents a silicon atom. )
The present invention provides an organic polymer siloxane having a mercapto group-containing hydrocarbon group and a sulfonic acid group, which is obtained by silylation with at least one silane compound represented by and then hydrolysis.

The present invention also has the general formula: X _n Si (R ₁ ).
_4-n (In the formula, n is an integer of 1 or more and 3 or less, X is at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom and an alkoxy group, and R ₁ is a mercapto group. A hydrocarbon group having at least one (SH group) and having 1 to 20 carbon atoms, a hydrocarbon group having an aromatic group having 6 to 20 carbon atoms, and a carbon number of 1 to 15 having at least one halogen atom. Alkyl group, at least one carbon, and having 2 or more carbon atoms having a carbon unsaturated bond 1
5 or less olefinic hydrocarbon groups and at least 1
Is at least one kind of hydrocarbon group selected from the group consisting of hydrocarbon groups having 2 to 15 carbon atoms and having 1 epoxy group, and Si represents a silicon atom. The organic polymer siloxane obtained by hydrolyzing at least one of the silane compounds represented by) is subjected to a sulfonation treatment to sulfonate the hydrocarbon group (R ₁ ) to obtain an organic polymer siloxane having a sulfonic acid group. After that, the general formula: X _n Si (R ₂ ) _4-n (where n is an integer of 1 or more and 3 or less, X is a chlorine atom,
At least one selected from the group consisting of a bromine atom, an iodine atom and an alkoxy group, R ₂ is a hydrocarbon group having 1 to 20 carbon atoms and at least one mercapto group (SH group), and Si is Represents a silicon atom. ) Is silylated with at least one silane compound represented by the formula (1) and then hydrolyzed, which is a method for producing an organic polymer siloxane having a mercapto group-containing hydrocarbon group and a sulfonic acid group.

The present invention also provides silica gels of the general formula: X
_n Si (R ₁ ) _4-n (wherein, n is an integer of 1 or more and 3 or less, X is at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom and an alkoxy group, R
₁ is a hydrocarbon group having at least one mercapto group (SH group) and having 1 to 20 carbon atoms, and 6 to 20 carbon atoms
The following hydrocarbon group having an aromatic group, an alkyl group having at least one halogen atom and having 1 to 15 carbon atoms, at least one carbon, and an olefin having 2 to 15 carbon atoms having a carbon unsaturated bond 2 or more carbon atoms having a hydrocarbon group and at least one epoxy group of 15
At least one selected from the group consisting of the following hydrocarbon groups
Is a hydrocarbon group of the species, where Si represents a silicon atom. ) Is silylated with at least one silane compound and then hydrolyzed to obtain an organic polymer siloxane, which is subjected to a sulfonation treatment to give an organic polymer siloxane having a sulfonic acid group, and then further represented by the general formula: X _n Si (R ₂ )
_4-n (wherein n is an integer of 1 or more and 3 or less, X is at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom and an alkoxy group, and R ₂ is a mercapto group (SH 1 or more and 20 or more carbon atoms having at least one group
It is the following hydrocarbon group, and Si represents a silicon atom. )
The method for producing an organic polymer siloxane having a mercapto group-containing hydrocarbon group and a sulfonic acid group, which comprises silylating with at least one of silane compounds represented by and then hydrolyzing.

The present invention will be described in detail below. Phenol and acetone used in the present invention do not need to be particularly purified, and their purity is not limited. It is preferably used in industrial purity or general reagent purity. It is also possible to dilute with a medium inert to the reaction such as saturated hydrocarbons before use.

The acid used as a catalyst in the present invention is not particularly limited, and any acid having a dehydration condensation activity such as a protonic acid or a Lewis acid may be used. Also, the form is not particularly limited,
Either a homogeneous acid catalyst that is uniformly dissolved in the reaction system or a heterogeneous acid catalyst that exists as a solid in the reaction system may be used. From the viewpoint of separation of the catalyst and the product, a heterogeneous acid catalyst is preferable, and one having high heat resistance is more preferable. Specifically, a part of the protons of the heteropolyacid is replaced with an alkali metal ion, an ammonium ion or the like to make a solid heterogeneous partially neutralized heteropolyacid, a heteropolyacid or a salt thereof is activated carbon, alumina, silica, diatomaceous acid. Examples of the heterogeneous acid catalyst include a supported acid catalyst supported on a carrier such as soil, zeolite, and a layered clay compound. In the present invention, of course, it is not limited to these heterogeneous acid catalysts, and other solid acid catalysts and homogeneous acid catalysts may be used.

The present invention uses an organic polymer siloxane having a mercapto group-containing hydrocarbon group as a cocatalyst together with the above acid catalyst. Further, it is preferable to use an organic polymer siloxane in which a mercapto group-containing hydrocarbon group which is an acid and a cocatalyst is simultaneously immobilized on a polymer siloxane, and further, an acid is a sulfonic acid group and a mercapto group-containing hydrocarbon group. The use of organic polymeric siloxanes having hydrogen groups is also recommended as a preferred embodiment.

The organic polymer siloxane having a hydrocarbon group containing a mercapto group used in the present invention is a hydrocarbon group partially having a mercapto group in a silica matrix composed of a siloxane bond. -A high-molecular-weight siloxane having a structure bonded by a silicon bond.

These organic polymer siloxanes have an average of 0.05 to 3, preferably 0.1 to 2, per silicon atom forming the siloxane due to a carbon-silicon bond.
More preferably, it is an organic polymer siloxane bonded to 0.2 to 1 hydrocarbon group having a mercapto group.

All of these hydrocarbon groups may have one or more mercapto groups, or some of the many hydrocarbon groups may have mercapto groups. It is preferable that all the hydrocarbon groups have a mercapto group. However, the organopolymer siloxane having a mercapto group-containing hydrocarbon group in the present invention is not limited by the amount of the mercapto group.

The organic polymer siloxane having a mercapto group-containing hydrocarbon group used as a co-catalyst in the present invention can be prepared, for example, by the following method. However, the present invention is not limited to only these preparation methods. As an easy preparation method, for example, a general formula:
X _n Si (R ₂ ) _4-n (where n is an integer of 1 or more and 3 or less, X is at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom and an alkoxy group, R
₂ is a hydrocarbon group having 1 to 20 carbon atoms having at least one mercapto group (SH group), and Si represents a silicon atom. ) Hydrolyze the silane compound represented by.

Alternatively, these silane compounds and the general formula:
SiX ₄ (wherein X is at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom and an alkoxy group, and Si is a silicon atom); It can be easily prepared by a method such as hydrolyzing a silane compound containing, and can be used in the reaction as a cocatalyst. In the present invention, the organic polymer siloxane having a mercapto group-containing hydrocarbon group obtained by these preparation methods or the like is used in a reaction with an acid as a cocatalyst.

Further, in the method of the present invention, sulfonic acid is used as an acid, and the sulfonic acid is simultaneously immobilized in an organic polymer siloxane having a mercapto group-containing hydrocarbon group. The organic polymer siloxane having a group can also be effectively used as a heterogeneous catalyst in the presence of an immobilization promoter. Here, the organic polymer siloxane having a sulfonic acid group and a mercapto group-containing hydrocarbon group in the present invention is
It is an organic polymer siloxane having a structure in which a hydrocarbon group partially having a sulfonic acid group and a hydrocarbon group partially having a mercapto group are directly bonded to a silicon atom by a carbon-silicon bond in a silica matrix composed of a siloxane bond.

These organic high-molecular-weight siloxanes have an average content of 0.01 to 1 per atom of silicon forming the siloxane.
2, preferably 0.05 to 1.5, more preferably 0.
It is bonded to a hydrocarbon group having a sulfonic acid group through 1 to 1 carbon-silicon bond, and further, it is 0.
01 to 2, preferably 0.05 to 1.5, more preferably 0.1 to 1 is a high molecular organic siloxane bonded to a hydrocarbon group having a mercapto group, a sulfonic acid group bonded to a silicon atom The sum of the hydrocarbon group having and the hydrocarbon group having a mercapto group bonded to a silicon atom is on average 0.05 to 3, preferably 0.1 per silicon atom.
˜2, more preferably 0.2 to 1 organic high molecular siloxane.

The method for preparing the organic polymer siloxane having a sulfonic acid group and a mercapto group-containing hydrocarbon group used as a catalyst in the present invention is not particularly limited, and it may be used in a polymer siloxane (silica) matrix. If there is a sulfonic acid group- and mercapto group-containing hydrocarbon group directly bonded to C by a carbon-silicon bond, it may be prepared by any preparation method. As an easy preparation method, for example, the following preparation method can be used. However, it is needless to say that the present invention is not limited to these preparation methods.

As an easy method, for example, the general formula: X
_n Si (R ₃ ) _4-n (wherein n is an integer of 1 or more and 3 or less, X is at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom and an alkoxy group,
R ₃ is at least one selected from the group consisting of hydrocarbon groups having at least one sulfonic acid group, and Si represents a silicon atom. ) And at least one silane compound represented by the general formula: X _n Si (R ₂ ) _4-n (wherein n is an integer of 1 or more and 3 or less, X is a chlorine atom, a bromine atom, an iodine atom and R ₂ is at least one selected from the group consisting of alkoxy groups, R ₂ is a hydrocarbon group having at least one mercapto group (SH group) and having 1 to 20 carbon atoms, and Si represents a silicon atom.) The silane compound represented by is hydrolyzed.

Alternatively, these silane compounds and the general formula: SiX ₄ (wherein X is at least one selected from the group consisting of chlorine atom, bromine atom, iodine atom and alkoxy group, and Si is a silicon atom) It is possible to hydrolyze and prepare a silane compound containing at least one silane compound represented by the formula (1).

Further, the general formula: X _n Si (R ₃ )
_4-n (wherein n is an integer of 1 or more and 3 or less, X is at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom and an alkoxy group, and R ₃ is a sulfonic acid group. Which is at least one selected from the group consisting of at least one hydrocarbon group, and Si represents a silicon atom), or at least one silane compound of the silane compounds represented by the general formula: SiX
₄ (in the formula, X is at least one selected from the group consisting of chlorine atom, bromine atom, iodine atom and alkoxy group, and Si is a silicon atom). An organic polymer siloxane having a sulfonic acid group prepared by hydrolyzing a contained silane compound is represented by the general formula: X _n Si (R ₂ ) _4-n (wherein n is an integer of 1 or more and 3 or less, X is a chlorine atom,
At least one selected from the group consisting of a bromine atom, an iodine atom and an alkoxy group, R ₂ is a hydrocarbon group having 1 to 20 carbon atoms and at least one mercapto group (SH group), and Si is Represents a silicon atom. It can also be prepared by silylation with a silane compound represented by (4) and hydrolysis.

At this time, the sulfonic acid group should be exchanged for protons in advance by subjecting the protons to the above-mentioned hydrolysis as sulfonic acid salts exchanged with metal cations and subjecting the obtained organic polymer siloxane to acid treatment. There is no problem in using a sulfonic acid group.

The silane compounds represented by the above general formula: X _n Si (R ₃ ) _4-n and the above general formula: X _n Si (R ₂ ) _4-n are sequentially or mixed on silica gel. An organopolymer siloxane having a sulfonic acid group and a mercapto group immobilized by simultaneous silylation can also be used as a catalyst.

Another preferred preparation method is represented by the general formula: X _n Si (R ₁ ) _4-n (wherein n is an integer of 1 or more and 3 or less, X is a chlorine atom, a bromine atom or an iodine atom). And at least one selected from the group consisting of alkoxy groups, R ₁ is a hydrocarbon group having at least one mercapto group (SH group) having 1 to 20 carbon atoms, and an aromatic having 6 to 20 carbon atoms. A hydrocarbon group having a group, an alkyl group having at least one halogen atom and having 1 to 15 carbon atoms, at least one carbon, and an olefinic hydrocarbon having 2 to 15 carbon atoms having a carbon unsaturated bond Group and a hydrocarbon group having at least one epoxy group and having from 2 to 15 carbon atoms, the hydrocarbon group being at least one kind selected from the group consisting of Si and Si. It hydrolyzes at least one of the orchid compounds, or these silane compounds and the general formula: SiX ₄ (wherein X is at least one selected from the group consisting of chlorine atom, bromine atom, iodine atom and alkoxy group). ,
Si is a silicon atom. ) The organic polymer siloxane obtained by hydrolyzing a silane compound containing at least one silane compound represented by the formula ( ₁ ) is sulfonated to give a sulfonate group to the hydrocarbon group (R ₁ ). After being made into an organic polymer siloxane, it is represented by the general formula: X _n Si (R ₂ ) _4-n (where n is an integer of 1 or more and 3 or less, X is a chlorine atom,
At least one selected from the group consisting of a bromine atom, an iodine atom and an alkoxy group, R ₂ is a hydrocarbon group having 1 to 20 carbon atoms and at least one mercapto group (SH group), and Si is Represents a silicon atom. A method can be employed in which an organic polymer siloxane having a mercapto group-containing hydrocarbon group and a sulfonic acid group is obtained by silylation with at least one silane compound represented by the formula (1) and then hydrolysis.

Further, silica gel may be represented by the general formula: X _n Si
(R ₁ ) _4-n (In the formula, n is an integer of 1 or more and 3 or less, and X is
Is at least one selected from the group consisting of chlorine atom, bromine atom, iodine atom and alkoxy group, and R ₁ is
Hydrocarbon group having at least one mercapto group (SH group) and having 1 to 20 carbon atoms, hydrocarbon group having from 6 to 20 aromatic groups, and having 1 or more carbon atoms having at least one halogen atom. 15 or less alkyl group, at least one carbon, carbon number 2 having a carbon unsaturated bond
Is at least one hydrocarbon group selected from the group consisting of hydrocarbon groups having 2 or more and 15 or less carbon atoms and having at least 15 or less olefinic hydrocarbon groups and at least one epoxy group, and Si is a silicon atom Represents ) Was silylated with at least one of the silane compound represented by and then sulfonating the polyorganosiloxane obtained by hydrolyzing a polyorganosiloxane having a sulfonic acid group, which further general formula: X _n Si (R ₂ ) _4-n (where n
Is an integer of 1 or more and 3 or less, X is at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom and an alkoxy group, and R ₂ is a mercapto group (SH
Is a hydrocarbon group having 1 to 20 carbon atoms and having 1 to 20 carbon atoms, and Si represents a silicon atom. A method can be employed in which an organic polymer siloxane having a mercapto group-containing hydrocarbon group and a sulfonic acid group is obtained by silylation with at least one silane compound represented by the formula (1) and then hydrolysis.

Here, the hydrocarbon groups R ₁ , R ₂ and R ₃ shown in all the above general formulas will be described in detail. R ₃ is at least one sulfonic acid group (—SO ₃
Any hydrocarbon group can be used in the present invention as long as it is a hydrocarbon group having H). However, it is preferably a hydrocarbon having at least one sulfonic acid group and having 1 to 20 carbon atoms. It is a base. Preferably a substituted or unsubstituted aromatic hydrocarbon group having at least one sulfonic acid group having 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms (the sulfonic acid group is directly substituted on the aromatic group. Or a hydrocarbon group substituted with an aromatic group and a sulfonic acid group substituted with a sulfonic acid group); or, preferably, having at least one sulfonic acid group and having 1 to 15 carbon atoms, and It is preferably at least one hydrocarbon group selected from the group consisting of a substituted or unsubstituted aliphatic or alicyclic hydrocarbon group having 1 to 10 carbon atoms.

Specifically, an aromatic group such as a phenyl group, a tolyl group, a naphthyl group, a methylnaphthyl group and the like, which is nuclear-substituted with at least one sulfonic acid group, and an aromatic substituted alkyl such as a benzyl group and a naphthylmethyl group. Groups, such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, substituted with at least one sulfonic acid group,
i-butyl group, t-butyl group, straight-chain or branched pentyl group, straight-chain or branched hexyl group, straight-chain or branched heptyl group, straight-chain or branched octyl group, cyclohexyl group, methyl Examples thereof include a cyclohexyl group and an ethylcyclohexyl group. Further, these aromatic or saturated aliphatic or alicyclic hydrocarbon groups are hydrocarbon groups having a substituent such as a halogen element, an alkoxy group, a nitro group, an amino group and a hydroxy group in addition to a sulfonic acid group. It doesn't matter.

R ₂ has 1 to 20 carbon atoms having at least one mercapto group represented by —SH as a rational formula.
At least one selected from the group consisting of the following hydrocarbon groups
It is a hydrocarbon group in which an —SH group is bonded to an aliphatic or alicyclic saturated hydrocarbon, unsaturated hydrocarbon or aromatic hydrocarbon. Preferably, it is a hydrocarbon group in which at least one SH group is bonded to an aliphatic or alicyclic saturated hydrocarbon group or an aromatic hydrocarbon group. As a specific example, a mercaptomethyl group, a 2-mercaptoethyl group, 3
-Mercaptoalkyl groups such as mercapto-n-propyl group, alicyclic hydrocarbon groups such as 4-mercaptocyclohexyl group and 4-mercaptomethylcyclohexyl group, p
-Mercapto aromatic groups such as -mercaptophenyl group and p-mercaptomethylphenyl group. Of course,
The present invention is not limited to these groups. Further, these aromatic or aliphatic or alicyclic hydrocarbon groups may be hydrocarbon groups having a substituent such as a halogen element, an alkoxy group, a nitro group, an amino group and a hydroxy group in addition to the mercapto group. Absent.

Further, R ₁ may be any hydrocarbon group as long as it is a hydrocarbon group capable of introducing a sulfonic acid group by various sulfonation treatments, but a preferable hydrocarbon group is a mercapto group (SH group). ) At least 1
Hydrocarbon group having 1 unit, hydrocarbon group having aromatic group, alkyl group having at least one halogen atom, olefinic hydrocarbon group having at least 1 carbon, carbon unsaturated bond, and at least 1 epoxy group Is at least one hydrocarbon group selected from the group consisting of hydrocarbon groups having

Taking the above hydrocarbon group (R ₁ ) as an example, the hydrocarbon group having at least one mercapto group is a hydrocarbon group having 1 to 20 carbon atoms, which is an aliphatic or alicyclic group. It is a hydrocarbon group in which a -SH group is bonded to a saturated hydrocarbon, an unsaturated hydrocarbon or an aromatic hydrocarbon.
A hydrocarbon group in which at least one SH group is bonded to an aliphatic or alicyclic saturated hydrocarbon group or an aromatic hydrocarbon group is preferable. Specific examples are a mercaptomethyl group, a 2-mercaptoethyl group, and a 3-mercapto- group.
Alicyclic hydrocarbon groups such as mercaptoalkyl groups such as n-propyl group, 4-mercaptocyclohexyl group and 4-mercaptomethylcyclohexyl group, mercapto aroma such as p-mercaptophenyl group and p-mercaptomethylphenyl group Group groups and the like can be mentioned. Of course, the present invention is not limited to these groups. Further, these aromatic or aliphatic or alicyclic hydrocarbon groups may be hydrocarbon groups having a substituent such as a halogen element, an alkoxy group, a nitro group, an amino group and a hydroxy group in addition to the mercapto group. Absent.

As the hydrocarbon group having an aromatic group, a hydrocarbon group having an aromatic group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, or a hydrocarbon group substituted with an aromatic group (for example, (Alkyl groups substituted with aromatic groups) etc., aromatic groups such as phenyl group, tolyl group, xylyl group, methylnaphthyl group, ethylnaphthyl group, etc., aromatic substituted alkyl groups such as benzyl group, naphthylmethyl group, etc. Is mentioned. Further, these hydrocarbon groups may be hydrocarbon groups having a substituent such as a halogen element, an alkoxy group, a nitro group, an amino group and a hydroxy group.

The alkyl group having at least one halogen atom is an alkyl group substituted with a halogen atom having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, and the substituted halogen The atom is preferably at least one selected from the group consisting of chlorine atom, bromine atom, and iodine atom. Specific examples of these alkyl groups include chloromethyl group, dichloromethyl group, bromomethyl group, dibromomethyl group, iodomethyl group, diiodomethyl group, 2-chloroethyl group,
1,2-dichloroethyl group, 2-bromoethyl group, 2-
Iodoethyl group, 3-chloro-n-propyl group, 3-bromo-n-propyl group, 3-iodo-n-propyl group,
An alkyl group substituted with a halogen atom such as a 4-chloro-n-butyl group and a 4-bromo-n-butyl group,
An alicyclic hydrocarbon group having a halogen atom as a substituent, such as a chlorocyclohexyl group and a 4-bromocyclohexyl group, also belongs to the halogenated alkyl group of the present invention. Further, these alkyl groups are, in addition to halogen atoms, alkoxy groups,
It may be an alkyl group having a substituent such as a nitro group, an amino group and a hydroxy group.

The olefinic hydrocarbon group having at least one carbon atom and a double bond is an olefinic hydrocarbon group having 2 to 15 carbon atoms, preferably an olefinic hydrocarbon group. 8 carbon atoms in the base
An aromatic hydrocarbon group of 15 or more and 15 or less or a carbon number of 2 or more and 1
A 0 or less aliphatic or alicyclic olefinic hydrocarbon group, specifically, an aromatic hydrocarbon group having an olefinic hydrocarbon group as a substituent includes 4-vinylphenyl group and 4-vinyl group. There are naphthyl group, 4-allylphenyl group and the like, and as the aliphatic or alicyclic olefinic hydrocarbon group, vinyl group, allyl group, n-butenyl group, cyclohexenyl group, methylcyclohexenyl group , Ethylcyclohexenyl groups and the like. Further, these groups may be hydrocarbon groups having a substituent such as a halogen element, an alkoxy group, a nitro group, an amino group or a hydroxy group as another substituent.

Further, the hydrocarbon group having at least one epoxy group is a hydrocarbon group having at least one epoxy group and having 2 to 15 carbon atoms, and preferably having an epoxy group as a substituent. An aromatic hydrocarbon group having 8 to 15 carbon atoms or an aliphatic or alicyclic hydrocarbon group having 2 to 10 carbon atoms having an epoxy bond, and specifically, an aromatic group having an epoxy group as a substituent As the group hydrocarbon group, a p-epoxyethylphenyl group,
4-epoxyethylnaphthyl group, p- (2,3-epoxypropyl) phenyl group, p- (3,4-epoxycyclohexyl) phenyl group, etc., which is an aliphatic or alicyclic hydrocarbon having an epoxy bond. As the group, epoxyethyl group, 2,3-epoxypropyl group, 3,4-
Examples thereof include an epoxycyclohexyl group, a 3-glycidoxypropyl group, and a 2- (3,4-epoxycyclohexyl) ethyl group. In addition to the epoxy group, these hydrocarbon groups also have a substituent such as a halogen element, an alkoxy group, a nitro group,
It may be a hydrocarbon group having a substituent such as an amino group and a hydroxy group. Of course, these hydrocarbon groups (R
₁ ) is merely an example, and any hydrocarbon group may be used as long as it is a hydrocarbon group capable of introducing a sulfonic acid group by various sulfonation treatments, and is not limited to these hydrocarbon groups. There is no such thing.

In the present invention, as described above, the general formula: X _n
The silane compound represented by Si (R ₁ ) _4-n or a mixture of these silane compounds and the silane compound represented by the general formula: SiX ₄ is hydrolyzed, or the general formula: X _n Si
The organic polymer siloxane obtained by silylating a silane compound represented by (R ₁ ) _4-n on silica gel and then hydrolyzing the silane compound is sulfonated to obtain an organic polymer siloxane having a sulfonic acid group. The siloxane compound is further silylated with a silane compound represented by the general formula: X _n Si (R ₂ ) _4-n and hydrolyzed to prepare an organic polymer siloxane having a sulfonic acid group and a mercapto group-containing hydrocarbon group. You can

The sulfonation referred to in the present invention is not particularly limited with respect to its formulation, and R ₁
Any formulation may be used as long as it is a formulation in which the hydrocarbon group represented by is a hydrocarbon group having a sulfonic acid group. Further, it is natural that the prescription differs depending on the type of R ₁ .

As the sulfonation treatment, a method that is easy to carry out is specifically illustrated. For example, in the case of an organic polymer siloxane obtained from a silane compound having a hydrocarbon group having at least one mercapto group, Organic polymers having a sulfonic acid group by being oxidized by contact with various oxidizing agents (for example, nitric acid, hydrogen peroxide, etc.) or by addition reaction with an olefin compound having a sulfonic acid group (addition of SH to olefin) It can be a siloxane. At this time, by adding the amount of the olefin compound having a sulfonic acid group in an amount smaller than the amount of the mercapto group in the organopolymer siloxane having a mercapto group, the following general formula: X _n Si (R ₂ ) An organic polymer siloxane having a sulfonic acid group and a mercapto group can be obtained without performing a silylation treatment with a silane compound represented by _{4- n} .

Specific examples of the olefin compound having a sulfonic acid group used for sulfonation include vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid and cyclohexene sulfonic acid. Of course, it is not limited to these olefinic sulfonic acids. Further, in the case of organic polymer siloxanes obtained from a silane compound having a hydrocarbon group having an aromatic group, these organic polymer siloxanes are subjected to a usual aromatic sulfonation treatment by contact with sulfuric acid or chlorosulfonic acid. Thus, an organic polymer siloxane having a sulfonic acid group can be obtained.

In the case of an organic polymer siloxane obtained from a silane compound having a halogenated alkyl group, the sulfonic acid group is removed by heating with a metal sulfite (eg sodium sulfite, potassium sulfite) solution and acid treatment. It can be an organic high molecular siloxane.

In the case of an organic polymer siloxane obtained from a silane compound having an olefinic hydrocarbon group having at least one carbon and a double bond, in the presence of an oxidizing agent (air, oxygen, etc.), An organic polymer siloxane having a sulfonic acid group can be obtained by contact with a solution of a metal hydrogen sulfite (sodium hydrogen sulfite, potassium hydrogen sulfite, etc.) and subsequent acid treatment.

Further, in the case of an organic polymer siloxane obtained from a silane compound having a hydrocarbon group having at least one epoxy bond (oxirane group), a metal hydrogen sulfite (sodium hydrogen sulfite, potassium hydrogen sulfite, etc.) is used. By contact with the solution of and subsequent acid treatment,
It can be an organic polymer siloxane having a sulfonic acid group.

Here, in the sulfonation using the metal bisulfite, coexistence of the metal sulfate is recommended as a preferable sulfonation method. However, it goes without saying that the method of the present invention is not limited to these sulfonation methods.

In the present invention, an organic polymer siloxane having a sulfonic acid group is formed by the above-mentioned methods, and then silylated with a silane compound represented by the general formula: X _n Si (R ₂ ) _4-n to obtain a hydrolyzed product. By decomposing, an organic polymer siloxane having a sulfonic acid group and a mercapto group-containing hydrocarbon group can be prepared.

Here, the silylation referred to in the present invention will be described. The silylation carried out in the present invention is fully achieved by the silylation carried out with conventional silylating agents. As a specific example of a silylation method that is easy to carry out, a silanol group (-Si-) contained in the organic polymer siloxane matrix having a sulfonic acid group obtained by the above formulation is used.
OH) group is directly reacted with a silane compound represented by the above general formula: X _n Si (R ₂ ) _4-n to form a siloxane bond (Si—O).
It is to immobilize the -Si-R ₂₎ to generate the polyorganosiloxane (including silica gel matrix). Furthermore, a large amount of mercapto group-containing hydrocarbon groups can be immobilized by a method of bringing a large amount of the above silylating agent into contact with an organic polymer siloxane having a sulfonic acid group in the coexistence of water.

At this time, the organic high-molecular-weight siloxane having a sulfonic acid group is previously silylated as a sulfonic acid salt in which the protons of the sulfonic acid group are exchanged with a metal cation, and then converted to a sulfonic acid group again with an acid. A silylation method such as conversion is recommended as a more preferable method.

In carrying out these silylations, alcohols, saturated aliphatic hydrocarbons (hexane, heptane, etc.) or aromatic hydrocarbons (inert to the silylating agent and the organic polymer siloxane having sulfonic acid groups) (aromatic hydrocarbons) It is also possible to dilute the silylating agent with a medium such as benzene or toluene) to carry out the silylation. In the present invention, the amount of silylation by the silylating agent is not particularly limited, but preferably in a weight percentage (as a weight increase amount after silylation and hydrolysis) relative to the organic polymer siloxane having a raw material sulfonic acid group. 0.5 to 2
It is recommended to be 00, preferably 1 to 100 weight percent. Of course, the present invention is not limited to these amount ranges.

Further, X in each of the above general formulas represents at least one selected from the group consisting of chlorine atom, bromine atom, iodine atom and alkoxy group, and the silicon-X bond is decomposed by hydrolysis, It is a group capable of forming a high-molecular siloxane bond. Specifically, examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a t-butoxy group, and other alkylalkoxy groups, a phenoxy group, and a naphthoxy group. Examples thereof include aromatic alkoxy groups such as groups. The present invention is not limited to only these alkoxy groups. It is also preferably a chlorine atom. Needless to say, X is not limited to these, and may be a mixed substituent of these.

The embodiments of the method of the present invention will be described below. Amount of phenol and acetone used as raw materials (volume ratio)
Is not particularly limited, but the molar ratio of phenol / acetone is preferably in the range of 0.1 to 100, and more preferably 0.5 to 50.
If the amount of phenol is too small, it is difficult to achieve a high conversion rate of raw material acetone, and if the amount of phenol is too large, it is possible to achieve a high conversion rate of acetone, but it is possible to increase the phenol content more than necessary. This is because the reactor is too large to be used and a large amount of phenol needs to be circulated, so that it cannot be produced efficiently.

The reaction temperature is not particularly limited in the present invention, but it is preferably in the range of 0 to 300 ° C, more preferably 30 to 300 ° C. If the reaction temperature is too low, an extremely long reaction time is required to achieve a high conversion rate of the raw materials, in other words, the reaction rate is extremely decreased and the productivity of the reaction product is decreased. On the other hand, if the reaction temperature is excessively high, undesirable side reactions and the like proceed to increase the amount of by-products, and the stability of the raw materials phenol and acetone and the product bisphenol A is not preferable, and the reaction selection is not preferable. It causes a decrease in the rate and is 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 carry out at a too low pressure. A generally preferred operating pressure range is 0.
1 to 200 atm, more preferably 0.5 to 100 atm
Atmospheric pressure. Of course, the invention is not limited to these pressure ranges. In carrying out the present invention, the amount of the catalyst (acid catalyst) used and the amount of the organopolymer siloxane having a mercapto group-containing hydrocarbon group as a cocatalyst are not particularly limited, but for example, the reaction is carried out in a batch system. When carried out, the acid catalyst and the cocatalyst are preferably 0.001 to 200% by weight with respect to the phenol as a raw material,
More preferably, it is recommended to carry out in the range of 0.1 to 50%.

Similarly, when an organic polymer siloxane having both a sulfonic acid group and a mercapto group-containing hydrocarbon group is used as a catalyst, the invention is not particularly limited, but preferably, with respect to the raw material phenol, 0.0
It is recommended to carry out in the range of 02 to 200%, more preferably 0.1 to 50%. Organosiloxane having too small amount of acid catalyst and mercapto group-containing hydrocarbon group,
Alternatively, the use of an organic polymer siloxane catalyst having a sulfonic acid group and a mercapto group-containing hydrocarbon group substantially lowers the reaction rate and becomes a problem in efficiency,
Also, if it is used in an excessively large amount, the stirring efficiency of the reaction solution and the like may be reduced, which may cause trouble.

In carrying out the present invention, an organic polymer siloxane having a mercapto group-containing hydrocarbon group as an acid catalyst and a cocatalyst in the reaction system, or an organic polymer having a sulfonic acid group and a mercapto group-containing hydrocarbon group It is also possible to add a solvent or gas which is inactive to siloxane and the reaction reagent, and perform the dilution. Specifically, aliphatic saturated hydrocarbons such as methane, ethane, propane, butane, hexane and cyclohexane, nitrogen,
An inert gas such as argon or helium, or hydrogen in some cases may be used as a diluent.

When carrying out the present invention, the method can be carried out in any of a batch type, a semibatch type and a continuous flow type. The reaction form is such that the acid catalyst is in a liquid homogeneous or solid heterogeneous state, and the organic polymer siloxane having a mercapto group-containing hydrocarbon group or the organic polymer siloxane having a sulfonic acid group and a mercapto group-containing hydrocarbon group is in a solid state. Liquid phase, gas phase,
It can be carried out in any form of the gas-liquid mixed phase. It is recommended to carry out the reaction in a liquid phase, preferably from the viewpoint of reaction efficiency.

The organic polymer siloxane having a mercapto group-containing hydrocarbon group as a cocatalyst and a solid acid catalyst, or the organic polymer siloxane having a sulfonic acid group and a mercapto group-containing hydrocarbon group as a catalyst can be filled in the following manner. Various methods such as a fixed bed, a fluidized bed, a suspension bed, and a fixed plate with trays are adopted, and any method may be used.
The reaction time (residence time or catalyst contact time in flow reaction) is not particularly limited, but is usually 0.1 second to 30 hours, preferably 0.5 second to 15 hours.

After the reaction, the reaction product can be separated and recovered from the cocatalyst, the acid catalyst and the like by a separation method such as filtration, extraction and distillation. Bisphenol A, which is the desired product, is separated from the recovered product by a sequential treatment method such as solvent extraction, distillation, alkali treatment, acid treatment or the like, or an ordinary combination such as an operation in which these treatments are combined appropriately. It can be obtained after separation and purification. Further, the unreacted raw material can be recovered and recycled to the reaction system for use.

In the case of a batch reaction, the acid catalyst and cocatalyst recovered by separating the reaction product after the reaction, or the catalyst on which the cocatalyst is immobilized at the same time is used as it is, or a part or all thereof is regenerated, and then the reaction is repeated. It can also be used again in the reaction. When the reaction is carried out in a fixed bed or fluidized bed flow continuous reaction system, some or all of the acid catalysts and co-catalysts are deactivated or reduced in activity by being subjected to the reaction. And / or the co-catalyst or the acid catalyst having the co-catalyst immobilized at the same time can be regenerated for use in the reaction, or a part of the co-catalyst can be continuously or intermittently withdrawn, and after regeneration, recycled to the reactor again. It can be reused. Furthermore, a new acid catalyst, a cocatalyst, or an acid catalyst to which a cocatalyst is simultaneously immobilized can be continuously or intermittently supplied to the reactor. When carrying out a moving bed flow continuous reaction or a homogeneous catalyst flow reaction system, an acid catalyst and / or a cocatalyst or an acid catalyst on which a cocatalyst is immobilized at the same time is separated and recovered as in the batch reaction, and is necessary. If there is, it can be regenerated and reused.

[0064]

EXAMPLES Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to these examples. A: Method for preparing mercapto group-containing organopolymer siloxane used as co-catalyst (a) Co-catalyst 1 500 ml three-necked flask equipped with stirrer and cooling tube
Ethanol, 100 ml, 3-mercaptopropyltrimethoxysilane [(HSCH ₂ CH ₂ CH ₂ ) Si (OMe) ₃ ], 10.0 g (51.7
(mmol) and stirred at room temperature for 2 hours, and then deionized water is required (1/2 of the molar amount of the alkoxy group in the added silane).
5 times mol (51.7 × 3 × 0.5 × 5 = 387.8 mmol) was slowly added dropwise, and the mixture was further stirred at room temperature for 1 hour. After 28% ammonia water 10.0 g was added dropwise to this with stirring for about 1 hour, the liquid temperature was adjusted to 80 ° C. and the mixture was heated and stirred all day and night. As a result, gelation of the liquid was confirmed. Then, the solvent and the like were distilled off under reduced pressure to obtain a solid. Pure water (500 ml) was added to this solid, and the mixture was stirred and washed at 80 ° C. for 4 hours. After cooling, the solid was separated by filtration, thoroughly washed with pure water, and then dried under reduced pressure at 100 ° C. for 4 hours to obtain an organic polymer siloxane having a mercapto group. This was used as a cocatalyst 1 in the reaction.

(B) Cocatalyst 2 to 4 3-Mercaptopropyltrimethoxysilane used in (a), 10.0 g of tetraethoxysilane was added to each of the amounts listed in Table 1, and the mixture was stirred as in (a). Then, pure water was charged, and a molar amount of 1/2 of the total molar amount of the methoxy group and the ethoxy group (necessary amount of hydrolysis) was added. Then, in the same manner as in the preparation method (a) of the cocatalyst 1, cocatalysts 2 to 4 were obtained.

(C) Promoter 5 3-mercaptopropyltrimethoxysilane was replaced with 3-mercaptopropyl-methyldimethoxysilane [(HSCH ₂ CH ₂ CH ₂ ) Si
(Me) (OMe) ₂ ] was used instead of (Me) (OMe) ₂ ], and the procedure and conditions were the same as those for the preparation of promoter 2. This was used as a cocatalyst 5 in the reaction. The promoters 1 to 5 are shown in Table 1.

(D) Promoter 6 Commercially available silica gel (MS gel: Dokai Chemical Industry Co., Ltd.) 1
After drying 0.0 g under reduced pressure at 100 ° C. for 4 hours, 3-mercaptopropyltrimethoxysilane [(HSCH ₂ CH ₂ CH ₂ ) Si (OM
e) ₃ ], 10.0 g (51.7 mmol) were added, and the mixture was heated with stirring at 100 ° C. for 4 hours. After allowing to cool, this was filtered and thoroughly washed with methanol and acetone. The amount of the mercapto group of the obtained organic polymer siloxane having a mercapto group-containing hydrocarbon group was 1.11 mgeq / g.

[0068]

[Table 1] Table 1 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ silane used for hydrolysis SH amount ── ────────────────────────────────── Cocatalyst Mercaptosilane (g) Silane (g) (mgeq / g) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Co-catalyst 1 (HSCH ₂ CH ₂ CH ₂ ) Si (OMe ) ₃ 10.0 Not used 0.0 1.77 Promoter 2 (HSCH ₂ CH ₂ CH ₂ ) Si (OMe) ₃ 10.0 Si (OEt) ₄ 10.0 2.71 Promoter 3 (HSCH ₂ CH ₂ CH ₂ ) Si (OMe) ₃ 10.0 Si (OEt) ₄ 5.0 2.99 Cocatalyst 4 (HSCH ₂ CH ₂ CH ₂ ) Si (OMe) ₃ 10.0 Si (OEt) ₄ 20.0 2.49 Cocatalyst 5 (HSCH ₂ CH ₂ CH ₂ ) Si (Me) (OMe) ₂ 10.0 Si (OEt) ₄ 10.0 2.55 Co-catalyst 6 1.11 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

Examples 1 to 6 In a 70 ml pressure-resistant reactor, 3.80 g (65.5 mmol) of acetone, 33.00 g (351.1 mmol) of phenol, and 2/3 of protons possessed by dodecatungstophosphoric acid as an acid catalyst were exchanged with ammonium cations. , Homogenized, partially neutralized salt [(NH ₄ ) ₂ HPW
₁₂ O ₄₀ ] 2.00 g, 0.60 g of any one of co-catalysts 1 to 6 was charged, and after pressurizing the pressure resistant reactor with nitrogen gas to 5 kg / cm ² gauge pressure, the mixture was heated and stirred at 100 ° C. for 2 hours to carry out the reaction. went. After completion of the reaction, the reaction solution was cooled to room temperature and released, and the reaction solution was taken out and analyzed and quantified by liquid chromatography. As shown in Table 2, bisphenol A was produced in good yield.

Comparative Example 1 The reaction was carried out under the same conditions as in Example 2 except that the promoter was not used. As shown in Table 2, the results show that the yield of bisphenol A also decreased and p,
The selectivity of p'-bisphenol A was also reduced. From this, it is understood that the organic polymer siloxane having a mercapto group in the present invention has an excellent effect as a cocatalyst.

[0071] carrying out the reaction under the same conditions as in Example 2 was used in place of the Example 7 the acid catalyst in dodecatungstophosphoric acid removal of the water of crystallization _{(H 3 PW 12 O 40 .0H} 2 O) 2.0g It was The results are shown in Table 2.

Comparative Example 2 The reaction was carried out under the same conditions as in Example 7 except that no cocatalyst was added. As shown in Table 2, the results showed that the yield and the selectivity of bisphenol A were lower than those of Example 7. As a result, it was found that the cocatalyst of the present invention is effective even when a homogeneous acid catalyst is used.

Example 8 As an acid catalyst, 2/3 of protons of dodecatungstophosphoric acid were exchanged with Cs cations to form a heterogeneous solidification catalyst (Cs ₂ HPW ₁₂ O ₄₀ ..
The reaction was carried out under the same conditions as in Example 2, except that 0H ₂ O) was changed to 2.0 g. The results are shown in Table 2.

Example 9 The reaction was carried out under the same conditions as in Example 2 except that 2.0 g of the strongly acidic cation exchange resin Amberlyst 15 was used instead of the acid catalyst. The results are shown in Table 2.

Comparative Example 3 The reaction was carried out under the same conditions as in Example 9 except that the organopolymer siloxane having a mercapto group as a cocatalyst was not used. As shown in Table 2, both the yield of bisphenol A and the selectivity were lower than those of Example 9 as shown in Table 2.

Example 10 All of Example 2 except that the charged amount of acetone was 1.90 g.
The reaction was performed under the same conditions as above. As shown in Table 2, bisphenol A was produced in a high yield with respect to acetone.

Example 11 The reaction was carried out under the same conditions as in Example 2 except that the reaction temperature was 120 ° C. and the reaction time was 1 hour. As shown in Table 2, bisphenol A was produced in high yield.

Example 12 The reaction was carried out under the same conditions as in Example 2 except that the amount of promoter 2 added was 1.2 g. The results are as shown in Table 2.
By increasing the amount of co-catalyst, the yield of bisphenol A was further increased and the selectivity was also improved.

Example 13 Silica tungstic acid (H ₄ SiW) obtained by removing water of crystallization from an acid catalyst was used.
₁₂ O ₄ 0.0H ₂ O) 2.0 g The reaction was carried out under the same conditions as in Example 2, except that 2.0 g was used. The results are shown in Table 2.

Comparative Example 4 The reaction was carried out under the same conditions as in Example 13 except that the organopolymer siloxane having a mercapto group as a cocatalyst was not used. As shown in Table 2, the bisphenol A yield and selectivity were lower than those of Example 13 as shown in Table 2.

Example 14 The reaction was carried out under the same conditions as in Example 2 except that 2.0 g of concentrated hydrochloric acid was used as the acid catalyst. The results are shown in Table 2.

Comparative Example 5 The reaction was carried out under the same conditions as in Example 14 except that the organopolymer siloxane having a mercapto group as a cocatalyst was not used. As shown in Table 2, both the yield of bisphenol A and the selectivity were lower than those of Example 14 as shown in Table 2.

Example 15 The cocatalyst used in Example 14 was taken out by filtering the reaction solution, thoroughly washed with methanol and then dried.
It was used again in the reaction under the same conditions as in Example 14. As a result, as shown in Table 2, the activity of the promoter effect was maintained.

[0084]

[Table 2] Table 2 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Co-catalyst Product yield (preparation) Acetone standard%) p, p'-BPA o, p'-BPA COD ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example 1 1 36.7 2.9 1.2 Example 2 2 47.2 3.0 1.6 Example 3 3 49.4 3.1 1.3 Example 4 4 46.1 3 .5 0.9 Example 5 5 47.0 2.9 1.0 Example 6 6 43.0 2.1 0.6 Comparative Example 1-2 77.9 5.1 2.0 Example 7 2 54. 4 2.8 1.1 Comparative Example 2-3 30.2 5.7 2.4 Example 8 2 30.5 2.1 0.8 Example 9 2 36.8 2.2 0.9 Comparative Example 3 − 12.4 1.3 0.7 Example 10 2 87.6 3. 3.0 Example 11 2 49.2 3.4 1.7 Example 12 2 55.3 2.8 1.5 Example 13 2 52.5 2.8 1.0 Comparative Example 4-29.0 5 .5 2.5 Example 14 2 52.1 2.0 1.0 Comparative Example 5-22.0 2.3 1.5 Example 15 2 52.4 2.1 1.0 ━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━p, p'-BPA: 2,2-bis (4'-oxyphenyl) propane o, p'-BPA: 2- (2'-oxyphenyl) -2- (4'-oxyphenyl) propanone (isomer) COD: 2,2,4-trimethyl-4- (4'-oxyphenyl) Chroman (reaction by-product)

B: Preparation Method of Organopolymer Siloxane Catalyst Having Sulfonic Acid Group and Hydrocarbon Group Containing Mercapto Group (The physical properties of the catalyst obtained by each preparation method are listed in Table 4.) (e) Catalyst 1 3 -The organic polymer siloxane having a mercapto group prepared from tetraethoxysilane of the same weight as mercaptopropyltrimethoxysilane (cocatalyst 2) 2.82 g (mercapto group content 7.64 mmol) was placed in a 100 ml eggplant flask, and styrene was added to this. Sodium sulfonate 1.57g (7.64mmo
l), 10 ml of water and 3 ml of concentrated hydrochloric acid were added, and the mixture was heated with stirring under reflux for 1 hour. This is left to cool and the filtered white solid is thoroughly washed with a large amount of water until the filtrate becomes neutral and dried at 100 ° C. for 4 hours to obtain an organic polymer having a sulfonic acid group- and mercapto group-containing hydrocarbon group. A siloxane was obtained. This was used as a catalyst 1 in the reaction.

(F) Catalysts 2 to 4 All of the same operating methods and conditions as in the preparation method of Catalyst 1 except that the organopolymer siloxane having a mercapto group was changed to the above-mentioned other cocatalysts listed in Table 3. It was prepared in. This was designated as catalyst 2-3.

(G) Catalysts 5 to 7 Instead of sodium styrenesulfonate, 9.62 mmol of sodium vinylsulfonate, sodium allylsulfonate or sodium methallylsulfonate listed in Table 3 was used.
All were prepared by the method of preparing catalyst 1 except for charging. This was designated as Catalyst 5-7. These catalysts 1 to 7 are listed in Table 3.

(H) Catalyst 8 A 1000 ml three-necked flask equipped with a stirrer and a cooling pipe.
Cl (CH ₂)₃Si (OMe)₃0.60m
ol, Si (OEt)_Four1.40 mol, ethanol 2
Add 00 ml and add 92 ml of 0.01N hydrochloric acid.
Was dripped. Heat this solution to 80-90 ° C and gently
Concentrate gently until ethanol does not evaporate.
Always make a viscous solution, and add hexane 180m to it.
l, 120 ml of ethanol was added, and 28%
Add a mixture of 100 ml near water and 540 ml water.
And stirred at room temperature for 4 hours. This was filtered off and the solid
The body was washed with a large amount of water and dried at 120 ° C. Obtained
High content of chloropropyl group in the silica matrix
15.0 g of organic organosiloxane, Na₂SO₃10.32
g and 60 ml of water were added, and the mixture was heated with stirring at 100 ° C. for 50 hours.
Was. After cooling, the solid was filtered off and washed with a large amount of water.
Treated with hydrochloric acid and treated with Na⁺From the mold to H⁺Ion exchange to mold,
Solid acid with sulfonic acid groups immobilized on the matrix
Prepared. This solid acid 6.0 g (acid amount 1.25 mgeq
/ G) with sodium chloride aqueous solution⁺Ion exchange to mold
And dried under reduced pressure at 120 ° C for 4 hours, containing mercapto group
As a silane compound, HS (CH₂)₃Si (OMe)₃1
By adding 0 g and heating and stirring at 100 ° C. for 4 hours,
Silylated. This is filtered off, methanol, then aceto
The solids are washed well with water to remove unreacted HS (CH₂)₃Si
(OMe)₃After removing the⁺Back to the mold,
It was thoroughly washed with a large amount of pure water to remove residual hydrochloric acid. this
Further, it was dried in an oven at 120 ° C for half a day to obtain a catalyst 8.
Was.

(I) Catalyst 9 10.0 g of high molecular organosiloxane containing mercapto group (co-catalyst 2) prepared from the same weight of tetraethoxysilane as 3-mercaptopropyltrimethoxysilane described above was gradually added to 20 ml of concentrated HNO _3. In addition, the mixture was stirred for 1 hour. After the reaction, the white solid was filtered off, and the obtained solid was washed with a large amount of water to prepare a solid acid having a sulfonic acid immobilized on a silica matrix. 6.0 g of this solid acid (acid amount 1.70
(mgeq / g) was ion-exchanged with a sodium chloride aqueous solution to form Na ^+, and dried under reduced pressure at 120 ° C. for 4 hours to obtain HS (CH ₂ ) ₃ Si (OM) as a mercapto group-containing silane compound.
e) ₃ 10 g was added and silylated by heating and stirring at 100 ° C. for 4 hours. This was filtered off, and the solid was thoroughly washed with methanol and then acetone to remove unreacted HS (C
After removing H ₂ ) ₃ Si (OMe) ₃ , H ^{+ was} added with 6N hydrochloric acid.
After returning to the mold, it was thoroughly washed with a large amount of pure water to remove residual hydrochloric acid. This is further dried in an oven at 120 ° C for half a day,
It was designated as catalyst 9.

(J) Catalyst 10 The mercapto group-containing silane compound HS (CH ₂ ) ₃ Si (OMe) ₃ used for silylation with Catalyst 8 was converted into HSCH ₂ Si (C
Catalyst 10 was obtained by the same procedure and conditions except that H ₃ ) ₂ (OEt) was used.

(K) Catalyst 11 The mercapto group-containing silane compound HS (CH ₂ ) ₃ Si (OMe) ₃ used for silylation with the catalyst 9 was converted into HSCH ₂ Si (C
Catalyst 11 was obtained by the same procedure and conditions except that H ₃ ) ₂ (OEt) was used.

(L) Catalyst 12 49.28 g (200 mmo) of 3-glycidoxypropyltrimethoxysilane in a 1000 ml three-necked flask.
l), triethoxysilane 41.66 g (200 mmo
400 ml of ethanol was added to l) and well stirred. Then, 60 g of water was slowly added dropwise, and then Na ₂ SO _{3 was} added.
A solution prepared by dissolving 7 g in 50 ml of water was added dropwise, and water 2
After dropping 00 ml, the mixture was heated with stirring at 80 ° C. for 24 hours, and then the solvent was distilled off. This was dried at 120 ° C. for 24 hours. The dried solid was thoroughly washed with water and then dried again to obtain an organic polymer siloxane having an organic epoxy group bonded to a silica matrix. Organopolymer siloxane 10 g and NaH obtained in 1000 ml two neck flask
SO ₃ 10.5 g, a solution of the Na ₂ SO ₃ 25 g was dissolved in water 250ml was added and 6.5 hours heating with stirring at 120 ° C.. After allowing to cool, this was filtered, and the obtained white solid was thoroughly washed with water. This white solid was placed in a 500 ml beaker, 200 ml of 1N hydrochloric acid was added, and the mixture was stirred at room temperature for 1 hour. After filtering this and applying the same acid treatment again,
The solid was thoroughly washed with water and dried at 110 ° C. The resulting sulfonated solid acid (acid amount 0.735 mgeq /
g) 6.0 g was converted to Na ⁺ type with an aqueous sodium chloride solution, and then dried under reduced pressure at 120 ° C. for 4 hours. A mercapto group-containing silane compound, HS (CH ₂ ) ₃ Si (OM
e) ₃ 10 g was added and silylated by heating and stirring at 100 ° C. for 4 hours. This was filtered off, and the solid was thoroughly washed with methanol and then acetone to remove unreacted HS (C
After removing H ₂ ) ₃ Si (OMe) ₃ , H ^{+ was} added with 6N hydrochloric acid.
After returning to the mold, it was thoroughly washed with a large amount of pure water to remove residual hydrochloric acid. This was further dried in an oven at 120 ° C. for half a day to obtain a catalyst 12.

(M) Catalyst 13 In a 1000 ml three-necked flask, 38.06 g (200 mmol) of vinyltriethoxysilane, 41.66 g (200 mmol) of triethoxysilane were added to 1 part of ethanol.
00 ml was added and stirred. This solution was stirred at room temperature for 2 hours, and then pure water was added in an amount 5 times the required amount (1/2 of the molar amount of the alkoxy group of the added silane) by mole (3.5 mol).
Was slowly added dropwise, and after stirring at room temperature for 1 hour, 28%
After 40.0 g of ammonia water was added dropwise with stirring over about 1 hour, the liquid temperature was adjusted to 80 ° C., and heating and stirring was performed overnight. As a result, gelation of the liquid was confirmed. Then, the solvent and the like were distilled off under reduced pressure to obtain a solid. Pure water 10
00 ml was added and the mixture was washed with stirring at 80 ° C. for 4 hours. After cooling, the solid is separated by filtration and washed thoroughly with pure water, then 100
It was dried under reduced pressure at 4 ° C. for 4 hours, and the obtained solid was used as an organic polymer siloxane having a vinyl group. Next, put the polyorganosiloxane 15g two-neck flask 1000 ml, which was added Na ₂ SO ₃ 50 g, a solution of NaHSO _3, 21g of water 500 ml. This was heated to 70 ° C. with stirring, heated and stirred with blowing air for 46 hours, filtered, and the white solid was sufficiently washed with water. Then, the white solid was placed in a 500 ml beaker and 1N hydrochloric acid 2
00 ml was added and the mixture was stirred at room temperature for 1 hour. This was filtered, treated with hydrochloric acid again, filtered, and the solid was thoroughly washed with water and dried at 110 ° C. for 8 hours to obtain an organic polymer siloxane having an organic sulfonic acid group in the silica matrix. This solid acid 6.0 g (acid amount 1.39 mgeq
/ G) was subjected to ion exchange with Na ⁺ form with an aqueous sodium chloride solution, and then dried under reduced pressure at 120 ° C for 4 hours.
10 g of (CH ₂ ) ₃ Si (OMe) ₃ was added, and the mixture was heated and stirred at 100 ° C. for 4 hours for silylation. This was filtered off, the obtained solid was washed with methanol and then with acetone to remove unreacted HS (CH ₂ ) ₃ Si (OMe) ₃ , and then
The mixture was returned to the H ⁺ type with 6N hydrochloric acid and sufficiently washed with a large amount of pure water to remove residual hydrochloric acid. This is further oven 120 ℃,
It was dried for half a day and used as catalyst 13.

(N) Catalyst 14 Commercially available silica gel (MS gel: Dokai Chemical Industry Co., Ltd.) 10
After being dried under reduced pressure at 100 ° C. for 4 hours, it was placed in a 100 ml eggplant-shaped flask, and vinyltriethoxysilane 2 was added thereto.
5 g was added, and the mixture was heated with stirring at 100 ° C. for 4 hours. After cooling down,
After filtration, the obtained white solid was thoroughly washed with methanol and then dried at 120 ° C. This organic polymer siloxane 15
g into a 1000 ml two-necked flask and add Na ₂
SO ₃ 50 g, NaHSO ₃ 21 g dissolved in 500 ml of water was added to the solution, and the mixture was blown with air at 70 ° C. to 4
After heating and stirring for 6 hours, the white solid obtained was thoroughly washed with water, put into a 500 ml beaker, 200 ml of 1N hydrochloric acid was added, and the mixture was stirred at room temperature for 1 hour. This was filtered, treated with hydrochloric acid again, filtered, and the solid was thoroughly washed with water and dried at 110 ° C. for 8 hours to obtain an organic polymer siloxane having an organic sulfonic acid group bonded to a silica matrix. This solid acid (6.0 g) (acid amount: 0.58 mgeq / g) was treated with an aqueous sodium chloride solution to give N.
After ion-exchanged to form a ⁺ , it was dried under reduced pressure at 120 ° C. for 4 hours, 10 g of HS (CH ₂ ) ₃ Si (OMe) ₃ , was added thereto, and the mixture was heated and stirred at 100 ° C. for 4 hours for silylation. This is filtered off and the solid is washed with methanol then acetone,
After unreacted HS (CH ₂ ) ₃ Si (OMe) ₃ was removed, it was returned to H ⁺ type with 6N hydrochloric acid, and sufficiently washed with a large amount of pure water to remove residual hydrochloric acid. 120 more in the oven
After drying at ℃ for half a day, it was designated as catalyst 14.

(O) Catalyst 15 Commercially available silica gel (MS gel: Dokai Chemical Industry Co., Ltd.) 10
After being dried under reduced pressure at 100 ° C. for 4 hours, it was placed in a 100 ml eggplant flask, and Cl (CH ₂ ) ₃ Si (OM
e) ₃ , 25 g was added and the mixture was heated and stirred at 100 ° C. for 4 hours for silylation. After allowing to cool, it was filtered, and the obtained white solid was thoroughly washed with methanol and then dried at 120 ° C.
15 g of this organic polymer siloxane was added to Na ₂ SO ₃ , 1
0.32 g and 60 ml of water were added and the mixture was heated with stirring at 100 ° C. for 50 hours. After cooling, the solid was filtered off, washed with a large amount of water, treated with dilute hydrochloric acid and ion-exchanged from Na ⁺ type to H ⁺ type to prepare a solid acid having a sulfonic acid fixed on a silica matrix. This solid acid 6.0 g (acid amount 0.79 mg
eq / g) was ion-exchanged with an aqueous sodium chloride solution to form Na ⁺ , and then dried under reduced pressure at 120 ° C. for 4 hours to obtain HS (C
H ₂ ) ₃ Si (OMe) ₃ , 10 g was added, and the mixture was heated at 100 ° C. for 4 hours.
Silylation was carried out by heating and stirring for an hour. This was filtered off, the solid was thoroughly washed with methanol and then with acetone to remove unreacted HS (CH ₂ ) ₃ Si (OMe) ₃ , and then 6
The mixture was returned to the H ⁺ type with N hydrochloric acid and thoroughly washed with a large amount of pure water to remove residual hydrochloric acid. This was further dried in an oven at 120 ° C. for half a day to obtain a catalyst 15.

(P) Catalyst 16 Commercially available silica gel (MS gel: Dokai Chemical Industry Co., Ltd.) 10
After being dried under reduced pressure at 100 ° C. for 4 hours, it was placed in a 100 ml eggplant flask, and HS (CH ₂ ) ₃ Si (OM
e) ₃ , 25 g was added, and the mixture was heated and stirred at 100 ° C. for 4 hours for silylation. After allowing to cool, it was filtered, and the white solid was thoroughly washed with methanol and then dried at 120 ° C. 15 g of the obtained organic polymer siloxane was gradually added to 30 ml of concentrated nitric acid, and the mixture was stirred at room temperature for 1 hour. After the reaction, the solid was filtered off, washed with a large amount of water, and then dried to prepare a solid acid having a sulfonic acid immobilized on a silica matrix. 6.0 g of this solid acid (acid amount 0.55 mgeq / g) was converted to Na ⁺ type with an aqueous sodium chloride solution, dried under reduced pressure at 120 ° C. for 4 hours, and then HS (CH ₂ ) ₃ Si (OMe) ₃ 10 g Was added, and the mixture was heated and stirred at 100 ° C. for 4 hours for silylation. This was filtered off, the solid was washed well with methanol and then with acetone, and unreacted HS (CH ₂ ) ₃ Si (OMe) ₃
After removing the residue, the mixture was returned to the H ⁺ type with 6N hydrochloric acid and sufficiently washed with a large amount of pure water to remove residual hydrochloric acid. This was further dried in an oven at 120 ° C. for half a day to obtain a catalyst 16.

(Q) Catalyst 17 36.06 g (0.04) of phenyltriethoxysilane was placed in a 1000 ml three-necked flask equipped with a stirrer and a cooling tube.
15 mol), 72.92 g of Si (OEt) ₄ (0.3
5 mol) and 62.5 ml of ethanol are added, and 16.7 ml of 0.01N hydrochloric acid is added dropwise thereto. The solution is heated to 80-90 ° C and slowly concentrated. Concentration until ethanol does not evaporate results in a very viscous solution. Add 15 ml of hexane and 2 parts of ethanol to this.
2.5 ml was added, and further 28% ammonia water 25.0
A mixture of 13 ml of water and 135.0 ml of water was added dropwise, and the mixture was stirred at room temperature for 4 hours. This was separated by filtration, washed with a large amount of water, and dried at 120 ° C. 100 ml of concentrated sulfuric acid was added to 10.0 g of a high molecular weight organosiloxane having a phenyl group as a functional group in the silica matrix thus obtained.
The mixture was heated and stirred at 0 ° C for 3 hours. After cooling, a large amount of water was added, the solid was filtered off, and washed with a large amount of water to prepare a solid acid having sulfonic acid immobilized on a silica matrix. After ion-exchange of 6.0 g of this solid acid (acid amount 0.86 mgeq / g) into Na ⁺ type with an aqueous sodium chloride solution, 120
After drying under reduced pressure at 4 ° C. for 4 hours, 10 g of HS (CH ₂ ) ₃ Si (OMe) ₃ was added as a mercapto group-containing silane compound,
Silylation was carried out by heating and stirring at 100 ° C. for 4 hours. This was filtered off, and the solid was thoroughly washed with methanol and then acetone to remove unreacted HS (CH ₂ ) ₃ Si (OMe) ₃
After removing the residue, the mixture was returned to the H ⁺ type with 6N hydrochloric acid and sufficiently washed with a large amount of pure water to remove residual hydrochloric acid. This was further dried in an oven at 120 ° C. for half a day to obtain a catalyst 17.

[0098]

[Table 3] Table 3 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ silane used for hydrolysis ──── ──────────────────────────────── mercapto group-containing polymer siloxane sulfonic acid compound catalyst ━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Co-catalyst 2 Sodium styrene sulfonate Catalyst 1 Co-catalyst 3 Sodium styrene sulfonate Catalyst 2 Co-catalyst 4 Styrene Sodium sulfonate Catalyst 3 Promoter 5 Sodium styrenesulfonate Catalyst 4 Promoter 2 Sodium vinyl sulfonate Catalyst 5 Promoter 2 Sodium allyl sulfonate Catalyst 6 Promoter 2 Sodium methallyl sulfonate Catalyst 7 ━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━ ━━━━━━━

[0099]

[Table 4] Table 4 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Analysis results ─────── ─────────────────────────────── SH amount Acid amount Catalyst (mgeq / g) (mgeq / g) Si / C atomic ratio ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Catalyst 1 2.17 0.50 0.451 Catalyst 2 2.39 0.54 0.359 Catalyst 3 1.99 0.48 0.605 catalyst 4 2.04 0.47 0.430 catalyst 5 2.00 0.67 0.561 catalyst 6 1.93 0.76 0.528 catalyst 7 1.80 0.90 0.500 catalyst 8 0.46 1.25 1.009 catalyst 9 0.20 1.70 0.625 catalyst 10 0.21 1.25 1.058 catalyst 11 0.13 1.70 0.632 catalyst 12 0.15 0.74 0.094 catalyst 13 0.55 1.39 0.631 catalyst 14 0.14 0.58 9.806 catalyst 15 0.15 0.79 5.477 catalyst 16 0.14 0.55 7.566 catalyst 17 0.16 0.86 0.170 ━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━

Examples 16 to 22 In a 70 ml pressure-resistant reactor, 3.80 g (65.5 mmol) of acetone, 33.00 g (351.1 mmol) of phenol, and 2.00 of any of catalysts 1 to 2.00
After charging g and pressurizing the pressure resistant reactor with nitrogen gas to a pressure of 5 kg / cm ² gauge, the mixture was heated and stirred at 100 ° C. for 2 hours to carry out the reaction. After completion of the reaction, the reaction solution was cooled to room temperature and released, and the reaction solution was taken out and analyzed and quantified by liquid chromatography. The results are shown in Table 5.
As shown in Table 1, bisphenol A was produced in good yield.

Example 23 All of Example 1 except that the charged amount of acetone was 1.90 g.
The reaction was carried out under the same conditions as in 6. As shown in Table 5, bisphenol A was produced in a high yield with respect to acetone.

Example 24 The reaction was carried out under the same conditions as in Example 16 except that the reaction temperature was 120 ° C. and the reaction time was 1 hour. As shown in Table 5, bisphenol A was produced in high yield.

Example 25 The reaction was carried out under the same conditions as in Example 16 except that the amount of catalyst 1 was 4.0 g. The results are as shown in Table 5.
By increasing the amount of catalyst, the yield of bisphenol A was further increased and the selectivity was also improved.

[0104]

Table 5 Table 5 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Catalyst product yield (charged acetone Reference%) p, p'-BPA o, p'-BPA COD ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example 16 1 36.5 1.9 1.2 Example 17 2 35.2 2.0 1.4 Example 18 3 35.4 2.1 1.1 Example 19 4 36.1 2. 5 0.9 Example 20 5 29.0 1.9 1.0 Example 21 6 29.4 1.8 1.1 Example 22 7 30.5 2.0 0.8 Example 23 1 55.8 2.2 1.1 Example 24 1 56.6 4.0 3.0 Example 25 1 50.2 2.2 1.5 ━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━ 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)

Examples 26-35 In a 70 ml pressure resistant reactor, 3.80 g (65.5 g) of acetone was added.
mmol) and phenol 33.0 g (351.1 mmo)
1), 2.00 g of any one of the catalysts 8 to 17 was charged,
After pressurizing the pressure resistant reactor to 5 kg / cm ² gauge pressure with nitrogen gas, the mixture was heated and stirred at 100 ° C. for 2 hours to carry out the reaction. After completion of the reaction, the reaction solution was cooled to room temperature and released, and the reaction solution was taken out and analyzed and quantified by liquid chromatography. The results are shown in Table 6
As shown in Table 1, bisphenol A was produced in a very good yield.

Comparative Example 6 The reaction was carried out under the same conditions as in Example 26 except that the sulfonic acid group-containing polymer siloxane before the silylation treatment was used as the catalyst in Example 26. The results are shown in Table 6
As described above, the yield of bisphenol A was low and the selectivity of p, p′-bisphenol A was low when the mercapto group was left unmodified.

Examples 36 to 37 The catalysts used in Examples 26 to 27 were taken out, thoroughly washed with methanol, dried, and reused under the same conditions as in Examples 26 to 27. The results showed that the activity was maintained as shown in Table 6.

Comparative Example 7 In Example 26, a mercapto group was modified by cation exchange of 15% of protons of a cation exchange resin (Amberlist 15 manufactured by Rohm and Haas Co.) in place of the catalyst 8 with cysteamine hydrochloride. It was used as a catalyst and reacted under the same conditions. The results are shown in Table 6.

Comparative Example 8 The catalyst used in Comparative Example 7 was taken out, washed thoroughly with methanol, dried, and reused under the same conditions as in Example 26. As a result, as shown in Table 6, the activity was slightly decreased, and the selectivity of p, p'-bisphenol A was also decreased.

Example 38 The reaction was carried out under the same conditions as in Example 26 except that the reaction temperature was 120 ° C. As shown in Table 6, the yield of bisphenol A was increased, but the selectivity of p, p'-bisphenol A was decreased.

Example 39 The amount of acetone charged in Example 26 was half that of 1.60 g (3
The reaction was carried out under the same conditions except that it was 2.8 mmol). As shown in Table 6, the yield of bisphenol A was increased by increasing the phenol / acetone ratio.

[0112]

[Table 6] Table 6 Product Yield (Acetone Reference Based on the Charge Acetone Based on the Acetone Charged in the Acetone Product) [Table 6] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ %) Catalyst ──────────────────────── p, p'-BPA o, p'-BPA COD ━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━ Example 26 8 45.7 1.6 0.5 Example 27 9 44.9 1.00 .3 Example 28 10 43.9 1.6 0.5 Example 29 11 40.1 1.0 0.5 Example 30 12 40.2 1.0 0.4 Example 31 13 48.7 1. 6 0.5 Example 32 14 39.1 1.4 1.0 Example 33 15 40.3 1.5 1.0 Example 34 16 38.9 1.0 0.5 Example 35 17 47.1 1.6 0.4 Example 36 8 46.0 1.6 0.5 Example 37 9 45.4 1.0 0.5 Example 38 8 65.1 2.4 1.0 Example 39 8 66.3 2.5 1.0 Comparison Example 6 3.2 1.0 0.5 Comparative Example 7 36.7 1.7 1.0 Comparative Example 8 32.1 1.6 1.0 ━━━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━p, p'-BPA: 2,2-Vise (4'-oxyphenyl) proton o, p'-BPA: 2- (2'-Oxyphenyl) -2- (4'-oxyphenyl) propane (isomer) COD: 2,2,4-trimethyl-4- (4'-oxyphenyl) chroman (reaction by-product)

[0113]

According to the present invention, the following effects can be obtained. (1) Bisphenol A can be produced with good yield and selectivity by the dehydration condensation reaction of acetone and phenol. (2) It is possible to produce bisphenol A, which is industrially important, significantly in terms of safety, process, and economy. As described above, according to the present invention, it is possible to provide the industrially excellent method for producing bisphenol A.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // C07B 61/00 300

Claims (11)

[Claims] 1. A process for producing bisphenol A, which comprises reacting phenol and acetone in the presence of an organic polymer siloxane having a mercapto group-containing hydrocarbon group and an acid. 2. The organic polymer siloxane having a mercapto group-containing hydrocarbon group and the acid are organic polymer siloxanes having a mercapto group-containing hydrocarbon group and a sulfonic acid group in the organic polymer siloxane. Method. 3. The method according to claim 2, wherein the sulfonic acid group is an aromatic sulfonic acid group. 4. The method according to claim 2, wherein the sulfonic acid group is an alkylsulfonic acid group. 5. The mercapto group-containing hydrocarbon group is a mercaptomethyl group, 2-mercaptoethyl group, 3-mercapto-n-propyl group, p-mercaptophenyl group or p.
-The method according to claim 1, 2, 3 or 4, which is at least one mercapto group-containing hydrocarbon group selected from the group consisting of mercaptomethylphenyl groups. 6. A general formula: X _n Si (R ₁ ) _4-n (wherein n is an integer of 1 or more and 3 or less, and X is a group consisting of a chlorine atom, a bromine atom, an iodine atom and an alkoxy group. It is at least one selected, and R ₁ is a carbon number of 1 or more and 2 having at least one mercapto group (SH group).
A hydrocarbon group having 0 or less, a hydrocarbon group having an aromatic group having 6 to 20 carbon atoms, an alkyl group having 1 to 15 carbon atoms having at least one halogen atom, at least one carbon, carbon unsaturated Number of carbon atoms having a bond of 2 or more 15
It is at least one hydrocarbon group selected from the group consisting of the following olefinic hydrocarbon groups and hydrocarbon groups having at least one epoxy group and having 2 to 15 carbon atoms, and Si represents a silicon atom. . The organic polymer siloxane obtained by hydrolyzing at least one of the silane compounds represented by) is subjected to a sulfonation treatment to sulfonate the hydrocarbon group (R ₁ ) to obtain an organic polymer siloxane having a sulfonic acid group. After that, the general formula: X _n Si (R ₂ ) _4-n (where n is an integer of 1 or more and 3 or less, X is a chlorine atom,
At least one selected from the group consisting of a bromine atom, an iodine atom and an alkoxy group, R ₂ is a hydrocarbon group having 1 to 20 carbon atoms and at least one mercapto group (SH group), and Si is Represents a silicon atom. ) An organopolymer siloxane having a mercapto group-containing hydrocarbon group and a sulfonic acid group, which is obtained by silylation with at least one silane compound represented by the formula (1) and then hydrolysis. 7. A general formula: X _n Si (R ₁ ) _4-n (wherein n is an integer of 1 or more and 3 or less, and X is a group consisting of a chlorine atom, a bromine atom, an iodine atom and an alkoxy group. It is at least one selected, and R ₁ is a carbon number of 1 or more and 2 having at least one mercapto group (SH group).
A hydrocarbon group having 0 or less, a hydrocarbon group having an aromatic group having 6 to 20 carbon atoms, an alkyl group having 1 to 15 carbon atoms having at least one halogen atom, at least one carbon, carbon unsaturated Number of carbon atoms having a bond of 2 or more 15
It is at least one hydrocarbon group selected from the group consisting of the following olefinic hydrocarbon groups and hydrocarbon groups having at least one epoxy group and having 2 to 15 carbon atoms, and Si represents a silicon atom. . In addition to the compound, at least one kind of silane compound represented by the general formula: SiX ₄ (wherein X is at least one kind selected from the group consisting of chlorine atom, bromine atom, iodine atom and alkoxy group) Yes,
Si is a silicon atom. The organic polymer siloxane having a mercapto group-containing hydrocarbon group and a sulfonic acid group according to claim 6, which contains at least one silane compound represented by the formula (4). 8. Silica gel of the general formula: X _n Si (R ₁ ).
_4-n (In the formula, n is an integer of 1 or more and 3 or less, X is at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom and an alkoxy group, and R ₁ is a mercapto group. 1 or more carbon atoms having at least one (SH group) 2
A hydrocarbon group having 0 or less, a hydrocarbon group having an aromatic group having 6 to 20 carbon atoms, an alkyl group having 1 to 15 carbon atoms having at least one halogen atom, at least one carbon, carbon unsaturated Number of carbon atoms having a bond of 2 or more 15
It is at least one hydrocarbon group selected from the group consisting of the following olefinic hydrocarbon groups and hydrocarbon groups having at least one epoxy group and having 2 to 15 carbon atoms, and Si represents a silicon atom. . ) Is silylated with at least one silane compound and then hydrolyzed to obtain an organic polymer siloxane, which is subjected to a sulfonation treatment to give an organic polymer siloxane having a sulfonic acid group, and then further represented by the general formula: X _n Si (R ₂ ) _4-n (where n is 1
It is an integer of 3 or more, X is at least one selected from the group consisting of chlorine atom, bromine atom, iodine atom and alkoxy group, and R ₂ is the number of carbon atoms having at least one mercapto group (SH group). It is a hydrocarbon group of 1 or more and 20 or less, and Si represents a silicon atom. ) An organopolymer siloxane having a mercapto group-containing hydrocarbon group and a sulfonic acid group, which is obtained by silylation with at least one silane compound represented by the formula (1) and then hydrolysis. 9. A compound represented by the general formula: X _n Si (R ₁ ) _4-n (wherein n is an integer of 1 or more and 3 or less, and X is a group consisting of a chlorine atom, a bromine atom, an iodine atom and an alkoxy group). It is at least one selected, and R ₁ is a carbon number of 1 or more and 2 having at least one mercapto group (SH group).
A hydrocarbon group having 0 or less, a hydrocarbon group having an aromatic group having 6 to 20 carbon atoms, an alkyl group having 1 to 15 carbon atoms having at least one halogen atom, at least one carbon, carbon unsaturated Number of carbon atoms having a bond of 2 or more 15
It is at least one hydrocarbon group selected from the group consisting of the following olefinic hydrocarbon groups and hydrocarbon groups having at least one epoxy group and having 2 to 15 carbon atoms, and Si represents a silicon atom. . The organic polymer siloxane obtained by hydrolyzing at least one of the silane compounds represented by) is subjected to a sulfonation treatment to sulfonate the hydrocarbon group (R ₁ ) to obtain an organic polymer siloxane having a sulfonic acid group. After that, the general formula: X _n Si (R ₂ ) _4-n (where n is an integer of 1 or more and 3 or less, X is a chlorine atom,
At least one selected from the group consisting of a bromine atom, an iodine atom and an alkoxy group, R ₂ is a hydrocarbon group having 1 to 20 carbon atoms and at least one mercapto group (SH group), and Si is Represents a silicon atom. ) A method for producing an organic polymer siloxane having a mercapto group-containing hydrocarbon group and a sulfonic acid group, which comprises silylating with at least one silane compound represented by the formula (1) and then hydrolyzing. 10. A compound represented by the general formula: X _n Si (R ₁ ) _4-n (wherein n is an integer of 1 or more and 3 or less, and X is a group consisting of a chlorine atom, a bromine atom, an iodine atom and an alkoxy group). It is at least one selected, and R ₁ is a carbon number of 1 or more and 2 having at least one mercapto group (SH group).
A hydrocarbon group having 0 or less, a hydrocarbon group having an aromatic group having 6 to 20 carbon atoms, an alkyl group having 1 to 15 carbon atoms having at least one halogen atom, at least one carbon, carbon unsaturated Number of carbon atoms having a bond of 2 or more 15
It is at least one hydrocarbon group selected from the group consisting of the following olefinic hydrocarbon groups and hydrocarbon groups having at least one epoxy group and having 2 to 15 carbon atoms, and Si represents a silicon atom. . In addition to the compound, at least one kind of silane compound represented by the general formula: SiX ₄ (wherein X is at least one kind selected from the group consisting of chlorine atom, bromine atom, iodine atom and alkoxy group) Yes,
Si is a silicon atom. The method for producing an organic polymer siloxane having a mercapto group-containing hydrocarbon group and a sulfonic acid group according to claim 9, which comprises at least one silane compound represented by the formula (1). 11. Silica gel is represented by the general formula: X _n Si (R ₁ ).
_4-n (In the formula, n is an integer of 1 or more and 3 or less, X is at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom and an alkoxy group, and R ₁ is a mercapto group. A hydrocarbon group having at least one (SH group) and having 1 to 20 carbon atoms, a hydrocarbon group having an aromatic group having 6 to 20 carbon atoms, and a carbon number of 1 to 15 having at least one halogen atom. Alkyl group, at least one carbon, and having 2 or more carbon atoms having a carbon unsaturated bond 1
5 or less olefinic hydrocarbon groups and at least 1
Is at least one kind of hydrocarbon group selected from the group consisting of hydrocarbon groups having 2 to 15 carbon atoms and having 1 epoxy group, and Si represents a silicon atom. ) Was silylated with at least one of the silane compound represented by, then after a polyorganosiloxane having a sulfonic acid group by hydrolysis The polyorganosiloxane obtained by sulfonation process, further the general formula: X _n Si (R ₂ ) _4-n (wherein n is an integer of 1 or more and 3 or less, X is a chlorine atom, a bromine atom,
At least one selected from the group consisting of an iodine atom and an alkoxy group, R ₂ is a hydrocarbon group having 1 to 20 carbon atoms and having at least one mercapto group (SH group), and Si is a silicon atom. Represent ) A method for producing an organic polymer siloxane having a mercapto group-containing hydrocarbon group and a sulfonic acid group, which comprises silylating with at least one silane compound represented by the formula (1) and then hydrolyzing.