WO2004029020A1 - 高純度4,4'−ジヒドロキシジフェニルスルホンの製造方法 - Google Patents
高純度4,4'−ジヒドロキシジフェニルスルホンの製造方法 Download PDFInfo
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- WO2004029020A1 WO2004029020A1 PCT/JP2003/012049 JP0312049W WO2004029020A1 WO 2004029020 A1 WO2004029020 A1 WO 2004029020A1 JP 0312049 W JP0312049 W JP 0312049W WO 2004029020 A1 WO2004029020 A1 WO 2004029020A1
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- WIPO (PCT)
- Prior art keywords
- dihydroxydiphenylsulfone
- polar solvent
- reaction
- purity
- solvent
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/06—Separation; Purification; Stabilisation; Use of additives
Definitions
- the present invention relates to a method for producing high-purity 4,4′-dihydroxydiphenylsulfone (hereinafter sometimes referred to as “4,4′-one BS”).
- 4,4′-one BS high-purity 4,4′-dihydroxydiphenylsulfone
- 4'-BS is an important compound in the chemical industry such as fibers and resins, and in recent years, higher purity is required in each field.
- ⁇ dihydroxydiphenylsulfone isomer mixture is treated with a mixed solvent consisting of 80 to 40% by weight of 0-dichlorobenzene and 20 to 60% by weight of phenol, and then the resulting treated product is filtered without heating to obtain a high-purity product.
- Isolation of 4,4'-BS from a mixture of dihydroxydiphenylsulfone isomers, characterized in that 4,4'-BS crystals are separated and picked up Japanese Patent Publication No. 51-36264.
- 4,4'-BS cannot be obtained in high yield by the above method.
- the phenol and sulfuric acid are reacted in an inert solvent at about 15-35% by weight of the reaction mixture to form a mixture of isomers, the water of the reaction is removed at a temperature of about 160-200 ° C, and water is removed. Maintain the temperature of the reaction product mixture at about 160-200 until no more occurs, cool the temperature of the reaction product mixture to about 80-120, and add an additional amount of inert solvent, if necessary, Forms a slurry that constitutes about 20-80% by weight of the reaction product mixture, and the slurry is partitioned to separate crystalline 4,4'_BS and a liquid containing dissolved 2,4'-BS.
- a method of synthesizing 4, 4'-BS comprising obtaining the compound (see Japanese Patent Publication No. 74347/74).
- An object of the present invention is to provide a method for producing dihydroxydiphenylsulfone, which effectively removes only tri-forms and coloring impurities without changing the isomer composition of dihydroxydiphenylsulfone.
- the present inventors have conducted a dehydration reaction between phenol and a sulfonating agent or phenolsulfonic acid in the presence of an aromatic non-polar solvent while suspending the generated dihydric xydiphenyl sulfone. It has been found that the above object can be achieved by mixing a polar solvent with the obtained reaction suspension and dissolving at least a part of dihydroxydiphenylsulfone and then crystallization, thereby completing the present invention. .
- the present invention relates to the following method for producing 4,4′-BS.
- the above-mentioned dehydration reaction is carried out while suspending the mixture, and a polar solvent is mixed with the obtained reaction suspension to dissolve at least a part of dihydric xyldiphenylsulfone, and then 4,4′-dihydroxydiphenylsulfone is dissolved.
- a method for producing 4,4′-dihydroxydiphenylsulfone by a dehydration reaction between phenol and a sulfonating agent or phenolsulfonic acid, wherein the dihydroxydiphenylsulfone formed in the presence of an aromatic non-polar solvent is The above-mentioned dehydration reaction is carried out while suspending, and a polar solvent is mixed with the obtained reaction suspension to dissolve at least a part of dihydrid xidiphenyl sulfone. Then, 4,4′-dihydroxydiphenyl sulfone is dissolved.
- 4,4'-dihydroxydiphenylsulfone is separated by filtration or decantation to produce 4,4'-dihydroxydiphenylsulfone.
- the solvent is evaporated to a suspension or distilled to dryness. Dissolve at least a part of the solid content or residue in a mixed solvent of a polar solvent and a non-polar solvent,
- the 4,4'-dihydroxydiphenylsulfone obtained by the secondary crystallization is added to the reaction system before or after the dehydration reaction between phenol and a sulfonating agent or phenolsulfonic acid.
- phenol and a sulfonating agent or phenolsulfonic acid are subjected to a dehydration reaction in the presence of an aromatic nonpolar solvent.
- the dehydration reaction proceeds while suspending the produced dihydric xydiphenyl sulfone.
- Dihydroxydiphenylsulfone (hereinafter sometimes referred to as “BS”) formed by the dehydration reaction is an isomer of 2,4'-85 and 2,4'-85, including a small amount of 2,4'-85, and 4,4'-BS It is a mixture.
- Known sulfonating agents can be used for the dehydration reaction, and examples thereof include concentrated sulfuric acid, sulfuric anhydride, fuming sulfuric acid, and chlorosulfonic acid.
- the ratio of the sulfonating agent or phenolsulfonic acid to phenol is not particularly limited and is appropriately selected from a wide range, but is usually at or near the stoichiometric ratio. More specifically, the molar ratio of phenol to 1 mol of sulfonating agent is about 1.9 to 2.1 mol, and the molar ratio of phenol to 1 mol of phenolsulfonic acid is about 0.9 to 1.1 mol. is there. By setting the content within the above range, 4,4'-BS having a high yield or a high purity can be obtained more reliably.
- reaction medium is preferably a solvent that does not substantially dissolve 4,4'-BS.
- aromatic non-polar solvent examples include benzene (boiling point: 132), benzene (boiling point: 180 :), benzene (boiling point: 121), and benzene (boiling point: 16). 2 ° C), 3,4-dichlorotoluene (boiling point 2101), dimethylbenzene (boiling point 1882), mesitylene (boiling point 165), tetralin (boiling point 207), etc. .
- the aromatic nonpolar solvents may be used alone or in a combination of two or more.
- the aromatic non-polar solvent may be used in combination with another non-polar solvent such as an aliphatic hydrocarbon solvent.
- another nonpolar solvent such as an aliphatic hydrocarbon solvent.
- the content of the aromatic nonpolar solvent is usually about 50% by weight or more, preferably about 70% by weight or more, based on the whole solvent.
- an aromatic non-polar solvent or a mixed solvent of an aromatic non-polar solvent and another non-polar solvent may be referred to as a “reaction medium”.
- aliphatic hydrocarbon solvent examples include linear aliphatic hydrocarbons such as n-decane; and branched hydrocarbons such as Isopar G and Isopar H manufactured by ExxonMobil. Element; alicyclic hydrocarbons such as decalin (boiling point of trans form: 185.5 ° C, boiling point of cis form: 195.7); halogenated aliphatics such as tetrachlorobenzene (boiling point: 144) Examples include hydrocarbons.
- the aliphatic hydrocarbon solvents may be used alone or in a combination of two or more.
- mesitylene As the aromatic nonpolar solvent, mesitylene, toluene with 3,4-dichloromethane, toluene with 3,4-dichloromethane, and getylbenzene are preferred, and mesitylene is particularly preferred.
- Mesitylene is preferable in that the reaction system can be easily stirred and the generated BS can be stably precipitated as fine particles, and furthermore, temperature control is also preferable.
- Use of mesitylene is preferred because 4,4′_BS is easily obtained with high purity and high yield.
- the amount of the reaction medium to be used is not particularly limited as long as it is an amount sufficient to stir the reaction solution.
- the weight ratio of the reaction medium to the theoretical yield of dihydroxydiphenylsulfone is usually 1: 0.1 to 5: 1. And preferably about 1: 0.2 to 3.
- an aromatic non-polar solvent and another non-polar solvent such as an aliphatic hydrocarbon solvent are used in combination, the total amount of the aromatic non-polar solvent and the other non-polar solvent is determined by the total amount of the reaction medium. Weight.
- the dehydration reaction is preferably allowed to proceed while removing by-product water out of the system.
- the reaction may be allowed to proceed while distilling water together with a reaction medium such as an aromatic non-polar solvent or an aliphatic hydrocarbon solvent. After separation and removal of water, a reaction medium such as an aromatic organic solvent or an aliphatic hydrocarbon solvent may be refluxed into the system.
- a reaction medium such as an aromatic organic solvent or an aliphatic hydrocarbon solvent may be refluxed into the system.
- Known reaction conditions such as temperature, pressure, and reaction time in the dehydration reaction can be applied. For example, conditions according to known methods described in Japanese Patent Publication No. 7-91261, Japanese Patent Publication No. 8-2861, and Japanese Patent Publication No. 8-2863 can be applied.
- the reaction temperature of the dehydration reaction is usually about 120 or more, preferably about 120 to 220, and more preferably about 140 ° C. to about 19 (TC.
- the dehydration reaction proceeds even at normal pressure.
- the reaction time may be set to a pressurized state or a depressurized state as necessary.
- the reaction time is not particularly limited and may be appropriately set depending on the reaction temperature and the like, but is usually about 1 to 30 hours, preferably 2 to 20 hours. It is about an hour.
- hydroxydiphenyl sulfone is suspended even after the dehydration reaction is completed.
- the temperature may be maintained at or above the isomerization temperature.
- the isomeric reaction from 2,4'-83 to 4,4'-BS proceeds.
- the holding temperature is not particularly limited as long as the isomerization reaction proceeds from 2,4′-BS to 4,4′-BS, but is usually about 120 ° C. or more, and preferably about 140 to about 175. . By setting the temperature in such a range, the isomerization reaction proceeds rapidly. After completion of the dehydration reaction, the time for maintaining the temperature at or above the isomerization temperature can be appropriately set according to the reaction temperature and the like, but is usually about 1 to 10 hours, and preferably about 2 to 5 hours. . Whether or not the dehydration reaction has been completed can be determined by, for example, whether or not the amount of by-product water has not increased. The isomerization reaction proceeds even at normal pressure, but may be in a pressurized state or a reduced pressure state as necessary.
- the isomerization reaction is preferably performed in the presence of an acid catalyst.
- the acid catalyst may be added to the reaction system together with the raw materials for the dehydration reaction. However, it may be added in the latter half of the dehydration reaction or after completion. To suppress the coloring of 4,4'-BS, it may be added in the latter half of the dehydration reaction or after completion.
- Phenolsulfonic acid also functions as an acid catalyst. Therefore, when phenol sulfonic acid is used as a reaction raw material, or when phenol sulfonic acid is generated as a reaction intermediate, a deficiency may be added as necessary, or the catalyst may have a more catalytic effect than phenol sulfonic acid. A high acid catalyst may be added. Examples of the acid catalyst having a higher catalytic effect than phenolsulfonic acid include, for example, an acid catalyst described below as a preferable acid catalyst.
- the acid catalyst examples include benzenesulfonic acid, black benzenesulfonic acid, benzene-1,3-disulfonic acid, chlorobenzene-1,2,4-disulfonic acid, brombenzene-1,2,4-disulfonic acid, fluorobenzene-1,2, 4-disulfonic acid, toluene-1,2,4-disulfonic acid, ethylbenzene-1,2,4-disulfonic acid, benzene-1,3,5-trisulfonic acid, chlorobenzene-1,2,4,6-trisulfonic acid, bromobenzene Aromatic compounds such as 1,2,4,6-trisulfonic acid, fluorobenzene-1,2,4,6-trisulfonic acid, toluene-1,2,4,6-trisulfonic acid and ethylbenzene-2,4,6-trisulfonic acid Sulfonic acids; aliphatic s
- the acid catalysts may be used alone or in combination of two or more.
- the amount of the acid catalyst used is not particularly limited as long as it is a catalytic amount, and can be appropriately selected from a wide range.
- the acid catalyst is usually used in an amount of about 0.5 to 10 mol%, preferably 2 to 5 mol% based on the sulfonating agent. It is about mol%.
- a polar solvent is mixed with the reaction suspension generated by the dehydration reaction to dissolve at least a part of the generated dihydroxy-opened xidiphenyl sulfone.
- impurities such as 2,4'-BS and phenolsulfonic acid dissolve in the liquid phase, and the desired high-purity 4,4'-BS can be obtained.
- the mode of mixing the polar solvent with the reaction suspension is not particularly limited, and a polar solvent may be added to the reaction suspension, or the reaction suspension may be added to the polar solvent.
- the reaction suspension after the isomerization reaction is mixed with a polar solvent to dissolve at least a part of the generated dihydroxydiphenyl sulfone.
- the amount of BS to be dissolved is not particularly limited as long as the effects of the present invention are exhibited, but the higher the amount of dissolution, the easier it is to obtain 4,4'-BS with higher purity and completely dissolve the suspended BS. Most preferably. For example, when it is desired to obtain 4,4'-BS having a purity of about 99.5% or more, it is preferable to completely dissolve the suspended BS.
- Examples of the polar solvent used include higher alcohols having 4 to 15 carbon atoms, polyhydric alcohols, and phenols.
- Examples of the higher alcohol include higher alcohols such as butanol, amyl alcohol, and octyl alcohol.
- polyhydric alcohols for example, Examples thereof include lenglycol, diethylene glycol, ethylene glycol monoethyl ether (for example, trade name: Echilse mouth solve), and ethylene glycol monobutyl ether (for example, trade name: butylse mouth solve).
- Examples of the phenols include, for example, phenol, cresol, xylenol and the like.
- As the polar solvent one kind may be used alone, or two or more kinds may be used in combination.
- phenol is particularly preferred.
- As the combination of the polar solvent and the non-polar solvent a combination of phenol and mesitylene is preferable.
- the amount of the polar solvent used is not particularly limited as long as the desired amount of BS is dissolved, but is usually about 10% by weight or more, preferably 30% by weight to 70% by weight, based on the total weight of the reaction medium and the polar solvent. %.
- an aromatic non-polar solvent and another non-polar solvent such as an aliphatic hydrocarbon solvent are used in combination, the total amount of the aromatic non-polar solvent and the other non-polar solvent is determined by the total amount of the reaction medium. Weight.
- the BS dissolves without heating, but may be heated if necessary.
- the heating temperature is not particularly limited as long as at least a part of the produced BS is dissolved, but is usually about 130 or more, preferably about 150 t: about 220 ⁇ , more preferably about 160 to 20 O: About.
- BS can be dissolved even at normal pressure, but it may be pressurized as needed, usually about 0.1 to 1] ⁇ « ⁇ , preferably 0.05 to 0.5 MPa Can be pressurized to a degree.
- pressure By applying pressure, the amount of a polar solvent such as phenol used can be reduced, and as a result, the yield can be further increased.
- the crystallization temperature is not particularly limited as long as 4,4′-BS is crystallized, but is usually about 150 or less, preferably about 100 or less, more preferably about 60 or less.
- the difference between the heating temperature and the crystallization temperature is usually about 20 ° C. or more, preferably about 50 or more, and more preferably about 50 to 15 (TC).
- High purity 4,4'-BS can be obtained by primary crystallization.
- the purity of the obtained 4,4'-BS is usually about 98% or more, preferably 99% or more under preferable conditions, and about 99.5% or more under more preferable conditions.
- Crystallized high purity 4,4'-BS can be separated and recovered by a known solid-liquid separation means such as filtration and decantation. If necessary, after separation and recovery, drying may be performed.
- the 4,4′_BS which has been primary crystallized is separated by a known solid-liquid separation means such as filtration or decantation, and the obtained separated liquid is converted into a suspension or distilled to dryness. Evaporate the solvent until the solid content in the obtained suspension or at least a part of the residue is dissolved in a mixed solvent of a polar solvent and an aromatic non-polar solvent, and then 4,4'-BS May be crystallized (secondary crystallization).
- the crystals obtained by the secondary crystallization may be referred to as “secondary crystals”.
- the 4,4'-BS precipitated by secondary crystallization may be separated by filtration or decantation.
- the heating temperature is not particularly limited as long as the distillation proceeds, but is preferably 12 (about TC or more, more preferably about 140 to 175.
- the reaction may be performed under reduced pressure or increased pressure according to the conditions.
- the holding temperature is not particularly limited as long as the isomerization reaction from 2,4'-83 to 4,4'-BS proceeds, but is usually about 120 ° C or more, preferably about 140T to 175: about . By setting the temperature in such a range, the isomerization reaction proceeds rapidly.
- the holding time can be appropriately set according to the holding temperature and the like, but is usually about 1 to 10 hours, preferably about 2 to 5 hours. The isomerization reaction proceeds even at normal pressure, but may be under reduced pressure or increased pressure as necessary.
- the solvent recovered by distillation or the like can be reused as a solvent for a dehydration reaction.
- a solvent other than phenol is used as the polar solvent, it can be reused as a solvent for a dehydration reaction after removing the polar solvent by a known method such as distillation. If phenol is used as the polar solvent, there is no need to remove the polar solvent.
- reusing as a solvent for dehydration reaction use phenol, sulfonating agent or phenolsulfonic acid, acid catalyst What should be added as needed.
- the aromatic non-polar solvent may be used in combination with another non-polar solvent such as an aliphatic hydrocarbon solvent.
- the content of the aromatic non-polar solvent is usually at least about 50% by weight, preferably at least 70% by weight, based on the entire non-polar solvent. It is about.
- the ratio between the polar solvent and the aromatic non-polar solvent contained in the mixed solvent is not particularly limited, but the concentration of the polar solvent is about 10 to 90% by weight, preferably 30 to 70% by weight based on the whole mixed solvent. % By weight.
- the mixing ratio is preferably about the same as the mixing ratio of phenol and aromatic non-polar solvent in the dehydration reaction.
- the amount of the mixed solvent used is not particularly limited as long as the desired amount of BS or residue is dissolved, but the weight ratio of the mixed solvent to the weight of BS or residue is usually about 1: 1 to 10, preferably 1: 2. ⁇ 5 or so.
- the crystallization temperature is not particularly limited as long as 4,4'-BS is crystallized, but is usually about 150 ° C or less, preferably about 100 or less, more preferably about 6 Ot: or less. It is.
- the difference between the heating temperature and the crystallization temperature is usually about 2 (T or more, preferably about 50 or more, and more preferably about 50 to 150.
- the secondary crystals may be separated and recovered by a known solid-liquid separation means such as filtration and decantation. If necessary, after separation and recovery, drying may be performed.
- the recovered secondary crystals have high purity as they are, they may be added to the reaction system before or after the dehydration reaction between phenol and a sulfonating agent or phenolsulfonic acid, and recrystallized.
- the secondary crystals When the secondary crystals are added to the reaction system after the dehydration reaction, they may be added at any stage before and after mixing the reaction suspension and the polar solvent.
- the secondary crystals When performing the isomerization reaction after the completion of the dehydration reaction, the secondary crystals may be added to the reaction system at any stage before and after the isomerization reaction. Again, before and after mixing the reaction suspension with the polar solvent The secondary crystal may be added at any stage.
- the separated solution generated by separating and collecting the secondary crystals can be reused as a solvent for a dehydration reaction.
- a solvent other than phenol is used as the polar solvent, it can be reused as a solvent for a dehydration reaction after removing the polar solvent by a known method such as distillation.
- phenol is used as a polar solvent, it is not necessary to remove the polar solvent, but it is preferable to purify it by distillation and then reuse it.
- a deficient phenol, a sulfonating agent or a phenolsulfonic acid, an acid catalyst, or the like may be added as needed.
- the obtained primary crystal or secondary crystal may be further purified if necessary.
- a mixture of primary and secondary crystals may further be formed.
- the primary crystals are mixed with a solvent such as water or alcohol (for example, methanol or ethanol); activated carbon; a reducing agent such as hydrosulfite; ethylenediaminetetraacetic acid (EDTA);
- a solvent such as water or alcohol (for example, methanol or ethanol); activated carbon; a reducing agent such as hydrosulfite; ethylenediaminetetraacetic acid (EDTA);
- EDTA ethylenediaminetetraacetic acid
- 4,4′-BS of extremely high purity (for example, about 98% or more, about 99% or more under preferable conditions, and about 99.5% or more under more preferable conditions) is produced. be able to.
- 4,4′-BS can be produced with high yield.
- 4,4'-BS can be produced with a higher yield.
- high purity 4,4'-BS can be manufactured only by a simple process, without passing through a complicated process.
- a dehydration reaction was performed according to the method described in Example 1. After the reaction was completed, 189 g of phenol was added to the reaction suspension. This was heated to about 180, and most of the crystals were dissolved, except that some of the crystals were in a suspended (slurry) state. Cooling crystallization and post-treatment were performed in the same manner as in Example 1 to obtain 208 g of a crystal.
- the dried product was mixed with 48 g of phenol and 36 g of mesitylene, dissolved by heating, and cooled to 40 to precipitate crystals.
- the obtained crystals were separated by filtration, washed and dried to obtain 28 g of secondary crystals.
- the 4,4′-dihydroxyphenylsulfone yield based on sulfuric acid was 11%.
- a dehydration reaction was performed in the same manner as in Example 1 except that 208 g of 3,4-dichlorotoluene was used instead of mesitylene, to obtain a reaction suspension.
- a dehydration reaction was performed in the same manner as in Example 1 except that 240 g of 1,2,4-trichlorobenzene was used instead of mesitylene, to obtain a reaction suspension.
- Example 2 After performing a dehydration reaction in the same manner as in Example 1, the mixture was cooled to 4 O: without adding phenol, and the precipitated crystals were separated by filtration, washed and dried.
- the obtained crystals contained 2% of sulfonic acids mainly composed of phenolsulfonic acid, and the 4,4′-BS yield based on the sulfuric acid charged was 89%.
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Abstract
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Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2003266552A AU2003266552A1 (en) | 2002-09-25 | 2003-09-22 | Process for producing high-purity 4,4'-dihydroxydiphenyl sulfone |
US10/529,074 US7456321B2 (en) | 2002-09-25 | 2003-09-22 | Process for producing high-purity 4,4′-dihydroxydiphenyl sulfone |
JP2004539473A JP4496381B2 (ja) | 2002-09-25 | 2003-09-22 | 高純度4,4’−ジヒドロキシジフェニルスルホンの製造方法 |
Applications Claiming Priority (2)
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JP2002-279199 | 2002-09-25 | ||
JP2002279199 | 2002-09-25 |
Publications (1)
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WO2004029020A1 true WO2004029020A1 (ja) | 2004-04-08 |
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PCT/JP2003/012049 WO2004029020A1 (ja) | 2002-09-25 | 2003-09-22 | 高純度4,4'−ジヒドロキシジフェニルスルホンの製造方法 |
Country Status (5)
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US (1) | US7456321B2 (ja) |
JP (1) | JP4496381B2 (ja) |
CN (1) | CN1314664C (ja) |
AU (1) | AU2003266552A1 (ja) |
WO (1) | WO2004029020A1 (ja) |
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CN104557637B (zh) * | 2014-12-11 | 2017-01-25 | 科迈化工股份有限公司 | 合成双酚s的脱水控制方法 |
EP3921303A1 (en) * | 2019-02-08 | 2021-12-15 | Basf Se | A process for obtaining 4,4'-dichlorodiphenyl sulfoxide |
CN114054088B (zh) * | 2022-01-17 | 2022-04-15 | 富海(东营)新材料科技有限公司 | 一种催化剂及该催化剂在合成双酚s中的应用 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0443046A1 (en) * | 1989-09-14 | 1991-08-28 | Konishi Chemical Ind. Co., Ltd. | Process for preparing 4,4'-dihydroxydiphenyl sulfone |
JPH04145061A (ja) * | 1990-10-02 | 1992-05-19 | Konishi Kagaku Kogyo Kk | 高純度4,4´―ジヒドロキシジフェニルスルホンの製造法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS5152153A (ja) | 1974-10-31 | 1976-05-08 | Konishi Chem Ind | Jihidorokishijifuenirusurupponiseitaikongobutsuyori 4 4** jihidorokishijifuenirusurupponotanrisuru hoho |
JPS61243059A (ja) * | 1985-04-19 | 1986-10-29 | Konishi Kagaku Kogyo Kk | 高純度4,4′−ジヒドロキシジフエニルスルホンの製造法 |
US5041677A (en) | 1985-10-04 | 1991-08-20 | Amoco Corporation | Process for synthesizing 4,4'-dihydroxydiphenyl sulfone |
JPH07107043B2 (ja) * | 1986-08-19 | 1995-11-15 | 日華化学株式会社 | ビスフエノ−ルスルホン類の精製方法 |
JPH0791261B2 (ja) | 1989-09-14 | 1995-10-04 | 小西化学工業株式会社 | 4,4′―ジヒドロキシジフェニルスルホンの製造法 |
JPH082861B2 (ja) | 1989-12-29 | 1996-01-17 | 小西化学工業株式会社 | 高純度4,4’―ジヒドロキシジフェニルスルホンの製造方法 |
US5241121A (en) * | 1989-12-29 | 1993-08-31 | Konishi Chemical Ind. Co., Ltd. | Process for preparation of 4,4'-dihydroxydiphenylsulfone |
WO1992002493A1 (en) * | 1990-08-06 | 1992-02-20 | Aristech Chemical Corporation | Preparation of relatively pure p, p-bisphenol s |
DE10018580A1 (de) * | 2000-04-14 | 2001-10-25 | Basf Ag | Semikontinuierliches Verfahren zur Herstellung von 4,4'-Dihydroxydiphenylsulfon |
-
2003
- 2003-09-22 AU AU2003266552A patent/AU2003266552A1/en not_active Abandoned
- 2003-09-22 US US10/529,074 patent/US7456321B2/en not_active Expired - Fee Related
- 2003-09-22 JP JP2004539473A patent/JP4496381B2/ja not_active Expired - Fee Related
- 2003-09-22 WO PCT/JP2003/012049 patent/WO2004029020A1/ja active Application Filing
- 2003-09-22 CN CNB038230445A patent/CN1314664C/zh not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0443046A1 (en) * | 1989-09-14 | 1991-08-28 | Konishi Chemical Ind. Co., Ltd. | Process for preparing 4,4'-dihydroxydiphenyl sulfone |
JPH04145061A (ja) * | 1990-10-02 | 1992-05-19 | Konishi Kagaku Kogyo Kk | 高純度4,4´―ジヒドロキシジフェニルスルホンの製造法 |
Also Published As
Publication number | Publication date |
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JPWO2004029020A1 (ja) | 2006-01-26 |
CN1684943A (zh) | 2005-10-19 |
US7456321B2 (en) | 2008-11-25 |
CN1314664C (zh) | 2007-05-09 |
AU2003266552A1 (en) | 2004-04-19 |
US20050272956A1 (en) | 2005-12-08 |
JP4496381B2 (ja) | 2010-07-07 |
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