CN1319942C - Method for producing dihydroxydiphenylsulfone isomer mixture - Google Patents
Method for producing dihydroxydiphenylsulfone isomer mixture Download PDFInfo
- Publication number
- CN1319942C CN1319942C CNB2005101269482A CN200510126948A CN1319942C CN 1319942 C CN1319942 C CN 1319942C CN B2005101269482 A CNB2005101269482 A CN B2005101269482A CN 200510126948 A CN200510126948 A CN 200510126948A CN 1319942 C CN1319942 C CN 1319942C
- Authority
- CN
- China
- Prior art keywords
- dds
- mixture
- weight
- dihydroxydiphenylsulisomer
- isomer mixture
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 19
- 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 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 15
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 34
- 238000002360 preparation method Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 18
- LROZSPADHSXFJA-UHFFFAOYSA-N 2-(4-hydroxyphenyl)sulfonylphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=CC=C1O LROZSPADHSXFJA-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 35
- 238000006317 isomerization reaction Methods 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 17
- 238000004128 high performance liquid chromatography Methods 0.000 description 12
- 229930195357 gramphenol Natural products 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 239000003999 initiator Substances 0.000 description 10
- 229930185605 Bisphenol Natural products 0.000 description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 4
- MIAUJDCQDVWHEV-UHFFFAOYSA-N benzene-1,2-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1S(O)(=O)=O MIAUJDCQDVWHEV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- AQZFTBDEQSSKMT-UHFFFAOYSA-N 3-chlorobenzene-1,2-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(Cl)=C1S(O)(=O)=O AQZFTBDEQSSKMT-UHFFFAOYSA-N 0.000 description 1
- MZSUDHKFNNYUGD-UHFFFAOYSA-N C(C)S(=O)(=O)O.[F] Chemical class C(C)S(=O)(=O)O.[F] MZSUDHKFNNYUGD-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- MHWVMMHIJHHXQP-UHFFFAOYSA-N benzene-1,2,3-trisulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(S(O)(=O)=O)=C1S(O)(=O)=O MHWVMMHIJHHXQP-UHFFFAOYSA-N 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
It is intended to provide a process for producing a mixture of dihydroxydiphenylsulfone isomers containing 2,4'-dihydroxydiphenylsulfone characterized in that 4,4'-dihydroxydiphenylsulfone or a mixture of dihydroxydiphenylsulfone isomers containing 85% by weight or more of 4,4'-dihydroxydiphenylsuflone is heated in the presence of phenol and sulfuric acid, or in the presence of phenol and sulfonic acid.
Description
The application is dividing an application of No. the 02818400.9th, Chinese patent application.
Technical field
The present invention relates to contain 2, the preparation method of the dihydroxydiphenylsulisomer isomer mixture of 4 '-dihydroxy diphenylsulphone.
Background technology
In various phenol type compounds, 2,4 '-dihydroxy diphenylsulphone (below be sometimes referred to as 2,4 '-DDS) and caused concern recently, so it is exceedingly useful with developer as temperature-sensitive paper.
2, the known preparation method of 4 '-DDS comprises from containing 2,4 '-DDS and 4,4 '-dihydroxy diphenylsulphone (below be sometimes referred to as in 4,4 '-DDS) the mixture and separate and purifying 24 '-DDS.
In addition, known in phenolic solvent, in the presence of acid catalyst, heating 4, during 4 '-DDS, isomerization takes place, thereby generate and contain 4 with about 75～about 25 (isomerization equilibriums) of weight ratio, 4 '-DDS and 2, the dihydroxydiphenylsulisomer isomer mixture of 4 '-DDS (Journal of the ChemicalSociety of Japan, 1985 (1), 70-74).But,, therefore industrially be difficult to utilize this isomerization reaction even because this isomerization reaction also needed 20 hours even the longer time reaches isomerization equilibrium under 190 ℃ or higher heating condition.
Disclosure of an invention
The purpose of this invention is to provide and contain more volume 2, the preparation method of the dihydroxydiphenylsulisomer isomer mixture of 4 '-DDS, this method be 4, and 4 '-DDS can reach isomerization equilibrium during by isomerization at short notice.
Other purpose of the present invention and feature will be apparent by following announcement.
The inventor has carried out extensive studies, and finds can reach isomerization equilibrium at short notice by heat 4,4 '-DDS in the presence of specified quantitative phenol and vitriolic.Finished the present invention based on this discovery.
In addition, the inventor finds that heating 4,4 '-DDS in the presence of phenol and sulfonic acid can reach isomerization equilibrium at short notice.Finished the present invention based on this discovery.
In other words, the invention provides the preparation method of following dihydroxydiphenylsulisomer isomer mixture.
1. one kind prepares and contains 2, the method of the dihydroxydiphenylsulisomer isomer mixture of 4 '-dihydroxy diphenylsulphone, this method is included in respect to 4, weight such as 4 '-dihydroxy diphenylsulphone is or the sulfuric acid that the phenol of weight such as is lower than and is not higher than 20 moles of % exist down, with 4, it is 160 ℃ or higher that 4 '-dihydroxy diphenylsulphone is heated to temperature.
2. one kind prepares and contains 2, the method of the dihydroxydiphenylsulisomer isomer mixture of 4 '-dihydroxy diphenylsulphone, this method is included in respect to weight such as this mixture is or the sulfuric acid that the phenol of weight such as is lower than and is not higher than 20 moles of % and exists down, to contain 4 of at least 85 weight %, it is 160 ℃ or higher that the dihydroxydiphenylsulisomer isomer mixture of 4 '-dihydroxy diphenylsulphone is heated to temperature.
3. one kind prepares and contains 2, and the existence that the method for the dihydroxydiphenylsulisomer isomer mixture of 4 '-dihydroxy diphenylsulphone, this method are included in phenol and sulfonic acid is heating 4,4 '-dihydroxy diphenylsulphone down.
4. one kind prepares and contains 2, the method of the dihydroxydiphenylsulisomer isomer mixture of 4 '-dihydroxy diphenylsulphone, this method is included in the following dihydroxydiphenylsulisomer isomer mixture that heats 4, the 4 '-dihydroxy diphenylsulphone that contains at least 85 weight % of existence of phenol and sulfonic acid.
Below, illustrate in greater detail the method for preparing dihydroxydiphenylsulisomer isomer mixture of the present invention:
[using the vitriolic method]
As single initiator of the present invention, 4, the purity of 4 '-DDS can be 99% or higher.
Contain 4 of at least 85 weight %, the dihydroxydiphenylsulisomer isomer mixture of 4 '-DDS also can be used as initiator.Preferred this isomer mixture contains 2, and 4 '-DDS is as another kind of isomer.
By in the presence of phenol and vitriolic, heating initiator, promptly 4,4 '-DDS or contain 4 of at least 85 weight %, the dihydroxydiphenylsulisomer isomer mixture of 4 '-DDS, isomerization takes place in it.
The consumption of phenol is an initiator, promptly 4,4 '-DDS or contain 4 of at least 85 weight %, the dihydroxydiphenylsulisomer isomer mixture of 4 '-DDS etc. weight or weight such as be lower than, be preferably its 0.1～0.8 times of weight.
The vitriolic consumption is with respect to initiator, and promptly 4,4 '-DDS or contain 4 of at least 85 weight %, the dihydroxydiphenylsulisomer isomer mixture of 4 '-DDS is not for being higher than 20 moles of %, preferred 1～10 mole of %.
Can use solvent or not use solvent.When using solvent, preferred heat-resisting and acid proof solvent is as tetramethylene sulfone etc.
The temperature of reaction of carrying out isomerization reaction is 160 ℃ or higher, preferred 170～210 ℃.Isomerization also can be carried out under pressurized state as required.
Reaction times is unrestricted.Can react up to reaching isomerization equilibrium.The preferred reaction times is 0.1～15 hour, more preferably 0.5～10 hour.
Target product of the present invention promptly contains 2, the dihydroxydiphenylsulisomer isomer mixture of 4 '-DDS, and mainly by 4,4 '-DDS and 2,4 '-DDS forms.Contain 2 of 15～30 weight % in the preferred mixture, 4 '-DDS more preferably contains 2 of 20～30 weight %, and 4 '-DDS especially preferably contains 2 of 22～30 weight %, 4 '-DDS.
Can use separation known and purification process to contain 2, separate 2 in the dihydroxydiphenylsulisomer isomer mixture of 4 '-DDS, 4 '-DDS from of the present invention.
The method according to this invention, when 4,4 '-DDS is during by isomerization, and isomerization equilibrium reaches at short notice, can obtain containing more volume 2, the dihydroxydiphenylsulisomer isomer mixture of 4 '-DDS.
[using the method for sulfonic acid]
As single initiator of the present invention, 4, the purity of 4 '-DDS can be 99% or higher.
Contain 4 of at least 85 weight %, the dihydroxydiphenylsulisomer isomer mixture of 4 '-DDS also can be used as initiator.Preferred this isomer mixture contains 2, and 4 '-DDS is as another kind of isomer.
By in the presence of phenol and sulfonic acid, heating initiator, promptly 4,4 '-DDS or contain 4 of at least 85 weight %, the dihydroxydiphenylsulisomer isomer mixture of 4 '-DDS, isomerization takes place in it.
The consumption of phenol is preferably initiator, and promptly 4,4 '-DDS or contain 4,2 times of weight of the dihydroxydiphenylsulisomer isomer mixture of 4 '-DDS or be lower than 2 times of weight, more preferably its 0.1～1 times of weight.
The example that can be used for sulfonic acid of the present invention comprise aromatics lists such as benzene trisulfonic acid, benzene disulfonic acid, chlorobenzene disulfonic acid, toluenesulphonic acids, sulfocarbolic acid-, two-or trisulfonic acid; Methylsulfonic acid, ethyl sulfonic acid, trifluoromethanesulfonic acid, five fluorine ethyl sulfonic acids etc. are optional by the fluorizated aliphatic sulfonic acid; Polymkeric substance sulfonic acid such as Nafion .In these sulfonic acid, preferred aromatics list-, two-, trisulfonic acid; More preferably benzene disulfonic acid, toluenesulphonic acids etc.
The consumption of sulfonic acid is with respect to initiator, and promptly 4,4 '-DDS or contain 4, the dihydroxydiphenylsulisomer isomer mixture of 4 '-DDS is preferably 20 moles of % or lower, more preferably 1～10 mole of %.
Can use solvent or not use solvent.When using solvent, preferred heat-resisting and acid proof solvent is as tetramethylene sulfone etc.
The temperature of reaction of carrying out isomerization reaction is 160 ℃ or higher, preferred 170～210 ℃.Isomerization also can be carried out under pressurized state as required.
Reaction times is unrestricted.Can react up to reaching isomerization equilibrium.The preferred reaction times is 0.1～15 hour, more preferably 0.5～10 hour.
Target product of the present invention promptly contains 2, the dihydroxydiphenylsulisomer isomer mixture of 4 '-DDS, and mainly by 4,4 '-DDS and 2,4 '-DDS forms.Contain 2 of 15～30 weight % in the preferred mixture, 4 '-DDS more preferably contains 2 of 20～30 weight %, and 4 '-DDS especially preferably contains 2 of 22～30 weight %, 4 '-DDS.
Can use separation known and purification process to contain 2, separate 2 in the dihydroxydiphenylsulisomer isomer mixture of 4 '-DDS, 4 '-DDS from prepared in accordance with the present invention.
The method according to this invention, when 4,4 '-DDS is during by isomerization, and isomerization equilibrium reaches at short notice, can obtain containing more volume 2, the dihydroxydiphenylsulisomer isomer mixture of 4 '-DDS.
The best mode that carries out an invention
Illustrate in greater detail the present invention by the following examples.
Example I-1
(contain 4 of 99.8 weight %, 2 of 4 '-DDS and 0.1 weight %, 4 '-DDS at 100 gram (0.4 mole) dihydroxy diphenylsulphones; Hereinafter referred to as bisphenol S (1)) middle 98% sulfuric acid that adds 50 gram phenol and 1.6 grams (0.016 mole is 4 moles of % with respect to bisphenol S (1)).With mixture heating up to 195 ℃ and under this temperature, stir.The result who stirs HPLC (high performance liquid chromatography) analysis of carrying out after 2 hours shows that this mixture contains 4,4 '-DDS and 2,4 '-DDS, its weight ratio 4,4 '-DDS/2,4 '-DDS are 85: 15, the mixture that stirs after 6 hours contains 4,4 '-DDS and 2,4 '-DDS, its weight ratio 4,4 ' DDS/2,4 '-DDS are 76: 24.
Example I-2
98% sulfuric acid that in 100 gram bisphenol Ss (1), adds 50 gram phenol and 4 grams (0.04 mole is 10 moles of % with respect to bisphenol S (1)).With mixture heating up to 180 ℃ and under this temperature, stir.The result who stirs the HPLC analysis of carrying out after 2 hours shows that this mixture contains 4,4 '-DDS and 2,4 '-DDS, its weight ratio 4,4 '-DDS/2,4 '-DDS are 86: 14, the mixture that stirs after 6 hours contains 4,4 '-DDS and 2,4 '-DDS, its weight ratio 4,4 '-DDS/2,4 '-DDS are 76: 24.
Example I-3
98% sulfuric acid that in 100 gram bisphenol Ss (1), adds 50 gram phenol and 4 grams (0.04 mole is 10 moles of % with respect to bisphenol S (1)).With mixture heating up to 210 ℃ and under this temperature, stir.The result who stirs the HPLC analysis of carrying out after 1 hour shows that this mixture contains 4,4 '-DDS and 2,4 '-DDS, its weight ratio 4,4 '-DDS/2,4 '-DDS are 75: 25, the mixture that stirs after 2 hours contains 4,4 '-DDS and 2,4 '-DDS, its weight ratio 4,4 '-DDS/2,4 '-DDS are 73: 27.
Example I-4
(contain 4 of 86 weight %, 2 of 4 '-DDS and 14 weight %, 4 '-DDS at 100 gram (0.4 mole) dihydroxy diphenylsulphones; Hereinafter referred to as bisphenol S (2)) middle 98% sulfuric acid that adds 50 gram phenol and 1.6 grams (0.016 mole is 4 moles of % with respect to bisphenol S (2)).With mixture heating up to 195 ℃ and under this temperature, stir.The result who stirs the HPLC analysis of carrying out after 2 hours shows that this mixture contains 4,4 '-DDS and 2,4 '-DDS, its weight ratio 4,4 '-DDS/2,4 '-DDS are 79: 21, the mixture that stirs after 6 hours contains 4,4 '-DDS and 2,4 '-DDS, its weight ratio 4,4 '-DDS/2,4 '-DDS are 75: 25.
Comparative Example I-1
98% sulfuric acid that in 15 gram (0.06 mole) bisphenol Ss (1), adds 36 gram phenol and 3 grams (0.03 mole is 50 moles of % with respect to bisphenol S (1)).With mixture heating up to 195 ℃ and under this temperature, stir.The result who stirs the HPLC analysis of carrying out after 2 hours shows that this mixture contains 4,4 '-DDS and 2,4 '-DDS, its weight ratio 4,4 ' DDS/2,4 '-DDS is 88: 12, the mixture that stirs after 6 hours contains 4,4 '-DDS and 2,4 '-DDS, its weight ratio 4,4 '-DDS/2,4 '-DDS are 82: 18, the mixture that stirs after 20 hours contains 4,4 '-DDS and 2,4 '-DDS, its weight ratio 4,4 ' DDS/2,4 '-DDS is 78: 22.
Example II-1
The benzene disulfonic acid that in 100 gram (0.4 mole) bisphenol Ss (1), adds 100 gram phenol and 5 grams (0.02 mole is 5 moles of % with respect to bisphenol S (1)).With mixture heating up to 180 ℃ and under this temperature, stir.The result who stirs the HPLC analysis of carrying out after 2 hours shows that this mixture contains 4,4 '-DDS and 2,4 '-DDS, its weight ratio 4,4 ' DDS/2,4 '-DDS is 81: 19, the mixture that stirs after 6 hours contains 4,4 '-DDS and 2,4 '-DDS, its weight ratio 4,4 '-DDS/2,4 '-DDS are 77: 23.
Example II-2
The toluenesulphonic acids that in 100 gram bisphenol Ss (1), adds 50 gram phenol and 3 grams (0.017 mole is 4 moles of % with respect to bisphenol S (1)).With mixture heating up to 195 ℃ and under this temperature, stir.The result who stirs the HPLC analysis of carrying out after 2 hours shows that this mixture contains 4,4 '-DDS and 2,4 '-DDS, its weight ratio 4,4 '-DDS/2,4 '-DDS are 79: 21, the mixture that stirs after 6 hours contains 4,4 '-DDS and 2,4 '-DDS, its weight ratio 4,4 '-DDS/2,4 '-DDS are 75: 25.
Example II-3
The toluenesulphonic acids that in 100 gram bisphenol Ss (1), adds 50 gram phenol and 6.9 grams (0.04 mole is 10 moles of % with respect to bisphenol S (1)).With mixture heating up to 180 ℃ and under this temperature, stir.The result who stirs the HPLC analysis of carrying out after 2 hours shows that this mixture contains 4,4 '-DDS and 2,4 '-DDS, its weight ratio 4,4 '-DDS/2,4 '-DDS are 86: 14, the mixture that stirs after 6 hours contains 4,4 '-DDS and 2,4 '-DDS, its weight ratio 4,4 '-DDS/2,4 '-DDS are 76: 24.
Example II-4
The toluenesulphonic acids that in 100 gram bisphenol Ss (1), adds 50 gram phenol and 6.9 grams (0.04 mole is 10 moles of % with respect to bisphenol S (1)).With mixture heating up to 210 ℃ and under this temperature, stir.The result who stirs the HPLC analysis of carrying out after 1 hour shows that this mixture contains 4,4 '-DDS and 2,4 '-DDS, its weight ratio 4,4 ' DDS/2,4 '-DDS is 75: 25, the mixture that stirs after 2 hours contains 4,4 '-DDS and 2,4 '-DDS, its weight ratio 4,4 '-DDS/2,4 '-DDS are 73: 27.
Example II-5
The toluenesulphonic acids that in 100 gram (0.4 mole) bisphenol Ss (2), adds 50 gram phenol and 3 grams (0.017 mole is 4 moles of % with respect to bisphenol S (2)).With mixture heating up to 195 ℃ and under this temperature, stir.The result who stirs the HPLC analysis of carrying out after 2 hours shows that this mixture contains 4,4 '-DDS and 2,4 '-DDS, its weight ratio 4,4 '-DDS/2,4 '-DDS are 77: 23, the mixture that stirs after 6 hours contains 4,4 '-DDS and 2,4 '-DDS, its weight ratio 4,4 '-DDS/2,4 '-DDS are 75: 25.
Comparative Example I I-1
98% sulfuric acid that in 15 gram (0.06 mole) bisphenol Ss (1), adds 36 gram phenol and 3 grams (0.03 mole is 50 moles of % with respect to bisphenol S (1)).With mixture heating up to 195 ℃ and under this temperature, stir.The result who stirs the HPLC analysis of carrying out after 2 hours shows that this mixture contains 4,4 '-DDS and 2,4 '-DDS, its weight ratio 4,4 '-DDS/2,4 '-DDS are 88: 12, the mixture that stirs after 6 hours contains 4,4 '-DDS and 2,4 '-DDS, its weight ratio 4,4 ' DDS/2,4 '-DDS is 82: 18, the mixture that stirs after 20 hours contains 4,4 '-DDS and 2,4 '-DDS, its weight ratio 4,4 '-DDS/2,4 '-DDS are 78: 22.
Claims (2)
1. preparation contains 2, and the method for the dihydroxydiphenylsulisomer isomer mixture of 4 '-dihydroxy diphenylsulphone, this method are included in the existence of phenol and sulfonic acid and heat 4,4 '-dihydroxy diphenylsulphone down,
The consumption of described phenol is for being higher than 4,2 times of weight of 4 '-dihydroxy diphenylsulphone, and the mole % of sulfonic acid is not for being higher than 4,20 moles of % of 4 '-dihydroxy diphenylsulphone.
2. preparation contains 2, and the method for the dihydroxydiphenylsulisomer isomer mixture of 4 '-dihydroxy diphenylsulphone, this method are included in the following dihydroxydiphenylsulisomer isomer mixture that heats 4, the 4 '-dihydroxy diphenylsulphone that contains at least 85 weight % of existence of phenol and sulfonic acid,
The consumption of described phenol contains 4 for not being higher than, 2 times of weight of the dihydroxydiphenylsulisomer isomer mixture of 4 '-dihydroxy diphenylsulphone, and the mole % of sulfonic acid contains 4 for not being higher than, 20 moles of % of the dihydroxydiphenylsulisomer isomer mixture of 4 '-dihydroxy diphenylsulphone.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001300933A JP4858897B2 (en) | 2001-09-28 | 2001-09-28 | Process for producing dihydroxydiphenylsulfone isomer mixture |
| JP300933/2001 | 2001-09-28 | ||
| JP300942/2001 | 2001-09-28 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028184009A Division CN1267415C (en) | 2001-09-28 | 2002-09-26 | The preparation method of dihydroxydiphenyl sulfone isomer mixture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1781905A CN1781905A (en) | 2006-06-07 |
| CN1319942C true CN1319942C (en) | 2007-06-06 |
Family
ID=19121423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101269482A Expired - Fee Related CN1319942C (en) | 2001-09-28 | 2002-09-26 | Method for producing dihydroxydiphenylsulfone isomer mixture |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4858897B2 (en) |
| CN (1) | CN1319942C (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5041677A (en) * | 1985-10-04 | 1991-08-20 | Amoco Corporation | Process for synthesizing 4,4'-dihydroxydiphenyl sulfone |
| US5241121A (en) * | 1989-12-29 | 1993-08-31 | Konishi Chemical Ind. Co., Ltd. | Process for preparation of 4,4'-dihydroxydiphenylsulfone |
| US5399772A (en) * | 1993-05-31 | 1995-03-21 | Nicca Chemical Co., Ltd. | Method of producing A 2,4'-dihydroxydiphenylsulfone |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE51863T1 (en) * | 1985-10-04 | 1990-04-15 | Amoco Corp | PROCESS FOR SYNTHESIS OF 4,4'DIHYDROXYDIPHENYLSULFONE. |
| JPH082861B2 (en) * | 1989-12-29 | 1996-01-17 | 小西化学工業株式会社 | Method for producing high-purity 4,4'-dihydroxydiphenyl sulfone |
| JPH07119196B2 (en) * | 1992-06-12 | 1995-12-20 | 日華化学株式会社 | Method for producing high-purity 2,4'-dihydroxydiphenyl sulfones |
-
2001
- 2001-09-28 JP JP2001300933A patent/JP4858897B2/en not_active Expired - Fee Related
-
2002
- 2002-09-26 CN CNB2005101269482A patent/CN1319942C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5041677A (en) * | 1985-10-04 | 1991-08-20 | Amoco Corporation | Process for synthesizing 4,4'-dihydroxydiphenyl sulfone |
| US5241121A (en) * | 1989-12-29 | 1993-08-31 | Konishi Chemical Ind. Co., Ltd. | Process for preparation of 4,4'-dihydroxydiphenylsulfone |
| US5399772A (en) * | 1993-05-31 | 1995-03-21 | Nicca Chemical Co., Ltd. | Method of producing A 2,4'-dihydroxydiphenylsulfone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1781905A (en) | 2006-06-07 |
| JP4858897B2 (en) | 2012-01-18 |
| JP2003104954A (en) | 2003-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1158271C (en) | Process for preparing 5-cyano-2-benzo [ c ] furanone | |
| CN1034531A (en) | Dehydrogenation method of cyclohexenone | |
| CN1054763A (en) | Process for making alkylated aromatic products using alkylated zeolites and dealkylated zeolites | |
| CN1211377C (en) | The preparation method of citalopram | |
| CN1319942C (en) | Method for producing dihydroxydiphenylsulfone isomer mixture | |
| CN1267415C (en) | The preparation method of dihydroxydiphenyl sulfone isomer mixture | |
| CN1651378A (en) | Novel hydrofluoroether and its preparation method | |
| CN1100084A (en) | Process for producing ortho-isopropylated phenol derivatives | |
| CN1218918C (en) | The synthetic method of geranyl geraniol | |
| CN1167664C (en) | Synthesis of Methylphenyl Oxalate and Diphenyl Oxalate Catalyzed by Supported Metal Oxide | |
| CN1277960A (en) | Method for preparing retinene, and intermediates for prepn. of retinene | |
| CN1213985C (en) | Process for production of t-butyl acetate from MTBE | |
| CN1566064A (en) | Process for preparing azelaic acid by oleic acid phase transfer catalytic oxidation | |
| CN1701066A (en) | Manufacture of Tocopheryl Acetate | |
| CN1090179C (en) | Fluorinated alkylthiocyanate process | |
| CN1203572A (en) | Method for c-alkylating hydroxylated aromatic compounds | |
| CN1263737C (en) | The preparation method of dihydroxydiphenyl sulfone isomer mixture | |
| EP4126347A1 (en) | Production of allyl alcohol from glycerol using a reusable catalyst made from rhenium | |
| JP4930668B2 (en) | Process for producing dihydroxydiphenylsulfone isomer mixture | |
| JPS63119432A (en) | Production of 4,4-dihydroxybiphenyl | |
| CN1583254A (en) | Preparation of loaded molybdenum oxide catalyst for synthesis of phenyloxalate by ester interchange process | |
| CN1314664C (en) | Process for producing high-purity 4,4'-dihydroxydiphenyl sulfone | |
| CN1138735C (en) | Process and intermediate compounds for preparation of pesticidal fluoroolefin compounds | |
| CN1013362B (en) | Process for producing hydroxybenzenes | |
| US12240805B2 (en) | Method for producing 1,4-dimethylnaphthalene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070606 Termination date: 20150926 |
|
| EXPY | Termination of patent right or utility model |