EP0495097A4 - Preparation of relatively pure p, p-bisphenol s - Google Patents
Preparation of relatively pure p, p-bisphenol sInfo
- Publication number
- EP0495097A4 EP0495097A4 EP19910919236 EP91919236A EP0495097A4 EP 0495097 A4 EP0495097 A4 EP 0495097A4 EP 19910919236 EP19910919236 EP 19910919236 EP 91919236 A EP91919236 A EP 91919236A EP 0495097 A4 EP0495097 A4 EP 0495097A4
- Authority
- EP
- European Patent Office
- Prior art keywords
- bps
- mixture
- reaction
- phenol
- solvent
- 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.)
- Withdrawn
Links
- 238000002360 preparation method Methods 0.000 title description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000000203 mixture Substances 0.000 claims abstract description 36
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 13
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 16
- 239000011541 reaction mixture Substances 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000006317 isomerization reaction Methods 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000002798 polar solvent Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 14
- 238000004821 distillation Methods 0.000 description 8
- 238000010992 reflux Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- 241001550224 Apha Species 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000003828 vacuum filtration Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- -1 p-dihydroxydiphenyl sulfone Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C317/22—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
Definitions
- This invention relates to the manufacture of p,p-dihydroxydiphenyl sulfone, known also as 4,4'-Bisphenol S (hereafter sometimes "4,4'-BPS”) , and particularly to a method of efficiently and/or continuously separating 4,4'-BPS from a product mixture containing significant quantities of 2,4'-BPS, which is typically produced along with the 4,4'-BPS.
- 4,4'-BPS 4,4'-Bisphenol S
- reaction of sulfuric acid and phenol to make BPS can be conducted quite efficiently by (a) forcing the dehydration reaction to completion (or near completion) by gradually distilling a mixture of water and phenol from the reaction mixture, (b) selectively precipitating 4,4'-BPS from the reaction mixture by adding a solvent such as toluene, (c) removing the 4,4'-BPS from the mixture by a separation step, i.e. filtration or centrifugation, and (d) the unrecovered material from the separation step is recycled to the dehydration reaction step.
- the purity of the product 4,4'-BPS is maintained at a high level by following this process, particularly in the detail described below; the color is excellent.
- Solvents which may be used other than toluene are benzene, chlorobenzene, xylene, o-dichlorobenzene, anisole, cumene, and the like.
- My invention comprises
- step (f) recycling the isolated BPS isomers from step (e) by adding the mixture to reaction step (a) to bring about isomerization of the 2,4'-BPS contained in the filtrate to 4,4'-BPS during the reaction cycle.
- (g) further purifying the crude 4,4'-BPS isolated from separation step (d) above by recrystallizing the compound from water or mixtures of water and solvents such as methanol, ethanol and acetone, preferably methanol.
- the water or water/solvent mixture should contain about 0.0005 to about 0.05 molar equivalents, preferably about 0.002 to 0.01 molar equivalents (based on the amount of BPS being recrystallized) of a reducing agent such as a thiosulfate, sulfite, bisulfite or borohydride salt, preferably sodium bisulfite, to reduce the amount of color in the final product.
- a reducing agent such as a thiosulfate, sulfite, bisulfite or borohydride salt, preferably sodium bisulfite
- a preferred process (best mode) is as follows:
- reaction mixture is then refluxed for an additional 1-1.5 hours, collecting distillate only when the still head temperature falls below 170°C.
- Toluene (a volume equivalent to the volume of phenol used in the reaction) is slowly added to the reaction mixture. This cools the reaction mixture to the boiling point of toluene (110°C) and reduces the solubility of BPS in the solution.
- the reaction mixture temperature reaches about 130 ⁇ C and the solvent is approximately 25-30% toluene, the 4,4'-isomer of BPS begins to precipitate from the solution as a fine pink powder. The remainder of the toluene is added while the precipitation continues.
- step (10) The precipitate from the distillation pot residue in step (9) is filtered from the slurry and is then recycled by adding it to a subsequent reaction batch of BPS between steps (2) and (3), above.
- Toluene (100 ml) was added over a period of 40 minutes while maintaining rapid stirring. After the addition was complete, the mixture was allowed to cool to 60°C. The product was removed from the suspension by vacuum filtration and rinsed with two portions of toluene (50 ml) and then dried to remove the residual toluene to yield 33.41 g of 4,4'-BPS with a purity of 97.5%.
- the crude product was dissolved in boiling methanol (25 ml) and hot water (225 ml) which contained sodium thiosulfate (0.10 g) was added while keeping the mixture boiling.
- the solution was cooled to 25°C and allowed to crystallize over a period of 3 hours at that temperature.
- the product was collected by vacuum filtration and the water removed from the crystals to yield 31.72 g of 4,4'-BPS with a purity >99.5% and an APHA color of ⁇ 20 for a 30% solution in methanol.
- Toluene 150 ml was added to the reaction mixture over a period of one hour and the mixture was allowed to cool to 65°C before the product was filtered from the mixture to produce 44.10 g of light pink material which was purified by the means described in Example 1 to give a final product with the >99.5% purity and APHA color of ⁇ 20 for a 30% methanolic solution.
- Phenol (151.40 g) and sulfuric acid (35.94 g, 96.0%) were reacted in the manner described in Example 1. After the addition of toluene (150 ml) and cooling of the reaction mixture to 70°C, 4,4'-BPS (52.1 g, 97.7%) was separated from the excess phenol and toluene by vacuum filtration.
- the filtrate was distilled under vacuum to remove the toluene and most of the phenol (78 g).
- the toluene was added to the distillation pot residue, causing the precipitation of a mixture of 2,4'-BPS and 4,4'-BPS (28.1 g).
- Phenol (182.2 g) and sulfuric acid (35.2 g) were mixed and heated to 130 ⁇ C for one hour.
- the mixture of BPS isomers from above was added to the mixture which was then heated to reflux (155°C) for one hour.
- the reaction was then carried out as in Example 1 with the mixture of water and phenol distilled off whenever the vapor temperature fell below 160°C.
- Toluene (180 ml) was added to the mixture and the product was collected after the mixture had cooled to 65°C.
- the crude 4,4'-BPS (74.2g) was recrystallized as described in Example 1 to produce a material with purity >99.5% and APHA color of 30 for a 30% methanolic solution.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process of preparing 4,4'-Bisphenol S wherein sulfuric acid is reacted with an excess of phenol while removing water; the product purity is improved with respect to the 2,4'-BPS isomer by adding toluene to the initial product mixture to crystallize and remove the desired 4,4'-BPS. The remaining material is recycled to isomerize the 2,4'-BPS to 4,4'-BPS.
Description
PREPARATION OF RELATIVELY PURE P,P-BISPHENOL S
Technical Field
This invention relates to the manufacture of p,p-dihydroxydiphenyl sulfone, known also as 4,4'-Bisphenol S (hereafter sometimes "4,4'-BPS") , and particularly to a method of efficiently and/or continuously separating 4,4'-BPS from a product mixture containing significant quantities of 2,4'-BPS, which is typically produced along with the 4,4'-BPS. The basic principle of reacting sulfuric acid with an excess of phenol is known.
Background of the Invention
It is known to react sulfuric acid with an excess of phenol to obtain Bisphenol S. In Ogata et al U.S. Patent 4,820,831 a process is described (col. 4) wherein the phenol/sulfuric acid (dehydration) reaction is conducted in the presence of a solvent which is distilled off along with the excess phenol to promote the production of 4,4'-BPS. In U. S. Patent 4,820,831, Ogata et al also adds an aromatic sulfuric acid to promote isomerization of 2,4'-BPS to 4,4'-BPS. However, there are disadvantages to this procedure, namely that the color of the reaction product deteriorates as the solvent and phenol are removed from the mixture and the colored materials formed as well as any catalysts added must be removed in subsequent purification steps.
In U.S. Patent 4,382,147, Kitamura et al cool the original dehydration reaction product (or, apparently, any mixture of BPS isomers) to separate out the 4,4'-BPS. No particular solvent is used; the 4,4'-BPS is separated as an adduct with phenol.
Summary of the Invention
I have found that the reaction of sulfuric acid and phenol to make BPS can be conducted quite efficiently by (a) forcing the dehydration reaction to completion (or near completion) by gradually distilling a mixture of water and phenol from the reaction mixture, (b) selectively precipitating 4,4'-BPS from the reaction mixture by adding a solvent such as toluene, (c) removing the 4,4'-BPS from the mixture by a separation step, i.e. filtration or centrifugation, and (d) the unrecovered material from the separation step is recycled to the dehydration reaction step. The purity of the product 4,4'-BPS is maintained at a high level by following this process, particularly in the detail described below; the color is excellent.
Solvents which may be used other than toluene are benzene, chlorobenzene, xylene, o-dichlorobenzene, anisole, cumene, and the like.
Detailed Description of the Invention
My invention comprises
(a) reacting sulfuric acid and phenol in a ratio of about 1:2 to about 1:10, preferably about
1:2.5 to about 1:5, at temperatures beginning at about 40 to about 100°C, preferably about 60 to about 70°C and increasing during the reaction to about 190 to about 205°C, preferably about 195 to about 200°C under an inert atmosphere such as nitrogen or argon, preferably at atmospheric pressure although a vacuum may be used.
(b) during the reaction, removing the water formed by distilling off the water as a mixture with phenol until the reaction is complete, or nearly complete.
(c) adding about 0.1 to about 5.0 equivalent volumes, preferably about 0.5 to about 1.5 volumes (based on the volume of phenol used for the reaction as one equivalent volume), of a solvent for Bisphenol S, preferably benzene, toluene, chlorobenzene, xylene, o-dichlorobenzene, anisole, or cumene, most preferably toluene, over a period of about 10 to about 200 minutes, preferably about 30 to about 60 minutes. During the addition the mixture should be cooled or allowed to cool to the boiling point of the solvent, then the mixture allowed to cool further to about room temperature to about 120βC, preferably about 55 to about 75°C to form crystals of 4,4'-BPS.
(d) separating the crystals of 4,4'-BPS from the reaction mixture preferably by filtration or centrifugation.
(e) isolating the BPS isomers from the filtrate from step (d) by removal of the solvent and phenol and crystallizing the BPS isomers, and
(f) recycling the isolated BPS isomers from step (e) by adding the mixture to reaction
step (a) to bring about isomerization of the 2,4'-BPS contained in the filtrate to 4,4'-BPS during the reaction cycle.
(g) further purifying the crude 4,4'-BPS isolated from separation step (d) above by recrystallizing the compound from water or mixtures of water and solvents such as methanol, ethanol and acetone, preferably methanol. The water or water/solvent mixture should contain about 0.0005 to about 0.05 molar equivalents, preferably about 0.002 to 0.01 molar equivalents (based on the amount of BPS being recrystallized) of a reducing agent such as a thiosulfate, sulfite, bisulfite or borohydride salt, preferably sodium bisulfite, to reduce the amount of color in the final product.
A preferred process ("best mode") is as follows:
(1) Molten phenol (purified, 4.75-5.0 molar equiv.) is placed in the reactor and the system is flushed with an inert atmosphere (nitrogen) .
(2) Concentrated sulfuric acid (1.0 molar equiv.) is added to the phenol and the mixture is heated to reflux (155°C) over a period of 30 minutes.
(3) A mixture of water and phenol is slowly distilled off until the reaction temperature reaches 195°C and the distillation head temperature reaches 170°C. This usually takes 2-2.5 hours.
(4) The reaction mixture is then refluxed for an additional 1-1.5 hours, collecting distillate only when the still head temperature falls below 170°C.
(5) Toluene (a volume equivalent to the volume of phenol used in the reaction) is slowly added to the reaction mixture. This cools the reaction mixture to the boiling point of toluene (110°C) and reduces the solubility of BPS in the solution. When the reaction mixture temperature reaches about 130βC and the solvent is approximately 25-30% toluene, the 4,4'-isomer of BPS begins to precipitate from the solution as a fine pink powder. The remainder of the toluene is added while the precipitation continues.
(6) After all the toluene has been added, the mixture is cooled to 65°C and then filtered.
(7) The solid is rinsed with toluene to remove some orange colored material and then dried to yield a light pink powder.
(8) The toluene and most of the phenol are distilled under vacuum from the filtrate from step (6).
(9) Toluene is added to the distillation residue from step (8) to precipitate the 2,4'-BPS isomer and the remainder of the 4,4'-isomer.
(10) The precipitate from the distillation pot residue in step (9) is filtered from the slurry and is then recycled by adding it to a subsequent reaction batch of BPS between steps (2) and (3), above.
(11) An additional one hour reflux period is added to the beginning of step (3) above, before any distillate is collected, for batches of BPS which contain recycled materials to help insure complete equilibration of the BPS isomers during the reaction cycle.
(12) The BPS from step (7) is dissolved in an equivalent weight of boiling methanol and treated with 0.005 molar equivalents of sodium sulfite as a 1.0 molar solution in water. The methanolic solution is then diluted with water (9 times the weight of the methanol used) keeping the mixture at its boiling point. After all of the water has been added the mixture is allowed to cool to room temperature. The solid is removed from the mixture by filtration and rinsed with water and dried to remove the excess solvent.
My process has been used successfully as is illustrated in the following examples of experiments performed:
Example 1
Sulfuric acid (22.62 g, 94.6%) was added to molten phenol (100.41 g) at 70°C with rapid stirring into a reaction flask equipped with a simple distillation apparatus. The mixture was heated to 130°C for one hour and then heated further to reflux temperature (155°C) and a mixture of water and phenol was gradually distilled from the reaction flask until the solution temperature reached 195°C and the distillation head temperature had reached 170βC. The distillate collection was stopped and the mixture was refluxed until the vapor temperature fell to below 160°C. The distillate was collected again until the distillation head temperature again rose to 170°C. The cycle of distillate collection and refluxing was continued until 2.5 hours had elapsed since the first distillate was collected.
Toluene (100 ml) was added over a period of 40 minutes while maintaining rapid stirring. After the addition was complete, the mixture was allowed to cool to 60°C. The product was removed from the suspension by vacuum filtration and rinsed with two portions of toluene (50 ml) and then dried to remove the residual toluene to yield 33.41 g of 4,4'-BPS with a purity of 97.5%.
The crude product was dissolved in boiling methanol (25 ml) and hot water (225 ml) which contained sodium thiosulfate (0.10 g) was added while keeping the mixture boiling. The solution was cooled to 25°C and allowed to crystallize over a period of 3 hours at that temperature. The product was collected by vacuum filtration and the water removed from the crystals to yield 31.72 g of 4,4'-BPS with a purity >99.5% and an APHA color of <20 for a 30% solution in methanol.
Example 2
Sulfuric acid (35.45 g, 93.5%) was added to molten phenol (150.38 g) at 70°C in a reaction flask equipped with a distillation head and the apparatus was evacuated to 350 mm Hg. The mixture was heated to reflux and the distillate was collected any time the distillation head temperature was below 140°C and the distillate collection was stopped any time the vapor temperature rose to 150°C. The reaction mixture was heated in this manner for five hours.
Toluene (150 ml) was added to the reaction mixture over a period of one hour and the mixture was allowed to cool to 65°C before the product was
filtered from the mixture to produce 44.10 g of light pink material which was purified by the means described in Example 1 to give a final product with the >99.5% purity and APHA color of <20 for a 30% methanolic solution.
Example 3
Sulfuric acid (35.20 g, 96.0%) was added to molten phenol (153.30 g) at 70°C in a reaction flask equipped with a Dean-Starke trap and the mixture was heated to 130°C. Cumene (90 ml) was added to the reaction mixture and the solution was heated to reflux, collecting the water of the reaction in the trap and continuously returning the cumene to the reaction vessel. The reaction mixture was refluxed for 7.5 hours at which point the cumene in the Dean-Starke trap was separated from the water and added to the reaction mixture along with an additional 60 ml cumene over a period of 15 minutes. The mixture was gradually cooled to 70°C allowing the product to slowly crystalize. The solid was collected by vacuum filtration, rinsed with two 50 ml portions of cumene and dried to remove the remainder of the solvent to yield 4,4'-BPS (60.1 g, 98.1%). After purification by the method described in Example 1, a product was obtained with a purity >99.5% and an APHA color of <20 for a 30% solution in methanol.
Example 4
Phenol (151.40 g) and sulfuric acid (35.94 g, 96.0%) were reacted in the manner described in Example 1. After the addition of
toluene (150 ml) and cooling of the reaction mixture to 70°C, 4,4'-BPS (52.1 g, 97.7%) was separated from the excess phenol and toluene by vacuum filtration.
The filtrate was distilled under vacuum to remove the toluene and most of the phenol (78 g). The toluene was added to the distillation pot residue, causing the precipitation of a mixture of 2,4'-BPS and 4,4'-BPS (28.1 g).
Phenol (182.2 g) and sulfuric acid (35.2 g) were mixed and heated to 130βC for one hour. The mixture of BPS isomers from above was added to the mixture which was then heated to reflux (155°C) for one hour. The reaction was then carried out as in Example 1 with the mixture of water and phenol distilled off whenever the vapor temperature fell below 160°C. Toluene (180 ml) was added to the mixture and the product was collected after the mixture had cooled to 65°C. The crude 4,4'-BPS (74.2g) was recrystallized as described in Example 1 to produce a material with purity >99.5% and APHA color of 30 for a 30% methanolic solution.
Claims
1. A process for making purified 4,4'-dihydroxydiphenyl sulfone comprising
(a) reacting sulfuric acid and phenol in a ratio of about 1:2 to about 1:10 at temperatures starting at about 40 to about 100°C and increasing during the reaction to temperatures of about 190 to about 205°C,
(b) during the reaction, removing the water formed by codistilling a mixture of water and phenol from the reaction mixture,
(c) adding about 0.1 to about 5.0 equivalent volumes of a solvent for 4,4'-Bisphenol S (based on the volume of phenol used in the reaction as 1.0 equivalent volume) and cooling the mixture to about room temperature to about 120°C to cause formation of crystals of 4,4'-Bisphenol S,
(d) separating the crystals of 4,4'-BPS from the reaction mixture,
(e) further purifying the crystal product by dissolving and recrystallizing the crystal product in mixtures of water and a polar solvent with the addition of about 0.0005 to about 0.05 molar equivalents of a reducing agent, and
(f) recycling at least some of the filtrate from step (d) to the dehydration step (a) after removal of the solvent to bring about the isomerization of the 2,4'-BPS.
2. Process of claim 1 wherein the solvent of step (c) is toluene.
3. Process of claim 1 wherein step (d) is performed by filtration.
4. Process of claim 1 wherein step (d) is performed by centrifugation.
5. Process of claim 1 wherein the solvent of step (e) is methanol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US56449390A | 1990-08-06 | 1990-08-06 | |
| US564493 | 2000-05-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0495097A1 EP0495097A1 (en) | 1992-07-22 |
| EP0495097A4 true EP0495097A4 (en) | 1993-01-13 |
Family
ID=24254698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19910919236 Withdrawn EP0495097A4 (en) | 1990-08-06 | 1991-06-24 | Preparation of relatively pure p, p-bisphenol s |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0495097A4 (en) |
| JP (1) | JPH05500522A (en) |
| CA (1) | CA2066178A1 (en) |
| WO (1) | WO1992002493A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10018580A1 (en) | 2000-04-14 | 2001-10-25 | Basf Ag | Semi-continuous process for the production of 4,4'-dihydroxydiphenylsulfone comprises reaction of phenol with a sulfonating agent and suspension of the resulting crude product in water |
| WO2003078388A1 (en) * | 2000-09-08 | 2003-09-25 | Nippon Soda Co.,Ltd. | Process for producing 4,4'-bisphenol sulfone |
| JP4531226B2 (en) * | 2000-09-08 | 2010-08-25 | 日本曹達株式会社 | Method for producing 4,4'-bisphenolsulfone |
| JP4562888B2 (en) * | 2000-09-08 | 2010-10-13 | 日本曹達株式会社 | Method for producing 4,4'-bisphenolsulfone |
| CN1332945C (en) * | 2002-03-20 | 2007-08-22 | 日本曹达株式会社 | Process for producing 4,4'-bisphenol sulphone |
| WO2004029020A1 (en) * | 2002-09-25 | 2004-04-08 | Konishi Chemical Ind. Co., Ltd. | Process for producing high-purity 4,4'-dihydroxydiphenyl sulfone |
| CN113683538B (en) * | 2021-07-23 | 2023-06-23 | 江阴长盛化工有限公司 | Preparation technology of bisphenol S with low cost and environmental protection |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3065274A (en) * | 1959-10-15 | 1962-11-20 | Shell Oil Co | Separation and purification of isomeric dihydroxy diphenyl sulfones |
| US3297766A (en) * | 1961-10-02 | 1967-01-10 | Dow Chemical Co | Semi-continuous process for preparing 4, 4'-sulfonyldiphenol |
| US4162270A (en) * | 1975-02-24 | 1979-07-24 | Konishi Chemical Industry Co., Ltd. | Process for producing 4,4'-dihydroxydiphenylsulfone of high purity |
| DE3141455A1 (en) * | 1980-10-31 | 1982-06-24 | Tokai Denka Kogyo K.K., Tokyo | METHOD FOR INSULATING 4,4'-DIHYDROXYDIPHENYL SULPHONE |
| EP0220004A1 (en) * | 1985-10-04 | 1987-04-29 | Amoco Corporation | Process for synthesizing 4,4'-dihydroxydiphenyl sulfone |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3250812A (en) * | 1963-01-16 | 1966-05-10 | Allied Chem | Preparation of alkyl aryl sulfones |
-
1991
- 1991-06-24 CA CA 2066178 patent/CA2066178A1/en not_active Abandoned
- 1991-06-24 EP EP19910919236 patent/EP0495097A4/en not_active Withdrawn
- 1991-06-24 JP JP3516588A patent/JPH05500522A/en active Pending
- 1991-06-24 WO PCT/US1991/004437 patent/WO1992002493A1/en not_active Ceased
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3065274A (en) * | 1959-10-15 | 1962-11-20 | Shell Oil Co | Separation and purification of isomeric dihydroxy diphenyl sulfones |
| US3297766A (en) * | 1961-10-02 | 1967-01-10 | Dow Chemical Co | Semi-continuous process for preparing 4, 4'-sulfonyldiphenol |
| US4162270A (en) * | 1975-02-24 | 1979-07-24 | Konishi Chemical Industry Co., Ltd. | Process for producing 4,4'-dihydroxydiphenylsulfone of high purity |
| DE3141455A1 (en) * | 1980-10-31 | 1982-06-24 | Tokai Denka Kogyo K.K., Tokyo | METHOD FOR INSULATING 4,4'-DIHYDROXYDIPHENYL SULPHONE |
| EP0220004A1 (en) * | 1985-10-04 | 1987-04-29 | Amoco Corporation | Process for synthesizing 4,4'-dihydroxydiphenyl sulfone |
Non-Patent Citations (2)
| Title |
|---|
| CHEMICAL ABSTRACTS, vol. 105, no. 7, 18 August 1986, Columbus, Ohio, US; abstract no. 60414j, S. AMAYA ET AL. 'Purification of dihydroxydiphenyl sulfone.' page 595 ;column 2 ; * |
| See also references of WO9202493A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05500522A (en) | 1993-02-04 |
| CA2066178A1 (en) | 1992-02-07 |
| WO1992002493A1 (en) | 1992-02-20 |
| EP0495097A1 (en) | 1992-07-22 |
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