CA1282797C - Process for preparing bisphenol a - Google Patents
Process for preparing bisphenol aInfo
- Publication number
- CA1282797C CA1282797C CA000584934A CA584934A CA1282797C CA 1282797 C CA1282797 C CA 1282797C CA 000584934 A CA000584934 A CA 000584934A CA 584934 A CA584934 A CA 584934A CA 1282797 C CA1282797 C CA 1282797C
- Authority
- CA
- Canada
- Prior art keywords
- reaction
- acetone
- phenol
- bisphenol
- exchange resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
- C07C39/16—Bis-(hydroxyphenyl) alkanes; Tris-(hydroxyphenyl)alkanes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
ABSTRACT
This invention is a process for the preparation of bisphenol A
from acetone and phenol. By this invention, the formation of by-products is extremely decreased and post treatment steps can be simplified.
This invention involves the following steps. (1) One mole of acetone is reacted with 4 to 12 moles of phenol in the presence of a sulfonic acid type cation exchange resin catalyst modified with a mercapto group-containing compound such as mercaptoethylamine to convert 20 to 60% of acetone, and (2) the reaction mixture containing unreacted acetone is successively reacted in the presence of the hydrochloric acid catalyst.
The formation of by-products such as 2-(2-hydroxyphenyl)-2-(4-hydroxyphenyl)propane, Dianin's compound and the like is remarkably reduced by the process of this invention.
This invention is a process for the preparation of bisphenol A
from acetone and phenol. By this invention, the formation of by-products is extremely decreased and post treatment steps can be simplified.
This invention involves the following steps. (1) One mole of acetone is reacted with 4 to 12 moles of phenol in the presence of a sulfonic acid type cation exchange resin catalyst modified with a mercapto group-containing compound such as mercaptoethylamine to convert 20 to 60% of acetone, and (2) the reaction mixture containing unreacted acetone is successively reacted in the presence of the hydrochloric acid catalyst.
The formation of by-products such as 2-(2-hydroxyphenyl)-2-(4-hydroxyphenyl)propane, Dianin's compound and the like is remarkably reduced by the process of this invention.
Description
1'~8X79'7 PROCESS FOR PREPARING BISPHENO~ A
BACKGROUND OF THE INVENTION
The present invention relates to a process for preparing bisphenol A of high purity, that is, 2,2-bis(4-hydroxyphenyl)propane of high purity.
Bisphenol A is used as a raw material for polycarbonate reslns or epoxy reslns. Colorless and highly purified bisphenol A is particularly required for polycarbonate resins.
Bisphenol A is prepared by the reaction of acetone with excess phenol in the presence of an acid catalyst or a combination of an acid catalyst and a cocatalyst such as sulfur compounds.
The reaction mixture contains, in addition to bisphenol A, catalyst, unreacted acetone, unreacted phenol, water and other by-products formed by the reaction.
Principal components oE the by-prod~lct~ nre 2-(Z-hydroxyphenyl)-2-(4-hydroxyphenyl)propane (herelnater re~erred to as o,p'-isomer) and 2,2,4-trimethyl-4-(4-hydroxyphenyl)chroman (hereinafter referred to as Dianin's compound). Other components such as trisphenol, polyphenol and unfavorable colored sustances are also included. These by-products deteriorate the properties of the resin prepared from bisphenol A.
As the catalyst of the condensation reaction, hydrochloric acid and strongly acidic ion exchange resins have been known to date.
~"
~8X~7~37 When hydrochloric acid is used as the catalyst, the reaction can proceed at lower temperatures with successive crystallization of adduct of bisphenol A and phenol. In the course of the reaction, the o,p'-isomer in the mother liquor is converted to bisphenol A and hence the amount of the o,p'-isomer is decreased. The reaction with hydrochloric acid catalyst, however, generates a large amount of Dianin's compound as a by-product. As a method for lowering the generation of Dianin's compound, the addition of water has been disclosed by Progil in Japanese Patent Publication, TOKKOSHO 40-7186 (1965). The addition of mercapto compounds has also been reported by Dow Chemical Co. in Japnnese Patent Publication, TOKKOSHO 27-5367 (1952). These methods, however, are unfavorable because of complex procedures for the separation and recovery of hydrochloric acid and mercapto compounds as well as the obnoxious odor resulting from mercapto compounds. The generation of Dianin's compound can be reduced by uslng a greater excess of phenol. On the other hand, the formation of o,p'-lsomer increases and a large excess of phenol used must be recovered.
When commonly used Lon exch~mge re~ln~ oE ~he ~trong acld type are employed, by~-products are produced in B large amount.
Particularly when an ion exchsnge resin is used Eor the catalyst, the lsomerizntion dlle to crystallizatlon of the adduct of bisphenol ~
and phenol cannot be utlllzed and thus o,p'-lsomer ls formed ln a much larger amount when compared to the use of hydrochloric acid catalyst.
When the functlonal groups of the ion exchange resln are modified with mercapto groups such as by reaction with a mercaptoalkylamine, it has been known to markedly decrease the amount of Dianin's compound produced. o,p'-Isomer, however, is st~ll formed as a by-product in a large amount because crystallization of the adduct cannot be utilized.
When an ion exchange resin is used, water formed in the reaction leads to insufficient conversion of acetone. As a result, dehydration of the ion exchange resin is needed in every batchwise reaction. An enormous amount of the resin is also required in a continuous reaction in order to proceed with the conversion of acetone to a significant extent. These results are disclosed by ~itsui Toatsu Chemicals, Inc. in Japanese Laid-Open Patent Publication, TOKKAISHO
61-78741 (1986).
As mentioned above, previously known processes for preparing bisphenol A could not satlsfactorily inhibit the formation of two typical impurities, although these processes have their own characteristics, respectively.
SUMMARY OF THE INVENTION
The ob~ect of thi~ inventlon 1~ to provide a proces~ for preparing blsphenol A o high purity with a mlnimum amount of by-products and impurities formed in the reaction as well as the simple~t procedure in post treatment steps.
8X~9~7 BRIEF DESC~IPTION OF Tl~ DRAWING
Figure 1 is a flow diagram illustrating an embodiment of this invention for the preparation of bisphenol A.
DETAILED DESCRIPTION OF THE INVENTION
The present inventors have carried out an intensive investigation in order to achieve the above mentioned objects. ~s a result, it has been found that the objects of this invention can be achleved by reactlng a part of the acetone with excess phenol in the presence of a specific ion exchange resln and then further reacting the resultant reaction mixture in the presence of a hydrochloric acid catalyst. Thus the present invention has been achieved.
That is, the present invention is a process for preparing bisphenol A by the reaction of acetone with phenol comprising:
(a) conducting the reaction of acetone with phenol in the presence o a suLfonic acld type cation exchange resln modified wLth a mercapto group-containing compound to convert 20 to 60~ o~ the acetone in the reaction; and (b) further reacting the resulting reaction mixture containing unreacted acetone in the presence of a hydrochloric acid catalyst.
In the process of this invention, 1 mole of acetone is usually reacted with 4 to 12 moles of phenol substantially in the absence of a solvent as a third component. The total amount of acetone may be ~ ' :
7~7 charged to the first reactor containing the cation exchange resin or a part of the acetone may be fed to the second reactor containing the hydrochloric acid catalyst. Each reaction step may be composed of one or several reactors connected with each other in series or in parallel. The reactors may be batchwise or continuous, respectively.
A preferred embodiment is to continuously carry out the reaction using the cation exchange resin catalyst and to feed the reaction mixture successively to a plurality of batch reactors containing the hydrochloric acid catalyst. The present invention can be most efEectively conducted by applylng such a reactlon system.
The first reaction i8 carried out in the presence of the cation exchange resin catalyst.
The reaction is usually conducted under atmospheric pressure at a pressure of 5 kg/cm2 and a temperature of 30 to 120C, preferably 50 to 100C. When the reaction temperature is lower than 30C, the reaction rate is too slow. A reaction temperature exceeding 120C
causes an unfavorable increase of by-product formation. The reactor~
are hea~ed or cooled, 1 nece~sary.
The reaction time, usually depends upon the type of reaction and particularly the reaction temperature. For example, in a batch reaction using a stirred reactor, the reaction time i8 usually 0.1 to 10 hours. In a plston-flow type continuous reaction using a fixed bed catalyst, the reaction $9 controlled 50 as to obtain a space velocity of 0.1 to 10/hr. Acetone conver~ion ratlo of 20 to 60% can be achieved by employing the reaction conditions mentioned above.
The resin used in the process of this invention is a sulfonic acid type cation exchange resin modified with a mercapto group-containing compound.
As to the sulfonic acid type cation exchange resin, commercial products usually available in the market can be used. Modification with mercapto group containing compounds are well known to those skilled in the art. The compounds used for the modification include, for example, mercaptoalkylamines, thiazalidine compounds and pyridinealkanethiols. These compounds are disclosed by Dow Chemicals Co. in Japanese Patent Publication TOKKOSHO 46-19953 (1~71) and Japanese Lald-Oyen Pa~ent Publication TOKKAISHO 48-71389 (1973) as well as by Mitsubishi Kasei Ltd. in Japanese Laid-Open Patent Publicatiin TOKKAISHO 57-35533 (1982).
The modification method of the resin has been known. The modification can be readily carried out by neutralizing a part of the sulfonic acid groups with mercapto groups as disclosed by Dow Chemlcals Co. in Japanese Patent Publication 46-19953 (1971) and by Shell International Research Ltd. in Japnnese Lald-Open Patent Publication TOKKAS~lO 53-1~680 (1978).
The modlfication ratio i9 usually 5 to 35 mole %, preferably 10 to 20 mole % of the sulfonic acid groups in the resin. A
modification ratio lower than 5 mole % causes a decrease in the reaction velocity and an increase in the Dianin's compound. A
modification ratio exceeding 35 mole % also leads to a decrease in the reaction velocity and conversion rate.
lX8X79~
The reaction using the resin catalyst is terminated at an acetone conversion of 20 to 60%. When a conversion sate of more than 60% is intended to be obtained, the conversion velocity decreases rapidly due to the generation of water and a huge amount of the catalyst is required a~ disclosed by Mitsui Toatsu Chemicals, Inc. in Japanese Laid-Open Patent TOKKAISHO 61-78741 (1986). ~hen the reaction proceeds along with continuous removal of generated water, a high conversion ratio can be obtained by a small amount of the resin, but the amount of o,p'-isomer cannot be lowered to less than that obtaLned by tl1e reaction ln the presence of resin.
The second reaction 1~ carried out in the presence of a hydrochloric acid catalyst. The hydrochloric acid catalyst may be supplied as the form of aqueous hydrochloric acid, hydrogen chloride or a mixture thereof. The reaction can be conducted a known manner except that the reaction mixture produced in the presence of the cation exchange resin catalyst is u~ed. The reaction is carried out under agitation at 30 to 85C, preferably at 35 to 60~C. Hydrogen chlorlde may be saturated prior to the reactlon or contlnuou~ly eed to the reactor. In con~ideratlotl o~ the e~othe~nlc ~bsorptlon Oe hydrogen chloride, the heat of reaction and the crystallization heat of the adduct, lt 18 preferred to feed hydrogen chloride both prior to and in the course of the reaction. Generated heat is removed by external cooling to control the reaction temperature within the range mentioned above.
Adduct cry~tal~ of bisphenol A and phenol are precipitated with the progres~ of tile reaction. The o,p'-i~omer in the ~olution ls ~8Z797 isomerized to bisphenol A accompanied by ~he crystallization of the adduct. Thus the concentration of the o,p'-isomer is decreased. The Dianin's compound generates only a slight amount because the acetone charged into the second reaction is in a low concentration.
Water, catalyst and excess phenol are removed from the reaction mixture thus obtained to give bisphenol A.
The resultant bisphenol A is used as the product as it is or can be subjected to further steps for purification and forming to give the product. Colorless bisphenol A of high purity can also be obtained by retnovlng phenol from the crystallized adduct of bisphenol A and phenol.
An example of a flow diagram for carrying out the process of this invention will be briefly described by way of Figure 1.
Phenol (1) and acetone (3) are mixed ln a mixing tank (2) and fed to the reactor (5) containing the cation exchange resin catalyst.
Reaction product ttlixture (6) from the reactor (5) contains unreacted acetone. A part (7) of the reaction product mixture (6) is mixed with the raw materlals and recycled again to the flrst reactor (5). The remainder (8) of the m:Lxture (6) i8 tran~earred to a h~drogen chlorlde absorptlon colutnn (9) und aaturated with hydrogen chlorlde (10). The resultant mixture ls then reacted ln the second reactor (14) which ls a hydrochloric acld catalyst reactor. The reactlon is conducted for several hours to react almost all of the acetone. Thereafter the reaction product (15) i9 transferred to the purification step. When the amount of hydrochloric acid is insufficient in the course of the a~7'~37 reaction in the reactor (14) mentioned above, hydrogen chloride or concentrated hydrochloric acid (11) is supplied to the reactor (14).
~XAMPLE
The process of this invention will hereinafter be described in detail by way of example and comparative examples.
Example 1 A sulfonic acld type cation exchange resin was used as the catalyst after modlfylng 12% of its sul~onlc acid groups with mercaptoethylamlne. The catalyst was used in the form of a packed layer having a diameter of 30 cm and a length of 200 cm.
A mixture of 564 kg/hr of phenol and 58 kg/hr of acetone was passed through the catalyst layer at 70C under atmospheric pressure and reacted continuously.
Hydrogen chloride was blown into the reaction mlxture in the hydrogen chlorlde ab~orptiotl column. The ml~ture thu~ o~talned Wll~
successively charged lnto ba~chwlse reactors every one hour. The second reaction was conducted with stirring for 8 hours.
The slurry obtained as the reaction product was analyzed.
Compounds havlng three aromatlc rlngs were almost undetected. The contents of the o,p'-isomer and Dlanin's compound in bisphenol A were 1.5 wt.% and 0.2 wt.%, respectively.
~'~827Y7 Comparative Example 1 The product obtained by the reaction in the presence of the cation exchange resin catalyst in Example f was analyzed. The acetone conversion ratio was 45%. The contents of the o,p'-isomer and Dianin's compound in the formed bisphenol A were 6.0 wt.% and O.l wt.%, respectively.
Comparative Example 2 The same reaction as described in Comparative Example 1 was repeated except that twlce the amount of the catalyst was used.
The acetone converslon rntio was lncreased to 55%. The contents of the o,p'-isomer and Dianin's compound in bisphenol A were 6.0 wt.%
and 0.1 wt.%, respectively. That is, no change was observed.
Comparative Example 3 The same procedures described in Example 1 were repeated except the cation exchange resin catalyst was omitted. After 8 hours, the acetone converslon ratlo was 99.0% nnd the contents o~ the o,p'-i~omer nnd ~ianin'~ compound ln ~lsphenoL A wer~ 1.6 wt.~ and 0,65 wt.%, respectively. After 10 hours, the acetone conversion ratio was 99.5%, and the contents of the o,p'-isomer and Dianin's compound ln bisphenol A were 1.5 wt.% and 0.7 wt.%, respectlvely.
BACKGROUND OF THE INVENTION
The present invention relates to a process for preparing bisphenol A of high purity, that is, 2,2-bis(4-hydroxyphenyl)propane of high purity.
Bisphenol A is used as a raw material for polycarbonate reslns or epoxy reslns. Colorless and highly purified bisphenol A is particularly required for polycarbonate resins.
Bisphenol A is prepared by the reaction of acetone with excess phenol in the presence of an acid catalyst or a combination of an acid catalyst and a cocatalyst such as sulfur compounds.
The reaction mixture contains, in addition to bisphenol A, catalyst, unreacted acetone, unreacted phenol, water and other by-products formed by the reaction.
Principal components oE the by-prod~lct~ nre 2-(Z-hydroxyphenyl)-2-(4-hydroxyphenyl)propane (herelnater re~erred to as o,p'-isomer) and 2,2,4-trimethyl-4-(4-hydroxyphenyl)chroman (hereinafter referred to as Dianin's compound). Other components such as trisphenol, polyphenol and unfavorable colored sustances are also included. These by-products deteriorate the properties of the resin prepared from bisphenol A.
As the catalyst of the condensation reaction, hydrochloric acid and strongly acidic ion exchange resins have been known to date.
~"
~8X~7~37 When hydrochloric acid is used as the catalyst, the reaction can proceed at lower temperatures with successive crystallization of adduct of bisphenol A and phenol. In the course of the reaction, the o,p'-isomer in the mother liquor is converted to bisphenol A and hence the amount of the o,p'-isomer is decreased. The reaction with hydrochloric acid catalyst, however, generates a large amount of Dianin's compound as a by-product. As a method for lowering the generation of Dianin's compound, the addition of water has been disclosed by Progil in Japanese Patent Publication, TOKKOSHO 40-7186 (1965). The addition of mercapto compounds has also been reported by Dow Chemical Co. in Japnnese Patent Publication, TOKKOSHO 27-5367 (1952). These methods, however, are unfavorable because of complex procedures for the separation and recovery of hydrochloric acid and mercapto compounds as well as the obnoxious odor resulting from mercapto compounds. The generation of Dianin's compound can be reduced by uslng a greater excess of phenol. On the other hand, the formation of o,p'-lsomer increases and a large excess of phenol used must be recovered.
When commonly used Lon exch~mge re~ln~ oE ~he ~trong acld type are employed, by~-products are produced in B large amount.
Particularly when an ion exchsnge resin is used Eor the catalyst, the lsomerizntion dlle to crystallizatlon of the adduct of bisphenol ~
and phenol cannot be utlllzed and thus o,p'-lsomer ls formed ln a much larger amount when compared to the use of hydrochloric acid catalyst.
When the functlonal groups of the ion exchange resln are modified with mercapto groups such as by reaction with a mercaptoalkylamine, it has been known to markedly decrease the amount of Dianin's compound produced. o,p'-Isomer, however, is st~ll formed as a by-product in a large amount because crystallization of the adduct cannot be utilized.
When an ion exchange resin is used, water formed in the reaction leads to insufficient conversion of acetone. As a result, dehydration of the ion exchange resin is needed in every batchwise reaction. An enormous amount of the resin is also required in a continuous reaction in order to proceed with the conversion of acetone to a significant extent. These results are disclosed by ~itsui Toatsu Chemicals, Inc. in Japanese Laid-Open Patent Publication, TOKKAISHO
61-78741 (1986).
As mentioned above, previously known processes for preparing bisphenol A could not satlsfactorily inhibit the formation of two typical impurities, although these processes have their own characteristics, respectively.
SUMMARY OF THE INVENTION
The ob~ect of thi~ inventlon 1~ to provide a proces~ for preparing blsphenol A o high purity with a mlnimum amount of by-products and impurities formed in the reaction as well as the simple~t procedure in post treatment steps.
8X~9~7 BRIEF DESC~IPTION OF Tl~ DRAWING
Figure 1 is a flow diagram illustrating an embodiment of this invention for the preparation of bisphenol A.
DETAILED DESCRIPTION OF THE INVENTION
The present inventors have carried out an intensive investigation in order to achieve the above mentioned objects. ~s a result, it has been found that the objects of this invention can be achleved by reactlng a part of the acetone with excess phenol in the presence of a specific ion exchange resln and then further reacting the resultant reaction mixture in the presence of a hydrochloric acid catalyst. Thus the present invention has been achieved.
That is, the present invention is a process for preparing bisphenol A by the reaction of acetone with phenol comprising:
(a) conducting the reaction of acetone with phenol in the presence o a suLfonic acld type cation exchange resln modified wLth a mercapto group-containing compound to convert 20 to 60~ o~ the acetone in the reaction; and (b) further reacting the resulting reaction mixture containing unreacted acetone in the presence of a hydrochloric acid catalyst.
In the process of this invention, 1 mole of acetone is usually reacted with 4 to 12 moles of phenol substantially in the absence of a solvent as a third component. The total amount of acetone may be ~ ' :
7~7 charged to the first reactor containing the cation exchange resin or a part of the acetone may be fed to the second reactor containing the hydrochloric acid catalyst. Each reaction step may be composed of one or several reactors connected with each other in series or in parallel. The reactors may be batchwise or continuous, respectively.
A preferred embodiment is to continuously carry out the reaction using the cation exchange resin catalyst and to feed the reaction mixture successively to a plurality of batch reactors containing the hydrochloric acid catalyst. The present invention can be most efEectively conducted by applylng such a reactlon system.
The first reaction i8 carried out in the presence of the cation exchange resin catalyst.
The reaction is usually conducted under atmospheric pressure at a pressure of 5 kg/cm2 and a temperature of 30 to 120C, preferably 50 to 100C. When the reaction temperature is lower than 30C, the reaction rate is too slow. A reaction temperature exceeding 120C
causes an unfavorable increase of by-product formation. The reactor~
are hea~ed or cooled, 1 nece~sary.
The reaction time, usually depends upon the type of reaction and particularly the reaction temperature. For example, in a batch reaction using a stirred reactor, the reaction time i8 usually 0.1 to 10 hours. In a plston-flow type continuous reaction using a fixed bed catalyst, the reaction $9 controlled 50 as to obtain a space velocity of 0.1 to 10/hr. Acetone conver~ion ratlo of 20 to 60% can be achieved by employing the reaction conditions mentioned above.
The resin used in the process of this invention is a sulfonic acid type cation exchange resin modified with a mercapto group-containing compound.
As to the sulfonic acid type cation exchange resin, commercial products usually available in the market can be used. Modification with mercapto group containing compounds are well known to those skilled in the art. The compounds used for the modification include, for example, mercaptoalkylamines, thiazalidine compounds and pyridinealkanethiols. These compounds are disclosed by Dow Chemicals Co. in Japanese Patent Publication TOKKOSHO 46-19953 (1~71) and Japanese Lald-Oyen Pa~ent Publication TOKKAISHO 48-71389 (1973) as well as by Mitsubishi Kasei Ltd. in Japanese Laid-Open Patent Publicatiin TOKKAISHO 57-35533 (1982).
The modification method of the resin has been known. The modification can be readily carried out by neutralizing a part of the sulfonic acid groups with mercapto groups as disclosed by Dow Chemlcals Co. in Japanese Patent Publication 46-19953 (1971) and by Shell International Research Ltd. in Japnnese Lald-Open Patent Publication TOKKAS~lO 53-1~680 (1978).
The modlfication ratio i9 usually 5 to 35 mole %, preferably 10 to 20 mole % of the sulfonic acid groups in the resin. A
modification ratio lower than 5 mole % causes a decrease in the reaction velocity and an increase in the Dianin's compound. A
modification ratio exceeding 35 mole % also leads to a decrease in the reaction velocity and conversion rate.
lX8X79~
The reaction using the resin catalyst is terminated at an acetone conversion of 20 to 60%. When a conversion sate of more than 60% is intended to be obtained, the conversion velocity decreases rapidly due to the generation of water and a huge amount of the catalyst is required a~ disclosed by Mitsui Toatsu Chemicals, Inc. in Japanese Laid-Open Patent TOKKAISHO 61-78741 (1986). ~hen the reaction proceeds along with continuous removal of generated water, a high conversion ratio can be obtained by a small amount of the resin, but the amount of o,p'-isomer cannot be lowered to less than that obtaLned by tl1e reaction ln the presence of resin.
The second reaction 1~ carried out in the presence of a hydrochloric acid catalyst. The hydrochloric acid catalyst may be supplied as the form of aqueous hydrochloric acid, hydrogen chloride or a mixture thereof. The reaction can be conducted a known manner except that the reaction mixture produced in the presence of the cation exchange resin catalyst is u~ed. The reaction is carried out under agitation at 30 to 85C, preferably at 35 to 60~C. Hydrogen chlorlde may be saturated prior to the reactlon or contlnuou~ly eed to the reactor. In con~ideratlotl o~ the e~othe~nlc ~bsorptlon Oe hydrogen chloride, the heat of reaction and the crystallization heat of the adduct, lt 18 preferred to feed hydrogen chloride both prior to and in the course of the reaction. Generated heat is removed by external cooling to control the reaction temperature within the range mentioned above.
Adduct cry~tal~ of bisphenol A and phenol are precipitated with the progres~ of tile reaction. The o,p'-i~omer in the ~olution ls ~8Z797 isomerized to bisphenol A accompanied by ~he crystallization of the adduct. Thus the concentration of the o,p'-isomer is decreased. The Dianin's compound generates only a slight amount because the acetone charged into the second reaction is in a low concentration.
Water, catalyst and excess phenol are removed from the reaction mixture thus obtained to give bisphenol A.
The resultant bisphenol A is used as the product as it is or can be subjected to further steps for purification and forming to give the product. Colorless bisphenol A of high purity can also be obtained by retnovlng phenol from the crystallized adduct of bisphenol A and phenol.
An example of a flow diagram for carrying out the process of this invention will be briefly described by way of Figure 1.
Phenol (1) and acetone (3) are mixed ln a mixing tank (2) and fed to the reactor (5) containing the cation exchange resin catalyst.
Reaction product ttlixture (6) from the reactor (5) contains unreacted acetone. A part (7) of the reaction product mixture (6) is mixed with the raw materlals and recycled again to the flrst reactor (5). The remainder (8) of the m:Lxture (6) i8 tran~earred to a h~drogen chlorlde absorptlon colutnn (9) und aaturated with hydrogen chlorlde (10). The resultant mixture ls then reacted ln the second reactor (14) which ls a hydrochloric acld catalyst reactor. The reactlon is conducted for several hours to react almost all of the acetone. Thereafter the reaction product (15) i9 transferred to the purification step. When the amount of hydrochloric acid is insufficient in the course of the a~7'~37 reaction in the reactor (14) mentioned above, hydrogen chloride or concentrated hydrochloric acid (11) is supplied to the reactor (14).
~XAMPLE
The process of this invention will hereinafter be described in detail by way of example and comparative examples.
Example 1 A sulfonic acld type cation exchange resin was used as the catalyst after modlfylng 12% of its sul~onlc acid groups with mercaptoethylamlne. The catalyst was used in the form of a packed layer having a diameter of 30 cm and a length of 200 cm.
A mixture of 564 kg/hr of phenol and 58 kg/hr of acetone was passed through the catalyst layer at 70C under atmospheric pressure and reacted continuously.
Hydrogen chloride was blown into the reaction mlxture in the hydrogen chlorlde ab~orptiotl column. The ml~ture thu~ o~talned Wll~
successively charged lnto ba~chwlse reactors every one hour. The second reaction was conducted with stirring for 8 hours.
The slurry obtained as the reaction product was analyzed.
Compounds havlng three aromatlc rlngs were almost undetected. The contents of the o,p'-isomer and Dlanin's compound in bisphenol A were 1.5 wt.% and 0.2 wt.%, respectively.
~'~827Y7 Comparative Example 1 The product obtained by the reaction in the presence of the cation exchange resin catalyst in Example f was analyzed. The acetone conversion ratio was 45%. The contents of the o,p'-isomer and Dianin's compound in the formed bisphenol A were 6.0 wt.% and O.l wt.%, respectively.
Comparative Example 2 The same reaction as described in Comparative Example 1 was repeated except that twlce the amount of the catalyst was used.
The acetone converslon rntio was lncreased to 55%. The contents of the o,p'-isomer and Dianin's compound in bisphenol A were 6.0 wt.%
and 0.1 wt.%, respectively. That is, no change was observed.
Comparative Example 3 The same procedures described in Example 1 were repeated except the cation exchange resin catalyst was omitted. After 8 hours, the acetone converslon ratlo was 99.0% nnd the contents o~ the o,p'-i~omer nnd ~ianin'~ compound ln ~lsphenoL A wer~ 1.6 wt.~ and 0,65 wt.%, respectively. After 10 hours, the acetone conversion ratio was 99.5%, and the contents of the o,p'-isomer and Dianin's compound ln bisphenol A were 1.5 wt.% and 0.7 wt.%, respectlvely.
Claims (14)
1. A process for preparing bisphenol A by the reaction of acetone with phenol comprising:
(a) conducting the reaction of acetone with phenol in the presence of a sulfonic acid type cation exchange resin modified with a mercapto group-containing compound to convert 20 to 60% of the acetone in the reaction; and (b) further reacting the resulting reaction mixture containing unreacted acetone in the presence of a hydrochloric acid catalyst.
(a) conducting the reaction of acetone with phenol in the presence of a sulfonic acid type cation exchange resin modified with a mercapto group-containing compound to convert 20 to 60% of the acetone in the reaction; and (b) further reacting the resulting reaction mixture containing unreacted acetone in the presence of a hydrochloric acid catalyst.
2. The process as claimed in claim 1 wherein the mole ratio of acetone to phenol is 1:4 to 1:12.
3. The process as claimed in claim 1 wherein 5 to 35 mole % of the sulfonic acid groups in said cation exchange resin are modified with the mercapto group-containing compound.
4. The process as claimed in claim 1 wherein 12 mole % of the sulfonic acid groups in said cation exchange resin are modified with mercaptoethylamine.
5. The process as claimed in claim 1 wherein said reaction in the presence of the cation exchange resin is conducted at a temperature of 30 to 120°C.
6. The process as claimed in claim 1 wherein said reaction in the presence of the hydrochloric acid catalyst is conducted at a temperature of 30 to 85°C.
7. The process as claimed in claim 1 wherein the reaction in the presence of the cation exchange resin is conducted continuously and the reaction in the presence of the hydrochloric acid catalyst is carried out batchwise.
8. A process for preparing bisphenol A of high purity by the reaction of acetone with phenol, wherein 4 to 12 moles of phenol are employed per mole of acetone and the reaction is con-ducted substantially in the absence of a solvent, the said process comprising:
(a) reacting acetone with phenol at a temperature of 30 to 120°C in the presence of a sulfonic acid type cation exchange resin modified with a mercapto group-containing compound, until 20 to 60% of acetone is converted, thereby obtaining a first reaction mixture which contains unreacted acetone, unreacted phenol, bisphenol A and 2-(2-hydroxyphenyl)-2-(4-hydroxyphenyl)propane;
(b) separating the first reaction mixture from the sulfonic acid type cation exchange resin;
(c) treating the separated first reaction mixture under agitation in the presence of saturated hydrogen chloride at a temperature of 30 to 85°C so as to react the unreacted acetone with the remaining phenol and to isomerize 2-(2-hydroxyphenyl)-2-(4-hydroxyphenyl)propane into bisphenol A, while precipitating crystals of bisphenol A/phenol adduct as the reaction progresses from a second reaction mixture which contains water, unreacted phenol, hydrochloric acid, bisphenol A and substantially no acetone;
(d) removing the water, the unreacted phenol and hydrochloric acid from the second reaction mixture, thereby obtaining bisphenol A which may be in a bisphenol A/phenol adduct form; and (e) where necessary, decomposing the bisphenol a/phenol adduct.
(a) reacting acetone with phenol at a temperature of 30 to 120°C in the presence of a sulfonic acid type cation exchange resin modified with a mercapto group-containing compound, until 20 to 60% of acetone is converted, thereby obtaining a first reaction mixture which contains unreacted acetone, unreacted phenol, bisphenol A and 2-(2-hydroxyphenyl)-2-(4-hydroxyphenyl)propane;
(b) separating the first reaction mixture from the sulfonic acid type cation exchange resin;
(c) treating the separated first reaction mixture under agitation in the presence of saturated hydrogen chloride at a temperature of 30 to 85°C so as to react the unreacted acetone with the remaining phenol and to isomerize 2-(2-hydroxyphenyl)-2-(4-hydroxyphenyl)propane into bisphenol A, while precipitating crystals of bisphenol A/phenol adduct as the reaction progresses from a second reaction mixture which contains water, unreacted phenol, hydrochloric acid, bisphenol A and substantially no acetone;
(d) removing the water, the unreacted phenol and hydrochloric acid from the second reaction mixture, thereby obtaining bisphenol A which may be in a bisphenol A/phenol adduct form; and (e) where necessary, decomposing the bisphenol a/phenol adduct.
9. The process as claimed in claim 8, wherein 5 to 35 mole % of the sulfonic acid groups in the cation exchange resin used in step (a) are modified with the mercapto group-containing compound.
10. The process as claimed in claim 8, wherein 10 to 20 mole % of the sulfonic acid groups in the cation exchange resin used in step (a) are modified with the mercapto group-containing compound.
11. The process as claimed in claim 9, wherein the mercapto group-containing compound is a mercaptoalkylamine, a thiazalidine compound or a pyridinealkanethiol.
12. The process as claimed in claim 8, 9 or 10, wherein the mercapto group-containing compound is mercaptoethylamine.
13. The process as claimed in claim 8, 9 or 10, wherein the reaction of step (a) is carried out at a temperature of 50 to 100°C.
14. The process as claimed in claim 8, 9 or 10, wherein the treatment of step (c) is carried out at a temperature of 35 to 60°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62305942A JPH07103058B2 (en) | 1987-12-04 | 1987-12-04 | Method for producing bisphenol A |
| JP62-305942 | 1987-12-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1282797C true CA1282797C (en) | 1991-04-09 |
Family
ID=17951153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000584934A Expired - Fee Related CA1282797C (en) | 1987-12-04 | 1988-12-02 | Process for preparing bisphenol a |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4918245A (en) |
| EP (1) | EP0319327B1 (en) |
| JP (1) | JPH07103058B2 (en) |
| KR (1) | KR910003252B1 (en) |
| CN (1) | CN1013364B (en) |
| CA (1) | CA1282797C (en) |
| DE (1) | DE3870172D1 (en) |
| ES (1) | ES2030874T3 (en) |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2658814B1 (en) * | 1990-02-28 | 1993-12-31 | Rhone Poulenc Chimie | PROCESS FOR THE MANUFACTURE OF BISPHENOL-A. |
| US5336813A (en) * | 1990-11-13 | 1994-08-09 | General Electric Company | Process for low color bisphenol |
| CN1080914A (en) * | 1993-02-17 | 1994-01-19 | 中国石油化工总公司 | A kind of 2, the manufacture method of 2-two (4-hydroxy phenyl) propane |
| RU2126706C1 (en) * | 1993-02-17 | 1999-02-27 | Чайна Петро-Кемикал Корпорейшн | Multistage method of suspension reaction steaming and device for its embodiment |
| US5315042A (en) * | 1993-03-22 | 1994-05-24 | General Electric Company | Use of partial acetone conversion for capacity increase and quality/yield improvement in the bisphenol-A reaction |
| US5414151A (en) * | 1994-05-02 | 1995-05-09 | General Electric Company | Method for making bisphenol |
| DE19540497A1 (en) * | 1995-10-31 | 1997-05-07 | Degussa | Inorganic support materials containing sulfonate and mercapto groups, process for their preparation and use as catalysts |
| DE19640710A1 (en) * | 1996-10-02 | 1998-04-09 | Phenolchemie Gmbh | Process for the transport and storage of phenol |
| ID30168A (en) * | 2000-01-07 | 2001-11-08 | Idemitsu Petrochemical Co | BISPHENOL A MAKING PROCESS |
| US6740684B2 (en) | 2000-09-19 | 2004-05-25 | Dow Global Technologies Inc. | Process for producing a strong-acid cation exchange resin |
| US6703530B2 (en) | 2002-02-28 | 2004-03-09 | General Electric Company | Chemical reactor system and process |
| US7112702B2 (en) * | 2002-12-12 | 2006-09-26 | General Electric Company | Process for the synthesis of bisphenol |
| US6858759B2 (en) * | 2002-12-20 | 2005-02-22 | General Electric Company | Process for manufacture of bisphenols |
| US6635788B1 (en) * | 2002-12-20 | 2003-10-21 | General Electric Company | Process for manufacture of bisphenols |
| US7132575B2 (en) * | 2003-07-01 | 2006-11-07 | General Electric Company | Process for the synthesis of bisphenol |
| US7041774B2 (en) | 2003-09-30 | 2006-05-09 | General Electric Company | Functionalized zeolite compositions and methods for their preparation and use |
| US8735634B2 (en) | 2011-05-02 | 2014-05-27 | Sabic Innovative Plastics Ip B.V. | Promoter catalyst system with solvent purification |
| US9290618B2 (en) | 2011-08-05 | 2016-03-22 | Sabic Global Technologies B.V. | Polycarbonate compositions having enhanced optical properties, methods of making and articles comprising the polycarbonate compositions |
| WO2013116697A1 (en) | 2012-02-03 | 2013-08-08 | Sabic Innovative Plastics Ip B.V. | Light emitting diode device and method for production thereof containing conversion material chemistry |
| US9287471B2 (en) | 2012-02-29 | 2016-03-15 | Sabic Global Technologies B.V. | Polycarbonate compositions containing conversion material chemistry and having enhanced optical properties, methods of making and articles comprising the same |
| WO2013130606A2 (en) | 2012-02-29 | 2013-09-06 | Sabic Innovative Plastics Ip B.V. | Polycarbonate made from low sulfur bisphenol a and containing converions material chemistry, and articles made therefrom |
| US9346949B2 (en) | 2013-02-12 | 2016-05-24 | Sabic Global Technologies B.V. | High reflectance polycarbonate |
| KR101961312B1 (en) | 2012-10-25 | 2019-03-22 | 사빅 글로벌 테크놀러지스 비.브이. | Light emitting diode devices, method of manufacture, uses thereof |
| KR102229148B1 (en) | 2013-05-29 | 2021-03-23 | 사빅 글로벌 테크놀러지스 비.브이. | Illuminating devices with color stable thermoplastic light-transmitting articles |
| CN106563502B (en) * | 2016-11-04 | 2019-01-25 | 凯瑞环保科技股份有限公司 | A kind of bisphenol-A synthetic resin catalyst and preparation method thereof |
| JP7117324B2 (en) * | 2017-04-24 | 2022-08-12 | バジャー・ライセンシング・エルエルシー | Catalyst system and process for producing bisphenol A |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3172916A (en) * | 1965-03-09 | Bisphenol axpreparation u using ion ex- change resin containing mercapto and sulfonic acid groups | ||
| US2359242A (en) * | 1941-08-23 | 1944-09-26 | Dow Chemical Co | Preparation of phenol-ketone condensation products |
| US3221061A (en) * | 1961-08-01 | 1965-11-30 | Union Carbide Corp | Process for the production of 2,2-bis-(4-hydroxyphenyl) propane |
| FR1342760A (en) * | 1962-02-16 | 1963-11-15 | Progil | Manufacture of aryl alkanes |
| DE1518321A1 (en) * | 1964-07-24 | 1972-03-09 | ||
| GB1578225A (en) * | 1977-07-11 | 1980-11-05 | Shell Int Research | Preparation of bisphenols |
| US4188496A (en) * | 1977-12-23 | 1980-02-12 | General Electric Company | Process for preparing 2,2-bis(4-hydroxy-phenyl) propane from distillation by-products thereof |
| US4308405A (en) * | 1978-07-05 | 1981-12-29 | Shell Oil Company | Preparation of bisphenols |
| US4584416A (en) * | 1983-11-14 | 1986-04-22 | General Electric Company | Method and catalyst for making bisphenol |
-
1987
- 1987-12-04 JP JP62305942A patent/JPH07103058B2/en not_active Expired - Lifetime
-
1988
- 1988-11-28 US US07/276,658 patent/US4918245A/en not_active Expired - Fee Related
- 1988-12-02 CA CA000584934A patent/CA1282797C/en not_active Expired - Fee Related
- 1988-12-02 ES ES198888311465T patent/ES2030874T3/en not_active Expired - Lifetime
- 1988-12-02 KR KR1019880016077A patent/KR910003252B1/en not_active IP Right Cessation
- 1988-12-02 DE DE8888311465T patent/DE3870172D1/en not_active Expired - Fee Related
- 1988-12-02 EP EP88311465A patent/EP0319327B1/en not_active Expired - Lifetime
- 1988-12-03 CN CN88108296A patent/CN1013364B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| KR910003252B1 (en) | 1991-05-25 |
| KR890009831A (en) | 1989-08-04 |
| ES2030874T3 (en) | 1992-11-16 |
| JPH01149746A (en) | 1989-06-12 |
| CN1034360A (en) | 1989-08-02 |
| US4918245A (en) | 1990-04-17 |
| DE3870172D1 (en) | 1992-05-21 |
| EP0319327A1 (en) | 1989-06-07 |
| CN1013364B (en) | 1991-07-31 |
| EP0319327B1 (en) | 1992-04-15 |
| JPH07103058B2 (en) | 1995-11-08 |
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