ES2348484T3 - METHOD FOR THE PREPARATION OF BISPHENOL IN THE PRESENCE OF A MODIFIED ACID ION EXCHANGE RESIN. - Google Patents

Abstract

The use of a modified acidic ion exchange resin as a catalyst to prepare bisphenol, wherein at least one class of cationic compound selected from the following (B) and (D) is ionically bound to an acid functional group of an exchange resin acidic ionic: (B) a cationic compound represented by the formula (2): ** (See formula) ** in which N represents a nitrogen atom, and R1, R2, R3 and R4 independently represent an alkyl group or a aryl group, each of which contains 1 to 20 carbon atoms and does not contain any mercapto group or precursor thereof or amide bond; (D) an N-substituted aromatic compound containing cationic nitrogen that does not contain any mercapto groups, nor precursor thereof or amide bond, wherein said N-substituted aromatic compound containing cationic nitrogen is an N-methylpyridinium salt, a cetylpyridinium salt, a dodecylpyridinium salt, an N-methylquinolinium salt or an N-ethylquinolinium salt.

Description

Method for the preparation of bisphenol in presence of a modified acidic ion exchange resin.

Technical field

The present invention relates to the use of a modified acidic ion exchange resin as catalyst and a a procedure for preparing bisphenol using the same. In In particular, the present invention relates to a catalyst of modified ion exchange resin that has a high reactive selectivity and a procedure to prepare bisphenol which comprises reacting phenolic compounds with ketone and / or aldehyde in the presence of the catalyst.

Prior art

Bisphenol A [2,2-bis- (4-hydroxyphenyl) propane] it is usually prepared by reacting phenol with acetone in presence of a homogeneous acid or a solid acid catalyst. The reaction mixture includes unreacted acetone, non phenol reacted, water and other by-products formed by the reaction, in addition to bisphenol A. The main component of the by-products is 2- (2-hydroxyphenyl) -2- (4-hydroxyphenyl) propane (hereinafter, designated as o, p'-BPA), and also includes trisphenol, a polyphenol compound, a compound of  Chroman and colored impurities.

Examples of homogeneous acid to use as Catalyst include hydrochloric acid and sulfuric acid. At in case the homogeneous acid is used, since it is possible that the reaction proceed with precipitation of crystals from an adduct of phenol with bisphenol A by reacting at lower temperatures, bisphenol A can be prepared with a high conversion from acetone and high selectivity reducing the amount of or, p'-BPA underproduced as isomer thereof. Without However, homogeneous acid such as hydrochloric acid requires the removal of the catalyst from the reaction mixture or the neutralization of the reaction mixture, and therefore the process. The homogeneous dissolution of the acid in the solution of reaction additionally causes corrosion of the apparatus used in the reaction. Therefore, the vessels of the reaction apparatus they should be made of expensive anticorrosive materials, being by both uneconomic.

As a solid acid catalyst, it is used usually an acid-type cation exchange resin sulfonic The reaction to prepare bisphenol A proceeds essentially only with an acid catalyst, but if said solid acid catalyst, the process in which the acetone diffuses from the surface of the particles of catalyst to an active catalyst site, and therefore Reduce reaction speed. Therefore, generally a procedure to improve catalytic activity and selectivity  comprises allowing a compound containing a group to coexist Mercapto in the reaction system. Specifically, it can mention a procedure to pass any type of compound containing a mercapto group, such as alkyl mercaptan, together with phenol and acetone as raw materials, through a fixed bed reactor filled with a resin cationic exchange of sulfonic acid type (publication of Japanese patent application examined no. 45-10337, U.S. Pat. No. 6414200), a procedure to covalently join a part of the groups sulfonic acid of the acid-type cation exchange resin sulfonic acid with a compound that contains a mercapto group, and a procedure to ionically bind a part of the acid groups sulfonic acid in an acid-type cation exchange resin sulfonic acid with a compound that contains a mercapto group (Japanese Patent Application Publication Examined No. 46-19953). In the procedure to pass a type any of a compound containing a mercapto group, such as alkyl mercaptan, together with phenol and acetone as raw materials, through a fixed bed reactor filled with a resin cationic exchange of sulfonic acid type, since usually a certain amount of a compound containing a mercapto group in the reaction system, the compound that contains a mercapto group can cause coloration of bisphenol A, although it is advantageous if the catalyst deterioration Therefore, the compound containing a Mercapto group should withdraw and recover. On the other hand, in the procedure to join a part of the sulfonic acid groups in a sulfonic acid type cation exchange resin with a compound that contains a mercapto group, it is advantageous that the loss of compound containing a mercapto group is small, and therefore it is not necessary to recover the compound it contains a mercapto group, compared to the procedure in which there is any type of compound that contains a group Mercapto in the reaction system. In particular, the publications Japanese unexamined patent application number 08-187436, 08-089819 and 10-211433 describe that a speed of sufficient reaction of acetone by modifying the structure of a compound that contains a mercapto group that binds to a resin of strongly acidic ion exchange.

On the other hand, for example, it has been reviewed also that improves the activity of an exchange resin sulfonic acid type cationic acid catalyst, which was less than that of the homogeneous acid described above. In first place, in the case where the resin particle diameter of cationic exchange of sulfonic acid type to be used be large, since the raw reaction materials are not they diffuse sufficiently in the particles, you don't get a Enough acetone conversion. Therefore, the publication of Japanese unexamined patent application no. 62-178532 proposes to use fine particles that have an effective diameter of 0.3 mm or less, or an exchange resin Sulfonic acid type cationic powder. Additionally, the Japanese Unexamined Patent Application Publication No. 6-340563 also provides a diameter of particle of an acid-type cation exchange resin a use and a degree of particle diameter distribution, and specify a more preferred range thereof. In addition, the Japanese Unexamined Patent Application Publications No. 4-268316 and 2002-253971 describe a procedure to form an exchange resin product cationic sulfonic acid type having a particle diameter wanted. As such, the particle diameter of a resin of cationic exchange of sulfonic acid type is a factor important to get a sufficient reaction conversion.

In addition, several kinds of improvements have been made to the structure of a resin product that is the basic material of a cationic exchange resin of the sulfonic acid type. The cationic exchange resin of sulfonic acid type is a resin obtained by sulfonating a copolymer of styrene-divinylbenzene obtained by copolymerizing styrene and divinylbenzene. He divinylbenzene in polymerization not only prevents a chain of Polystyrene dissolves in an organic solvent, but also It is an important factor to control pore size (micropore gel) of the acid-type cation exchange resin sulfonic formed by capturing a polar solvent by its content, or The mechanical strength of the cation exchange resin of sulfonic acid type. In other words, an exchange resin cationic sulfonic acid type with a low content of divinylbenzene has a high catalytic activity due to a Large gel micropore, but the mechanical strength is low. In addition, if the content of the content is high, the mechanical resistance increases, but the gel micropore size is reduces, which causes reduced activity. For a resin of ion exchange of which the degree of crosslinking increases by increase the content of divinylbenzene, one can be mentioned that it forms a large hole in the particles that has a size of 20 nm or more, designated as "macropore", by a treatment physical to improve diffusion in particles.

However, in the case where a resin of ion exchange that has macroporos adsorbs molecules that they have a high polarity, such as water, a structure crosslinked tends to inhibit particle agglomeration caused by swelling, which if necessary collapses when it cannot withstand more swelling pressure. The publications of Japanese unexamined patent application no. 5-97741 and 6-320009 describe a procedure that complements the respective defects by filling simultaneously an acid-type cation exchange resin sulfonic having a low divinylbenzene content and a resin of cationic exchange of sulfonic acid type which has a high Divinylbenzene content in a reactor. Additionally, the WO 2000/00454 (Nippon Steel Chemical Co., Ltd.) reviews a improved reaction conversion, suggesting a resin of cationic exchange of sulfonic acid type that has micropores large gel by using large molecules such as divinylbiphenyl instead of divinylbenzene.

As such, various have been examined technologies for the catalyst, but none has been satisfactory with respect to selectivity. Even when the activity is slightly reduce, if possible develop a catalyst that have a high selectivity, the burden of the procedure of by-product recovery can be reduced in the procedure of preparation and the phenol / acetone ratio as raw materials can be reduced by raising the reaction temperature without harming the selectivity, and therefore the recovery cost of phenol It can be greatly reduced. Here, the reduced level of activity can be compensated by increasing the size of the reactor, so that the cost increase in the preparation of bisphenol is extremely small. Additionally, with a view to the applications industrial, it is desirable to improve the life of the catalysts. By therefore, the development of a catalyst that has a High selectivity and a long life.

[Patent document 1]: US patent nº 6,414,200.

[Patent document 2]: publication of Japanese unexamined patent application no. 08-089819.

US 2002/123656 A1 discloses the condensation catalyzed by phenol acid with acetone in the presence of a thiol promoter to produce bisphenol A. The catalyst used is an acid resin catalyst modified with amine prepared from acid resins such as polystyrene sulfonated by neutralizing a portion of the groups functional acids with an amine such as pyridine.

US 4,303,551 A discloses solid fluorocarbon polymers containing acid groups sulfonic slopes supported on a solid substrate that prepared using an intermediate that is thermoplastic or soluble in a measurable measure in a solvent. The intermediate conforms to the desired form and then the intermediate is converted as desired in the form of sulfonic acid for use as a catalyst.

According to US 6,281,400 B1, it refers to a procedure for the preparation of a microcomposite material catalytic from a silicate and an exchange resin highly fluorinated ionic, and discloses functional groups sulfonate represented by the formula SO3 NR4, in which R_ {1} -R4 {are the same or different and they represent H, CH 3 or C 2 H 5.

US 4,629,710 A refers to a polyvinyl aromatic resin comprising SO 3 H groups, of which 50% have been neutralized with alkali ions, alkaline earth or ammonium ions.

Disclosure of the invention

It is an object of the present invention provide an ion exchange resin catalyst that have greater bisphenol selectivity, compared to conventional ion exchange resins, used in a procedure for preparing bisphenol by reacting compounds phenolics with ketone, and a procedure to prepare the same.

The present inventors have carried out extensive studies to solve the problems, and as a result, they have found that using as an catalyst an acidic ion exchange resin in which at least one class of cationic compound selected from compounds represented by the formula (2) and a N- substituted nitrogen-containing aromatic compound is ionically bound to an acid functional group of the acidic ion exchange resin, bisphenol selectivity can be increased and the activity or selectivity of a catalyst can also be maintained for a longer period of time, and consequently bisphenol can be obtained in high yield. Therefore, they have completed the present invention.

In other words, the present invention provides the use of an acidic ion exchange resin as a catalyst for preparing bisphenol, wherein said acidic ion exchange resin is neutralized with at least one class of cationic compound selected from compounds represented by the formula ( 2) and a nitrogen-containing N- substituted aromatic compound, wherein said nitrogen-containing N- substituted aromatic compound is an N- methylpyridinium salt, a cetylpyridinium salt, a dodecylpyridinium salt, an N- methylquinolinium salt or an ethylquinolinium salt, a catalyst comprising the ion exchange resin and a process for preparing bisphenol using the catalyst.

Best way to carry out the invention

As the ion exchange resin used in the present invention an ion exchange resin is preferable acidic and includes, for example, one in which a group is introduced sulfone in a styrene-divinylbenzene copolymer which is designated as a strongly ion exchange resin general acid and a sulfonic acid based resin perfluoroalkylated such as Nafion.

A modified acidic ion exchange resin used as a catalyst to prepare bisphenol according to the present invention can be obtained by ionically binding at least one class of cationic compound selected from compounds represented by formula (2) and an N- substituted aromatic compound containing nitrogen, in wherein said N- substituted aromatic compound containing nitrogen is an N- methylpyridinium salt, a cetylpyridinium salt, a dodecylpyridinium salt, an N- methylquinolinium salt or an ethylquinolinium salt, with an acidic ion exchange resin.

one

in which N represents an atom of nitrogen and R 1, R 2, R 3 and R 4 represent independently an alkyl group or an aryl group, each of which contains 1 to 20 carbon atoms and does not contain any mercapto group or precursor thereof or link amide.

The cationic compound represented by the formula (2) that is used in the present invention is the compound in which N represents a nitrogen atom and R 1, R 2, R 3 and R 4 represent independently a hydrogen atom or an alkyl group, an aryl group or an alkoxy group, each of which contains 1 to 20 carbon atoms, preferably 1 to 16 carbon atoms, and more preferably 1 to 12 carbon atoms, and it does not contain any mercapto group or precursor thereof or amide bond, and at least one of R 1, R 2, R 3 and R 4 represents an alkyl group, an aryl group or an alkoxy group, each of which contains 1 to 20 carbon atoms, preferably 1 to 16 carbon atoms, and more preferably 1 to 12 carbon atoms and does not contain any mercapto groups or precursor thereof or amide bond. The expression "independently" indicates that R1, R2, R3 and R4 may be the same or different in structure. The structures of R 1, R 2, R 3 and R 4 are not particularly limited to other structures if they do not contain any mercapto group or precursor thereof or amide bond. They may contain a functional group such as an amino group, an ammonium group, a carbonyl group, a carboxyl group, a sulfonyl group, a sulfone group, a hydroxyl group, a nitrile group, a nitro group and an alkoxy group and an atom of halogen Additionally, R 1, R 2, R 3 and R 4 can be joined together to form a ring. In addition, a precursor of a mercapto group indicates a precursor producing a mercapto group, for example, such as thiazolidines, thioethers and
disulfides

Additionally, an N- substituted aromatic compound containing cationic nitrogen used in the present invention does not contain a mercapto group and / or a precursor of a mercapto group. In addition, a ring containing a nitrogen atom in the N- substituted aromatic compound containing cationic nitrogen preferably represents a 3 to 8 member ring, and more preferably a 5 to 7 member ring. In addition, this compound may be a monocyclic compound or a polycyclic compound having a condensed ring, and the number of nitrogen atoms may be one, two or more. The N- substituted aromatic compound containing cationic nitrogen includes, for example, a compound having a pyridine ring and a compound having a quinoline ring, and preferably an N- methylpyridinium salt, a cetylpyridinium salt, a Dodecylpyridinium salt, an N-methylquinolinium salt, an N- ethylquinolinium salt, etc.

In addition, in the process for preparing bisphenol by reacting phenolic compounds with ketone, at least one class of cationic compounds selected from compounds represented by the formula (2) and an N- substituted aromatic compound containing nitrogen in which said aromatic compound N - Nitrogen-containing substituted is an N- methylpyridinium salt, a cetylpyridinium salt, a dodecylpyridinium salt, an N-methylquinolinium salt or an N- ethylquinolinium salt, it may contain an amide bond.

The modified acidic ion exchange resin used as a catalyst to prepare bisphenol in the present invention can use at least one class of cationic compounds selected from compounds represented by the formula (2) and an N- substituted aromatic compound containing nitrogen, alone or in combination of two or more. Additionally, it may be partially neutralized with a cation other than at least one class of cationic compound selected from compounds represented by formula (2) and an N- substituted aromatic compound containing nitrogen, such as an ammonium cation and a metal cation.

In the preparation of the modified acidic ion exchange resin catalyst of the present invention, at least one class of cationic compound selected from compounds represented by formula (2) and an N- substituted aromatic compound containing nitrogen with a group can be ionically bound functional just before use in the reaction. Thus, the modified acidic ion exchange resin catalyst can be prepared using the cationic compound and / or the N- substituted aromatic compound containing cationic nitrogen in said state, directly or the precursors thereof. The modification procedure is not particularly limited. For example, as a simple and easy procedure, a process can be used to dissolve them in a solvent such as water and contact an organic solvent with a liquid phase, and in the case of using a volatile material, it can be contacted with a resin ion exchange in the gas phase to modify the resin. Additionally, a method can be used to accordingly provide a form of a modified acidic ion exchange resin in which an equivalent weight or an excess amount of a cationic compound or precursor thereof is used to neutralize an ion exchange resin, and The ion exchange resin is then contacted with an acid solution to be partially acidic or similar again.

For an acidic ion exchange resin used as a catalyst to prepare bisphenol, can be used preferably the resin containing a sulfonic acid group. The modified amount of ion exchange resin catalyst modified acid in the present invention is 1 to 50% of the total sulfonic acid groups. In this way, it is possible to express the effect of modification to a maximum extent without reducing notably the activity due to the reduction in the amount of acid.

The amount of acid in the exchange resin ionic used as catalyst to prepare bisphenol can be calculated using a measure of exchange capacity general of an acidic ion exchange resin. At the moment invention, 0.2 g of a dry resin was stirred in 200 ml of a 10% aqueous NaCl solution for 1 hour, and the Total amount of filtrate with an aqueous solution of 0.05 NaOH N, obtaining a titration curve from which determined the amount of acid.

A reaction to prepare bisphenol A proceeds essentially with only one acid catalyst, but usually in a procedure to improve catalytic activity and selectivity, a compound containing a group is coexisted Mercapto as cocatalyst. In the present invention, it is preferable make a compound that contains a mercapto group coexist. Saying procedure includes a procedure in which a compound containing a mercapto group such as alkyl mercaptan in a small amount with a mixture of phenol and acetone that are the raw materials, and the resulting mixture is used, and a procedure in which a compound containing a group is attached mercapto with an acid functional group of an exchange resin acidic ionic, and any such procedure can be used. Both of the mixing procedure can also be used at the same time. of the compound with raw materials and the procedure to join the compound to the acid functional group.

A compound that contains a mercapto group that mixed with a mixture of phenol and acetone is not particularly limited to any structure if it contains a mercapto group in a molecule. It includes, for example, mercaptoalkyl groups such as a mercaptomethyl group, a 2-mercaptoethyl group and a group 3-mercapto-n-propyl;  alicyclic hydrocarbon groups such as a group 4-mercaptocyclohexyl and a group 4-mercaptomethylcyclohexyl; and groups mercaptoaromatics such as a group p-mercaptophenyl and a group p-mercaptomethylphenyl. Additionally, these groups aromatic or aliphatic or alicyclic hydrocarbons can be hydrocarbon groups having a substituent such as an atom of halogen, an alkoxy group, a nitro group and a hydroxyl group, In addition to a mercapto group. The amount of compound it contains a mercapto group added to the mixture of phenol and acetone is preferably in the range of 100 ppm by weight to 5% by weight. From In this way, it is possible to exhibit the cocatalytic effect to a degree maximum with a small amount of a cocatalyst.

A compound containing a mercapto group that binds to a portion of the acidic functional groups of an acidic ion exchange resin is not particularly limited if it is a compound that ionically binds to the acidic functional group of the acidic ion exchange resin. Said compound includes mercaptoalkylamines such as 2-mercaptoethylamine (cysteamine), 3-mercaptopropylamine and N, N- dimethyl-3-mercaptopropylamine, mercaptoalkylpyridine such as 3-mercaptomethylpyridine, 3-mercapoethylpyridine and 4-mercaptoethylpyridine, such as thiazoline, 2, thiazol 2-dimethylthiazolidine, 2-methyl-2-phenylthiazolidine and 3-methylthiazolidine. The ratio of compound containing a mercapto group to bind with an acid functional group is 0.5 to 70%, and preferably 5 to 30%, of the total sulfonic acid groups of the sulfonic acid type cation exchange resin. In this way, it is possible to exhibit the cocatalytic effect to a maximum extent without causing the reduction of activity due to the reduction in the amount of acid. For a process in which a compound containing a mercapto group binds to an acidic ion exchange resin, a conventionally known method can be used as disclosed in the Japanese Patent Application Publication Examined No. 46-19953, etc.

In the present invention, as a phenol for use as a crude material to prepare bisphenol A, a commonly available technical phenol can be used. Industrial phenol includes those obtained by a process with cumene, a process of oxidation of toluene, etc., and any of them can be used. Generally, phenol having a purity of 98% or more is commercially available. Said industrial phenol can be used as such in the bisphenol A synthesis reaction, but preferably phenol is used which is preliminary treated with a strong acid-type cation exchange resin in a continuous reaction or in a discontinuous reaction before carrying out the reaction at a treatment temperature of 50 to 120 ° C for a contact time of 5 minutes to 10 hours, and the acetone-derived carbonyl compounds are then removed. Even more preferably, phenol is used which is contacted with a strong acid type cation exchange resin and then subjected to a normal pressure distillation treatment at reduced pressure of 1.33 kPa at a temperature of 70 to
200 ° C

Acetone for use in the present invention does not It is particularly limited, but it is commercially acetone industrial that is usually available. Generally, it is available acetone having a purity of 99% or more.

The amounts (quantitative ratio) of phenol and acetone used as raw materials are not particularly limited, but a molar ratio of phenol / acetone in the range of 0.1 to 100, and more preferably in the range of 0.5 to 50. If the amount of phenol is extremely small, it is difficult to get a high conversion of Acetone as raw material. While the amount of phenol is too large, the reactor becomes unreasonably large because the phenol is used in an amount greater than necessary, and a massive circulation of phenol is also required, although it can get a high conversion of acetone. Therefore, it cannot get an effective preparation.

In addition, as described in EP document 583712, a mixture of these raw materials may include 1% or less moisture previously.

In the present invention, the temperature of reaction is not particularly limited but is preferably in the range of 0 to 300 ° C, and more preferably in the range of 30 to 200 ° C. If the reaction temperature is extremely low, the reaction rate is reduced and the Productivity of a reaction product is reduced as well. By on the other hand, if the reaction temperature is extremely high, an undesirable side reaction proceeds, etc., leading by both the increase in the quantity of by-products and the reduction of the stability of phenol as a raw material or of bisphenol A as product, and reaction selectivity. Therefore it is not economic.

The reaction can be carried out under pressure. reduced, at applied pressure or at normal pressure. Overlooking the reaction efficiency (the reaction efficiency per unit of volume), it is preferable not to carry out the reaction under pressure Too low. Usually, the pressure to carry out the reaction is preferably in the range of 10.1 kPa to 20,265 kPa, and more preferably in the range of 50.7 to 10,133 kPa. By  of course, the present invention is not limited to said pressure ranges

In addition, when this is carried out invention, the amount of catalyst used is not particularly limited but, for example, when the reaction is carried out discontinuously, it is recommended to carry out the invention of such that the amount of catalyst is preferably in the range of 0.001 to 200% by weight, and more preferably in the range of 0.1 to 50% by weight with respect to phenol.

When the present invention is carried out, it is possible to add a solvent or gas that is inert against a catalyst and a reaction reagent in the reaction system, which It can be used in a diluted state. Specifically, they can be used as diluent aliphatic hydrocarbons such as methane, ethane, propane, butane, hexane and cyclohexane, and an inert gas such as nitrogen, argon and helium, and if necessary, an atom of hydrogen.

When the present invention is carried out, the procedure can be carried out in batch flow system,  semicontinuous or continuous. It can be carried out in any of one liquid phase, a gas phase or a mixed phase gas-liquid Preferably, overlooking the effectiveness of the reaction, it is recommended that the reaction be carried out in liquid phase. As a way to load a catalyst, they can use various kinds of modes that use, for example, a bed fixed, a fluidized bed, a suspended bed or a fixed bed of plates, any of them can be used.

The reaction time (retention time or catalytic contact time in the flow system) is not particularly limited, but is usually 0.1 seconds at 30 hours, and preferably from 0.5 seconds to 15 hours. After finish the reaction, the reaction product can be separated and recover from catalysts and so on by a procedure separation such as filtration, extraction or distillation. He Bisphenol A as a target product can be separated from the mixture of reaction and can be obtained by separation and purification performing a sequential solvent extraction treatment, distillation, alkaline treatment and acid treatment, or a ordinary separation and purification procedure that combines properly both. In addition, raw unreacted materials can be recovered and recycled in the reaction system for use.

In the case of a discontinuous reaction, the catalyst that separates and recovers from the reaction product after the reaction it can be used as such, or partially regenerated or totally to be used repeatedly for the reaction. When carries out the reaction in a fixed bed flow system or fluidized bed, the catalyst can be provided to the reaction, and additionally if part or all of the catalyst is inactivated or impaired in its activity, the reaction may stop to regenerate the catalyst, which can be provided to the reaction. Alternatively, it can be extracted continuously or intermittently a part of the catalyst and regenerate, and then recycled to the reactor for reuse. Further, a catalyst can be intermittently supplied to the reactor recent. When the reaction is carried out in a flow system from the moving bed, the catalyst can be separated, recovered and, if it is necessary to regenerate, as in the discontinuous reaction.

The catalyst can be regenerated by any procedure, for example, washing with water or a organic solvent, or further modifying after washed with an acid solution, provided that the catalyst performance. Additionally, the catalyst can wash several times with an acid solution and a solution alkaline in turn, and finally with an acid solution, and modify then.

Examples

Hereinafter, the present invention will be will describe in more detail with reference to examples. But nevertheless, The present invention is not intended to be limited to examples.

Example one

(1) Preparation of a resin catalyst of modified ion exchange

Shaking vigorously Amberlyst 31 swollen with water (dry weight 4 g) with 80 ml of ion exchange water, se slowly added 40 ml of a solution to it slowly aqueous n-tetrabutylammonium chloride having a concentration of 0.153 mol / l. After completing the addition dropwise, the mixture was further stirred for 5 hours and then filtered and washed repeatedly with ion exchange water. After that, it was dried under vacuum at 80 ° C for 10 hours or more to obtain catalyst 1. The results of the quantity measurement of acid and catalyst elemental analysis are shown in the Table 1.

(2) Bisphenol A synthesis reaction

6.63 g of phenol, 0.37 g of acetone and 0.35 g of catalyst 1 prepared in (1) in a reactor resistant to the pressure of 70 ml, and put in the same acid 3-mercaptopropionic so that the concentration outside 3,000 ppm. He put himself under pressure then with nitrogen gas the pressure-resistant reactor at 5 kg / cm2 of pressure gauge, and stirred with heating at 75 ° C for 2 hours to effect the reaction. After completing the reaction, cooled to room temperature. After the pressure discharge, The reaction solution was removed and subjected to analysis quantitative by liquid chromatography. The results in Table 2.

Example 2

In the same way as in (1) of example 1, except that an aqueous solution of chloride of tetramethylammonium having a concentration of 0.153 mol / l in instead of an aqueous solution of tetrabutylammonium chloride, it performed the operation to obtain catalyst 2. The Acid quantity measurement results and analysis elementary of the catalyst in Table 1. In addition, in the same conditions as in (2) of example 1, except that the catalyst 2 instead of catalyst 1, the reaction of synthesis of bisphenol A. The results were shown in the Table 2.

Example 3

In the same way as in (1) of example 1, except that an aqueous solution of chloride of n-dodecyltrimethylammonium having a concentration 0.153 mol / l instead of an aqueous chloride solution of tetrabutylammonium, the operation was performed to obtain the catalyst 3. The results of the quantity measurement are shown of acid and the elemental analysis of the catalyst in Table 1. In addition, under the same conditions as in (2) of example 1, except because catalyst 3 was used instead of catalyst 1, it performed the bisphenol A synthesis reaction. results in Table 2.

Example 4

In the same way as in (1) of example 1, except that an aqueous solution of chloride of hexamethonium having a concentration of 0.077 mol / l instead of an aqueous solution of tetrabutylammonium chloride, the operation to obtain catalyst 4. Results are shown of the measurement of the amount of acid and the elemental analysis of the catalyst in Table 1. In addition, under the same conditions as in (2) of Example 1, except that catalyst 4 was used instead of catalyst 1, the bisphenol synthesis reaction was carried out A. The results were shown in Table 2.

Example 5

In the same way as in (1) of example 1, except that an aqueous solution of chloride of cetylpyridinium having a concentration of 0.153 mol / l instead of an aqueous solution of tetrabutylammonium chloride, was effected the operation to obtain catalyst 5. The Acid quantity measurement results and analysis elementary of the catalyst in Table 1. In addition, in the same conditions as in (2) of example 1, except because it was used catalyst 5 instead of catalyst 1, the reaction of synthesis of bisphenol A. The results were shown in the Table 2.

Reference Example 6

In the same way as in (1) of example 1, except that an aqueous solution of chloride of tetrabutylphosphonium having a concentration of 0.153 mol / l in instead of an aqueous solution of tetrabutylammonium chloride, it Performed the operation to obtain catalyst 6. The Acid quantity measurement results and analysis elementary of the catalyst in Table 1. In addition, in the same conditions as in (2) of example 1, except that the catalyst 6 instead of catalyst 1, the reaction of synthesis of bisphenol A. The results were shown in the Table 2.

Reference Example 7

In the same way as in (1) of the example of reference 1, except that an aqueous solution of tetraphenylphosphonium chloride having a concentration of 0.153 mol / l instead of an aqueous chloride solution of tetrabutylammonium, the operation was performed to obtain the catalyst 7. The results of the quantity measurement are shown of acid and the elemental analysis of the catalyst in Table 1. In addition, under the same conditions as in (2) of example 1, except because catalyst 7 was used instead of catalyst 1, it was carried out the bisphenol A synthesis reaction. The results were shown in Table 2.

Reference Example 8

In the same way as in (1) of example 1, except because acetonitrile was used instead of exchange water ionic, and a 0.153 mol / l solution of chloride was used hydroxymethyltriphenylphosphonium in acetonitrile instead of a aqueous tetrabutylammonium chloride solution, the operation to obtain catalyst 8. Results are shown of the measurement of the amount of acid and the elemental analysis of the catalyst in Table 1. In addition, under the same conditions as in (2) of Example 1, except that catalyst 8 was used instead of catalyst 1, the bisphenol A synthesis reaction was carried out. They showed the results in Table 2.

Reference Example 9

In the same way as in (1) of example 1, except that a chloride solution of bis (triphenylphosphoraniliden) ammonium in ethanol that has a concentration of 0.153 mol / l instead of an aqueous solution of tetrabutylammonium chloride, the operation was performed to obtain the catalyst 9. The results of the measurement of amount of acid and the elemental analysis of the catalyst in the Table 1. In addition, under the same conditions as in (2) of the example 1, except that catalyst 9 was used instead of catalyst 1, performed the bisphenol A synthesis reaction. results in Table 2.

Reference Example 10

In the same way as in (1) of example 1, except that an aqueous solution of chloride of tetraethylphosphonium having a concentration of 0.153 mol / l in instead of an aqueous solution of tetrabutylammonium chloride, it Performed the operation to obtain catalyst 10. The Acid quantity measurement results and analysis elementary of the catalyst in Table 1. In addition, in the same conditions as in (2) of example 1, except because it was used catalyst 10 instead of catalyst 1, the reaction of synthesis of bisphenol A. The results were shown in the Table 2.

Reference Example eleven

In the same way as in (1) of example 1, except because acetonitrile is used instead of exchange water ionic, and a solution of triphenylphosphine 0.153 mol / l was used in acetonitrile instead of an aqueous chloride solution of tetrabutylammonium, the operation was performed to obtain the catalyst 11. The results of the quantity measurement are shown of acid and the elemental analysis of the catalyst in Table 1. In addition, under the same conditions as in (2) of example 1, except because catalyst 11 was used instead of catalyst 1, it performed the bisphenol A synthesis reaction. results in Table 2.

Reference Example 12

In the same way as in (1) of example 1, except because acetonitrile is used instead of exchange water ionic, and a solution of diphenylethoxyphosphine was used in acetonitrile having a concentration of 0.153 mol / l instead of an aqueous solution of tetrabutylammonium chloride, the operation to obtain catalyst 12. The Acid quantity measurement results and analysis elementary in Table 1. In addition, under the same conditions as in (2) of Example 1, except that catalyst 12 was used instead of catalyst 1, the bisphenol A synthesis reaction was carried out. They showed the results in Table 2.

Reference Example 1st

In the same way as in (1) of example 1, except that an aqueous solution of hydrochloride of trimethylamine having a concentration of 0.153 mol / l instead of an aqueous solution of tetrabutylammonium chloride, the operation to obtain catalyst 13. Results are shown of the measurement of the amount of acid and the elemental analysis of the catalyst in Table 1. In addition, under the same conditions as in (2) of Example 1, except that catalyst 13 was used instead of catalyst 1, the bisphenol A synthesis reaction was carried out. They showed the results in Table 2.

Reference Example 2nd

In the same way as in (1) of example 1, except that an aqueous pyridine solution was used which has a concentration of 0.153 mol / l instead of an aqueous solution of tetrabutylammonium chloride, the operation was performed to obtain catalyst 14. Measurement results are shown of amount of acid and of the elemental analysis of the catalyst in the Table 1. In addition, under the same conditions as in (2) of the example 1, except that catalyst 14 was used instead of catalyst 1, the bisphenol A synthesis reaction was carried out. results in Table 2.

Comparative example one

Under the same conditions as in (2) of the example 1, except that Amberlyst 31 was sufficiently dried that it is commercially available instead of catalyst 1, it was made the reaction. The results were shown in Table 2. In addition, show the results of the measurement of the amount of acid and the elementary analysis of a commercially available Amberlyst 31 in Table 1

Comparative example 2

In the same way as in (1) of example 1, except that an aqueous solution of ammonia was used that has a concentration of 0.153 mol / l instead of an aqueous solution of tetrabutylammonium chloride, the operation was performed to obtain catalyst 15. Measurement results are shown of amount of acid and of the elemental analysis of the catalyst in the Table 1. In addition, under the same conditions as in (2) of the example 1, except that catalyst 15 was used instead of catalyst 1, the bisphenol A synthesis reaction was carried out. results in Table 2.

Example 13

6.50 g of phenol, 0.50 g of acetone and 0.35 g of catalyst 1 prepared in (1) in a resistant reactor at the pressure of 70 ml, and put in the same acid 3-mercaptopropionic so that the concentration outside 3,000 ppm. He put himself under pressure then with nitrogen gas the pressure-resistant reactor at 5 kg / cm2 of gauge pressure, and stirred with heating at 85 ° C for 2 hours to effect the reaction. After completing the reaction, cooled to room temperature. After the pressure discharge, The reaction solution was removed and subjected to analysis quantitative by liquid chromatography. The results in Table 2.

Comparative example 3

Under the same conditions as in example 12, except that a commercially available Amberlyst 31 was used which is sufficiently dried instead of catalyst 1, it performed the bisphenol A synthesis reaction. results in Table 2.

Example 14

(1) Preparation of a resin catalyst of modified ion exchange

Shaking vigorously Amberlyst 31 swollen with water (dry weight 4 g) with 80 ml of ion exchange water, se slowly added 40 ml of a solution to it slowly mixed aqueous of 0.077 mol / l tetramethylammonium chloride and 0.077 mol / l of aminoethanothiol hydrochloride. After completing the dropwise addition, the mixture was further stirred for 5 hours and filtered and washed repeatedly then with water of ion exchange After that, it was dried under vacuum at 80 ° C for 10 hours or more to obtain catalyst 16. The Acid quantity measurement results and analysis Elemental catalyst in Table 1.

(2) Bisphenol A synthesis reaction

6.63 g of phenol, 0.37 g of acetone and 0.35 g of catalyst 16 prepared in (1) in a resistant reactor at the pressure of 70 ml. It was then pressed with nitrogen gas the pressure resistant reactor at 5 kg / cm2 pressure manometric, and stirred with heating at 75 ° C for 2 hours to effect the reaction. After completing the reaction, it cooled to room temperature. After the pressure discharge, it  removed the reaction solution and underwent quantitative analysis by liquid chromatography. The results were shown in the Table 2.

Reference Example fifteen

In the same way as in (1) of the example of reference 14, except that tetraphenylphosphonium chloride was used instead of tetramethylammonium chloride, the operation was performed to obtain catalyst 17. The results of the measurement of acid quantity and catalyst elemental analysis in Table 1. In addition, under the same conditions as in (2) of the example 14, except that catalyst 17 was used instead of catalyst 16, the bisphenol A synthesis reaction was carried out. The results were shown in Table 2.

Reference Example 16

(1) Preparation of a resin catalyst of modified ion exchange

Shaking vigorously Amberlyst 31 swollen with water (dry weight 4 g) with 80 ml of ion exchange water, se slowly added dropwise thereto 40 ml of a solution of hydroxymethyltriphenylphosphonium chloride 0.077 mol / l in acetonitrile After completing the dropwise addition, it was stirred additionally the mixture for 5 hours, and filtered and washed repeatedly then with ion exchange water. After this was dried under vacuum at 80 ° C for 10 hours or more to obtain a solid. The solid obtained was dispersed in 80 ml of water ion exchange and slowly added dropwise thereto ml of an aqueous solution of aminoethanethiol hydrochloride 0.077 mol / l with stirring. After completing the dropwise addition, it  continuously stirred the mixture for 5 hours and filtered and washed then repeatedly with ion exchange water. After this was dried under vacuum at 80 ° C for 10 hours or more to obtain the catalyst 18. The results of the quantity measurement are shown of acid and the elemental analysis of the catalyst in the Table one.

(2) Bisphenol A synthesis reaction

Under the same conditions as in (2) of the example 14, except that catalyst 18 was used instead of catalyst 16, the bisphenol A synthesis reaction was performed. They were shown the results in Table 2.

Reference Example 17

In the same way as in (1) of example 14, except that tetraethyl phosphonium chloride was used instead of tetramethylammonium chloride, the operation was performed to obtain the catalyst 19. The results of the quantity measurement are shown of acid and the elemental analysis of the catalyst in Table 1. In addition, under the same conditions as in (2) of example 14, except that catalyst 19 was used instead of catalyst 16, it was performed the bisphenol A synthesis reaction. results in Table 2.

Example 18

In the same way as in (1) of example 14, except that cetylpyridinium chloride was used instead of chloride of tetramethylammonium, the operation was performed to obtain the catalyst 20. In addition, under the same conditions as in (2) of the example 14, except that catalyst 20 was used instead of catalyst 16, the reaction synthesis of bisphenol A was carried out. The results were shown in Table 2.

Reference Example 19

In the same way as in (1) of example 16, except that triphenylphosphine was used instead of hydroxymethyltriphenylphosphonium, the operation was performed to obtain the catalyst 21. The results of the measurement of amount of acid and the elemental analysis of the catalyst in the Table 1. In addition, under the same conditions as in (2) of the example 14, except that catalyst 21 was used instead of catalyst 16, the bisphenol A synthesis reaction was carried out. results in Table 2.

Reference Example twenty

In the same way as in (1) of example 16, except that diphenylethoxyphosphine was used instead of hydroxymethyltriphenylphosphonium, the operation was performed to obtain the catalyst 22. The results of the measurement of amount of acid and the elemental analysis of the catalyst in the Table 1. In addition, under the same conditions as in (2) of the example 14, except that catalyst 22 was used instead of catalyst 16, the bisphenol A synthesis reaction was carried out. results in Table 2.

Reference Example 3rd

In the same way as in (1) of example 14, except that pyridine was used instead of tetramethylammonium, the operation was performed to obtain the catalyst 23. The results of the quantity measurement are shown of acid and the elemental analysis of the catalyst in Table 1. In addition, under the same conditions as in (2) of example 14, except that catalyst 23 was used instead of catalyst 16, it was performed the bisphenol A synthesis reaction. results in Table 2.

Reference Example 4th

In the same way as in (1) of example 14, except that trimethylamine hydrochloride was used instead of tetramethylammonium chloride, the operation was performed to obtain the catalyst 24. The results of the quantity measurement are shown of acid and the elemental analysis of the catalyst in Table 1. In addition, under the same conditions as in (2) of example 14, except that catalyst 24 was used instead of catalyst 16, it was performed the bisphenol A synthesis reaction. results in Table 2.

Comparative example 4

Shaking vigorously Amberlyst 31 swollen with water (dry weight 4 g) with 80 ml of ion exchange water, se slowly added dropwise thereto 40 ml of a solution aqueous of aminoetanothiol hydrochloride 0.077 mol / l. After complete the addition dropwise, the mixture was further stirred for 5 hours, and filtered and washed repeatedly then with water ion exchange After that, it was dried under vacuum at 80 ° C for 10 hours or more to obtain catalyst 25. They are shown the results of the acid quantity measurement and the analysis Elemental catalyst in Table 1.

In addition, under the same conditions as in (2) of the example 14, except that catalyst 25 was used instead of catalyst 16, the bisphenol A synthesis reaction was carried out. They showed the results in Table 2.

Example twenty-one

(1) Preparation of a resin catalyst of modified ion exchange

Shaking vigorously Amberlyst 31 swollen with water (dry weight 4 g) with 80 ml of ion exchange water, se slowly added dropwise thereto 40 ml of a solution mixed aqueous tetramethylammonium chloride 0.077 mol / l and 4-pyridinetanothiol hydrochloride 0.077 mol / l. After completing the dropwise addition, it was stirred additionally the mixture for 5 hours and filtered and washed repeatedly then with ion exchange water. After this was dried under vacuum at 80 ° C for 10 hours or more to obtain the catalyst 26. Results of quantity measurement are shown of acid and the elemental analysis of the catalyst in the Table one.

(2) Bisphenol A synthesis reaction

6.63 g of phenol, 0.37 g of acetone and 0.35 g of catalyst 26 prepared in (1) were placed in a 70 ml pressure resistant reactor. The pressure-resistant reactor was then pressurized with nitrogen gas at 5 kg / cm 2 of manometric pressure, and stirred with heating at 75 ° C for 2 hours to effect the reaction. After completing the reaction, it was cooled to room temperature. After the pressure discharge, the reaction solution was removed and subjected to quantitative analysis by liquid chromatography. The results are shown in the
Table 2.

Reference Example 22

In the same way as in (1) of example 21, except that tetraphenylphosphonium chloride was used instead of tetramethylammonium chloride, the operation was performed to obtain the catalyst 27. Results of quantity measurement are shown of acid and the elemental analysis of the catalyst in Table 1. In addition, under the same conditions as in (2) of example 21, except that catalyst 27 was used instead of catalyst 26, it was performed the bisphenol A synthesis reaction. results in Table 2.

Reference Example 2. 3

(1) Preparation of a resin catalyst of modified ion exchange

Shaking vigorously Amberlyst 31 swollen with water (dry weight 4 g) with 80 ml of acetonitrile, were added to the same slowly drop 40 ml of chloride solution hydroxymethyltriphenylphosphonium 0.077 mol / l in acetonitrile. After if the addition was completed dropwise, the stirring was further stirred mixture for 5 hours and filtered and then washed repeatedly with ion exchange water. After that, it was dried under vacuum at 80 ° C for 10 hours or more. The solid obtained was dispersed in 80 ml of ion exchange water and added dropwise thereto slowly 40 ml of an aqueous solution of hydrochloride 4-pyridinetanothiol 0.077 mol / l with stirring. After completing the dropwise addition, it was continuously stirred. the mixture for 5 hours, and then filtered and washed repeatedly with ion exchange water. After that, it dried under vacuum at 80 ° C for 10 hours or more to obtain the catalyst 28. Results of quantity measurement are shown of acid and elemental analysis in Table 1.

(2) Bisphenol A synthesis reaction

Under the same conditions as in (2) of the example 21, except that catalyst 28 was used instead of catalyst 26, the bisphenol A synthesis reaction was performed. They were shown the results in Table 2.

Reference Example 24

In the same way as in (1) of example 21, except that tetraethyl phosphonium chloride was used instead of tetramethylammonium chloride, the operation was performed to obtain the catalyst 29. Results of quantity measurement are shown of acid and the elemental analysis of the catalyst in Table 1. In addition, under the same conditions as in (2) of example 21, except that catalyst 29 was used instead of catalyst 26, it was performed the bisphenol A synthesis reaction. results in Table 2.

Example 25

In the same way as in (1) of example 21, except that cetylpyridinium chloride was used instead of chloride of tetramethylammonium, the operation was performed to obtain the catalyst 30. Results of quantity measurement are shown of acid and elemental analysis in the catalyst in Table 1. In addition, under the same conditions as in (2) of example 21, except that catalyst 30 was used instead of catalyst 26, it was performed the bisphenol A synthesis reaction. results in Table 2.

Reference Example 26

In the same way as in (1) of example 23, except that triphenylphosphine was used instead of hydroxymethyltriphenylphosphonium, the operation for the obtain catalyst 31. Measurement results are shown of amount of acid and of the elemental analysis of the catalyst in the Table 1. In addition, under the same conditions as in (2) of the example 21, except that catalyst 31 was used instead of catalyst 26, the bisphenol A synthesis reaction was carried out. results in Table 2.

Reference Example 27

In the same way as in (1) of example 23, except that diphenylethoxyphosphine was used instead of hydroxymethyltriphenylphosphonium, the operation was performed to obtain the catalyst 32. The results of the measurement of amount of acid and the elemental analysis of the catalyst in the Table 1. In addition, under the same conditions as in (2) of the example 21, except that catalyst 32 was used instead of catalyst 26, the bisphenol A synthesis reaction was carried out. results in Table 2.

Reference Example 5th

In the same way as in (1) of example 21, except that pyridine was used instead of tetramethylammonium, the operation was performed to obtain the catalyst 33. The results of the quantity measurement are shown of acid and the elemental analysis of the catalyst in Table 1. In addition, under the same conditions as in (2) of example 21, except that catalyst 33 was used instead of catalyst 26, it was performed the bisphenol A synthesis reaction. results in Table 2.

Reference Example 6th

In the same way as in (1) of example 21, except that trimethylamine hydrochloride was used instead of tetramethylammonium chloride, the operation was performed to obtain the catalyst 34. The results of the quantity measurement are shown of acid and elemental analysis in Table 1. In addition, in the same conditions as in (2) of example 21, except that it was used catalyst 34 instead of catalyst 26, the reaction was carried out of synthesis of bisphenol A. The results were shown in the Table 2.

Comparative example 5

Shaking vigorously Amberlyst 31 swollen with water (dry weight 4 g) with 80 ml of ion exchange water, se slowly added dropwise thereto 40 ml of a solution aqueous 4-pyridinetanothiol hydrochloride 0.077 mol / l. After completing the dropwise addition, it was stirred additionally the mixture for 5 hours and filtered and washed then repeatedly with ion exchange water. After this was dried under vacuum at 80 ° C for 10 hours or more to obtain the catalyst 35. The results of the quantity measurement are shown of acid and the elemental analysis of the catalyst in Table 1.

In addition, under the same conditions as in (2) of the example 21, except that catalyst 35 was used instead of catalyst 26, the bisphenol A synthesis reaction was carried out. They showed the results in Table 2.

Example 28

A reactor was filled with 3.5 g of catalyst 2 cylindrical (internal diameter: 21.4 mm, length: 470 mm). From the bottom of the reactor, the raw material solution was supplied to which was added 3-mercaptopropionic acid to a phenol / acetone mixture that had a 6: 1 molar ratio thereby that the concentration be 3,000 ppm to proceed to the reaction of synthesis of bisphenol A at a reaction temperature of 85 ° C. When the amount of acetone flow reached 7 g, the amount of solution of raw material supplied in such a way that the acetone conversion was about 65%, and it was fixed so. When the amount of acetone flow reached 7 g and 200 g, respectively, the reaction product was analyzed by liquid chromatography to determine reduced levels of conversion of acetone and selectivity by p, p'-bisphenol A, respectively. The results in Table 3.

In addition, [reduced level of conversion (%)] = [conversion (%) when the amount of acetone flow is 7 g] - [conversion (%) when the amount of acetone flow is 200 g], [reduced level of selectivity (%)] = [selectivity (%) when the amount of acetone flow is 7 g] - [selectivity (%) when the amount of acetone flow is 200 g], and the following this way.

Example 29

The bisphenol A synthesis reaction was carried out under the same conditions as in example 28, except because used catalyst 5 instead of catalyst 2 to determine reduced levels of acetone conversion and selectivity by p, p'-bisphenol A, respectively. The results in Table 3.

Example 30

The bisphenol A synthesis reaction was carried out under the same conditions as in example 28, except because used catalyst 7 instead of catalyst 2 to determine the reduced levels of acetone conversion and selectivity by p, p'-bisphenol, respectively. The results in Table 3.

Reference Example 31

The bisphenol A synthesis reaction was carried out under the same conditions as in example 28, except because used catalyst 10 instead of catalyst 2 to determine reduced levels of acetone conversion and selectivity by p, p'-bisphenol A, respectively. The results in Table 3.

Reference Example 32

The bisphenol A synthesis reaction was carried out under the same conditions as in example 28, except because used catalyst 11 instead of catalyst 2 to determine the reduced levels of acetone conversion and selectivity by p, p'-bisphenol A, respectively. The results in Table 3.

Reference Example 33

The bisphenol A synthesis reaction was carried out under the same conditions as in example 28, except because used catalyst 12 instead of catalyst 2 to determine the reduced levels of acetone conversion and selectivity by p, p'-bisphenol A, respectively. The results in Table 3.

Comparative example 6

The bisphenol A synthesis reaction was carried out under the same conditions as in example 28, except because used catalyst 13 instead of catalyst 2 to determine the reduced levels of acetone conversion and selectivity by p, p'-bisphenol A, respectively. The results in Table 3.

Comparative example 7

The bisphenol A synthesis reaction was carried out under the same conditions as in example 28, except because used catalyst 14 instead of catalyst 2 to determine the reduced levels of acetone conversion and selectivity by p, p'-bisphenol A, respectively, were shown results in Table 3.

Example 3. 4

It was filled with 3.5 g of catalyst 16 a cylindrical reactor (internal diameter: 21.4 mm, length: 470 mm). From the bottom of the reactor, the phenol / acetone mixture was supplied which had a 6: 1 molar ratio as a solution of raw material to proceed to the synthesis reaction of bisphenol A at a reaction temperature of 85 ° C. When the amount of flow of acetone reached 7 g, the amount of solution of raw material supplied in such a way that the conversion of Acetone was about 65%, and it was then fixed. When the amount of acetone flow reached 7 g and 200 g, respectively, The reaction product was analyzed by liquid chromatography to determine reduced levels of acetone conversion and of selectivity for p, p'-bisphenol A, respectively. The results were shown in Table 3.

Reference Example 35

The bisphenol A synthesis reaction was carried out under the same conditions as in example 34, except because used catalyst 17 instead of catalyst 16 to determine the reduced levels of acetone conversion and selectivity by p, p'-bisphenol A, respectively. The results in Table 3.

Reference Example 36

The bisphenol A synthesis reaction was carried out under the same conditions as in example 34, except because used catalyst 18 instead of catalyst 16 to determine the reduced levels of acetone conversion and selectivity by p, p'-bisphenol A, respectively. The results in Table 3.

Reference Example 37

The bisphenol A synthesis reaction was carried out under the same conditions as in example 34, except because used catalyst 19 instead of catalyst 16 to determine the reduced levels of acetone conversion and selectivity by p, p'-bisphenol A, respectively. The results in Table 3.

Example 38

The bisphenol A synthesis reaction was carried out under the same conditions as in example 34, except because used catalyst 20 instead of catalyst 16 to determine the reduced levels of acetone conversion and selectivity by p, p'-bisphenol A, respectively. The results in Table 3.

Reference Example 39

The bisphenol A synthesis reaction was carried out under the same conditions as in example 34, except because used catalyst 21 instead of catalyst 16 to determine the reduced levels of acetone conversion and selectivity by p, p'-bisphenol A, respectively. The results in Table 3.

Reference Example 40

The bisphenol A synthesis reaction was carried out under the same conditions as in example 34, except because used catalyst 22 instead of catalyst 16 to determine the reduced levels of acetone conversion and selectivity by p, p'-bisphenol A, respectively. The results in Table 3.

Comparative example 8

The bisphenol A synthesis reaction was carried out under the same conditions as in example 34, except because used catalyst 23 instead of catalyst 16 to determine the reduced levels of acetone conversion and selectivity by p, p'-bisphenol A, respectively. The results in Table 3.

Comparative example 9

The bisphenol A synthesis reaction was carried out under the same conditions as in example 34, except because used catalyst 24 instead of catalyst 16 to determine the reduced levels of acetone conversion and selectivity by p, p'-bisphenol A, respectively. The results in Table 3.

Comparative example 10

The bisphenol A synthesis reaction was carried out under the same conditions as in example 34, except because used catalyst 25 instead of catalyst 16 to determine reduced levels of acetone conversion and selectivity by p, p'-bisphenol A, respectively. The results in Table 3.

Example 41

It was filled with 3.5 g of catalyst 26 a cylindrical reactor (internal diameter: 21.4 mm, length: 470 mm). From the bottom of the reactor, the phenol / acetone mixture was supplied which had a 6: 1 molar ratio as a solution of raw material to proceed to the synthesis reaction of bisphenol A at a reaction temperature of 85 ° C. When the amount of flow of acetone reached 14 g, the amount of solution of raw material supplied in such a way that the conversion of Acetone was about 65%, and it was then fixed. When the amount of acetone flow was 14 g and 400 g, respectively, The reaction product was analyzed by liquid chromatography to determine reduced levels of acetone conversion and of selectivity for p, p'-bisphenol A, respectively. The results were shown in Table 3.

Reference Example 42

The bisphenol A synthesis reaction was carried out under the same conditions as in example 41, except because used catalyst 27 instead of catalyst 16 to determine the reduced levels of acetone conversion and selectivity by p, p'-bisphenol A, respectively. The results in Table 3.

Reference Example 43

The bisphenol A synthesis reaction was carried out under the same conditions as in example 41, except because used catalyst 28 instead of catalyst 26 to determine the reduced levels of acetone conversion and selectivity by p, p'-bisphenol A, respectively. The results in Table 3.

Reference Example 44

The bisphenol A synthesis reaction was carried out under the same conditions as in example 41, except because used catalyst 29 instead of catalyst 26 to determine the reduced levels of acetone conversion and selectivity by p, p'-bisphenol A, respectively. The results in Table 3.

Example Four. Five

The bisphenol A synthesis reaction was carried out under the same conditions as in example 41, except because used catalyst 30 instead of catalyst 26 to determine the reduced levels of acetone conversion and selectivity by p, p'-bisphenol A, respectively. The results in Table 3.

Reference Example 46

The bisphenol A synthesis reaction was carried out under the same conditions as in example 41, except because used catalyst 31 instead of catalyst 26 to determine the reduced levels of acetone conversion and selectivity by p, p'-bisphenol A, respectively. The results in Table 3.

Reference Example 47

The bisphenol A synthesis reaction was carried out under the same conditions as in example 41, except because used catalyst 32 instead of catalyst 26 to determine the reduced levels of acetone conversion and selectivity by p, p'-bisphenol A, respectively. The results in Table 3.

Comparative example eleven

The bisphenol A synthesis reaction was carried out under the same conditions as in example 41, except because used catalyst 33 instead of catalyst 26 to determine the reduced levels of acetone conversion and selectivity by p, p'-bisphenol A, respectively. The results in Table 3.

Comparative example 12

The bisphenol A synthesis reaction was carried out under the same conditions as in example 41, except because used catalyst 34 instead of catalyst 26 to determine the reduced levels of acetone conversion and selectivity by p, p'-bisphenol A, respectively. The results in Table 3.

Comparative example 13

The bisphenol A synthesis reaction was carried out under the same conditions as in example 41, except because used catalyst 35 instead of catalyst 26 to determine the reduced levels of acetone conversion and selectivity by p, p'-bisphenol A, respectively. The results in Table 3.

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TABLE 2

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TABLE 3

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Industrial applicability

According to the process of the present invention, Bisphenol can be prepared with good yield and selectivity, and can be provided with excellent security, processing and economy.

Claims (12)

1. The use of an ion exchange resin acid modified as catalyst to prepare bisphenol, in which at least one class of cationic compound selected from the Following (B) and (D) ionically binds to an acid functional group of an acidic ion exchange resin: (B) a cationic compound represented by the formula (2): 8 in which N represents an atom of nitrogen, and R 1, R 2, R 3 and R 4 represent independently an alkyl group or an aryl group, each of which contains 1 to 20 carbon atoms and does not contain any mercapto group or precursor thereof or link amide; (D) an N- substituted aromatic compound containing cationic nitrogen that does not contain any mercapto groups, nor precursor thereof or amide bond, wherein said N- substituted aromatic compound containing cationic nitrogen is an N- methylpyridinium salt, a cetylpyridinium salt, a dodecylpyridinium salt, an N-methylquinolinium salt or an N- ethylquinolinium salt. 2. The use according to claim 1, wherein from 0.1 to 50 mol% of the total acid functional groups that are present in the acidic ion exchange resin bind ionically with the cationic compound. 3. The use according to claim 1 or 2, in the that the acidic ion exchange resin is one in which introduces a sulfone group into a styrene polymer and / or a styrene-divinylbenzene copolymer. 4. A procedure for preparing bisphenol that comprises reacting phenolic compounds with ketone and / or aldehyde, in which the exchange resin is used as catalyst modified acidic ionic according to any one of claims 1 to 3. 5. The procedure for preparing bisphenol according to claim 4, wherein additionally an ionically bonded nitrogen-containing compound that contains a mercapto group at modified acidic ion exchange resin according to any of claims 1 to 3. 6. The procedure for preparing bisphenol according to claim 4, wherein it is allowed to coexist at least one compound containing a mercapto group with reaction materials crude and the ion exchange resin is used as catalyst modified acid according to any one of claims 1 to 3. 7. The procedure for preparing bisphenol according to claim 4, comprising reacting compounds phenolics with ketone. 8. The procedure for preparing bisphenol according to claim 7, wherein 0.1 to 50 mol% of the groups total acid functional that are present in the resin of acidic ion exchange ionically bind with the compound cationic 9. The procedure for preparing bisphenol according to claim 7 or 8, wherein the ion exchange resin acid is one in which a sulfone group is introduced into a polymer of styrene and / or a styrene / divinylbenzene copolymer. 10. The procedure for preparing bisphenol according to any of claims 7 to 9, wherein additionally a compound containing ionically binds nitrogen containing a mercapto group to the exchange resin modified acidic ionic. 11. The procedure for preparing bisphenol according to any of claims 7 to 9, wherein  coexist at least one compound that contains a mercapto group with raw reaction materials. 12. The procedure for preparing bisphenol according to any of claims 7 to 9, wherein the ketone It is acetone and the phenolic compounds are phenol.