CN102336690A - Method for separating and purifying high-purity 4,4'-dihydroxydiphenylsulfone - Google Patents
Method for separating and purifying high-purity 4,4'-dihydroxydiphenylsulfone Download PDFInfo
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- CN102336690A CN102336690A CN 201110346529 CN201110346529A CN102336690A CN 102336690 A CN102336690 A CN 102336690A CN 201110346529 CN201110346529 CN 201110346529 CN 201110346529 A CN201110346529 A CN 201110346529A CN 102336690 A CN102336690 A CN 102336690A
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Abstract
The invention discloses a method for separating and purifying high-purity 4,4'-dihydroxydiphenylsulfone, which comprises the following steps: heating phenol and sulfonating agent under reflux to react in the presence of an aromatic solvent; after the reaction finishes, continuing heating to 160-210 DEG C, separating the liquid mixture, blowing the residual solid material with aromatic solvent steam until no liquid mixture flows out; and adding water to the residual solid material, and carrying out azeotropic distillation to remove the residual aromatic solvent, wherein the pressure of the aromatic solvent steam for blowing is 1-10kgf/cm<2>, and the stream speed is 100-200L/kg.H. The method has the advantages of environmental protection, high security and energy saving, and can obtain high-yield high-purity 4,4'-dihydroxydiphenylsulfone.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of high purity 4,4 '-separating and purifying method of dihydroxy diphenylsulphone.
Background technology
4,4 '-dihydroxy diphenylsulphone has another name called bisphenol S, is white solid, is soluble in aliphatic hydrocarbon, is dissolved in pure and mild ether, is slightly soluble in aromatic hydrocarbons, is insoluble in water.Contain two hydroxyls and the sulfuryl that electrophilic is very strong in this article molecule, so acid stronger than other phenols.Bisphenol S can be used as dispersion agent, the resol hardening accelerator of laking agent, solution additive, leather retanning agent, dispersed dye high temperature dyeing, and resin fire retardant etc. also are the midbodys of agricultural chemicals, dyestuff, auxiliary agent simultaneously.As the surrogate of dihydroxyphenyl propane, can be used as the raw material of polycarbonate, epoxy resin, polyester, resol, and the raw material of polysulfones, polyethersulfone.These article also are used to make color photographic materials, photograph contrast enhancement agents, thermal recording medium (developer), daily tensio-active agent and high-efficiency deodorant etc.In recent years, the demand to bisphenol S increased fast on the market.
Present 4,4 '-the synthetic of dihydroxy diphenylsulphone mainly is to adopt the vitriol oil and phenol dehydration reaction generation sulfocarbolic acid, sulfocarbolic acid is 4,4 with the phenol dehydrating condensation again '-dihydroxy diphenylsulphone.Because ortho position and the contraposition of phenolic hydroxyl group are relatively active, so 4,4 '-must have in the synthetic process of dihydroxy diphenylsulphone by product 2,4 '-generation of dihydroxy diphenylsulphone and a spot of trihydroxy-triphenyl two sulfones.
Highly purified 4,4 in order to obtain '-dihydroxy diphenylsulphone, must remove in the synthetic product not 2,4 of transposition '-impurity such as dihydroxy diphenylsulphone and a spot of trihydroxy-triphenyl two sulfones.Chinese invention patent CN01251275 is raw material with phenol, with concentrated acid sulfonation synthetic 4,4 '-dihydroxy diphenylsulphone; With 1,2, the 4-trichlorobenzene is made dewatering agent; With the aromatic series disulfonic acid do isomer 2,4 '-suppressor factor of dihydroxy diphenylsulphone, water is refining; Obtain 4,4 '-the dihydroxy diphenylsulphone white crystals.Britain patent of invention GB2216125A provides a kind of purifying 4; 4 '-method of dihydroxy diphenylsulphone, the bisphenol S bullion is dissolved in the alkali, transfer pH value through adding acid; Making bisphenol S form monometallic salts out; Other impurity is dissolved in the alkali, filters the monometallic salt that obtains bisphenol S then, and the monometallic salt acid adjustment with bisphenol S obtains highly purified bisphenol S again.Also be reported in phenol and sulphonating agent or sulfocarbolic acid and carry out in the presence of the aromatics non-polar solvent, carrying out dehydration reaction after the dehydration reaction, the dihydroxy diphenylsulphone that obtains is suspended in wherein, hybrid reaction suspension-s and polar solvent; To be partly dissolved dihydroxy diphenylsulphone at least; Make 4,4 then '-the dihydroxy diphenylsulphone deposition, through filtering or decant separates; Obtain 4,4 '-dihydroxy diphenylsulphone.
The bisphenol S process for refining that aforesaid method adopted respectively has relative merits.Make a concrete analysis of as follows: Chinese invention patent CN02151275 makes isomer 2 with the aromatic series disulfonic acid; 4 '-suppressor factor of dihydroxy diphenylsulphone, last water is made with extra care, and this method must be made with extra care and with a large amount of water washings with 30 times water; Can produce great amount of wastewater, be unfavorable for environmental protection.Britain patent of invention GB2216125A is dissolved in the bisphenol S bullion in the buck; Transfer pH value through adding acid, make bisphenol S form monometallic and salt out, other impurity is dissolved in the alkali; Filter the monometallic salt that obtains bisphenol S then; Monometallic salt acid adjustment with bisphenol S obtains highly purified bisphenol S again, and this method also can produce great amount of wastewater, is unfavorable for environmental protection.In addition, adopt the aromatics non-polar solvent to separate bisphenol S, in sepn process, must use a large amount of aromatics non-polar solvents, consuming lot of energy reclaims the aromatics non-polar solvent on the one hand, causes more solvent loss on the other hand easily.
Summary of the invention
The objective of the invention is to the deficiency to above-mentioned prior art, a kind of environmental protection is provided, can obtains high yield safe, energy-conservation the time, highly purified 4,4 '-separating and purifying method of dihydroxy diphenylsulphone.
The objective of the invention is to realize in the following manner:
A kind of high purity 4,4 '-separating and purifying method of dihydroxy diphenylsulphone, comprise that phenol and sulphonating agent carry out heating reflux reaction in the presence of aromatic solvent; After it is characterized in that reaction is reached home; Continue to be warming up to 160～210 ℃, separate liquid form mixt (under the partial material molten state), do not go out to there being liquid mixture flow with aromatic solvent steaming out residue solid substances; In the residue solid substances, add water, component distillation is removed residual aromatic solvent; Wherein, the pressure that purges used aromatic solvent steam is 1～10Kgf/cm
2, gas speed is 100L/Kg.H～200L/Kg.H.Through this process can obtain purity up to 99.5% 4,4 '-the dihydroxy diphenylsulphone bullion.
After the said process preferred reaction is reached home, continue to be warming up to 180～200 ℃.The preferred pressure that purges used aromatic solvent steam is 2～5Kgf/cm
2Gas speed is 100L/Kg.H～200L/Kg.H (being that the per kilogram solid substances per hour uses the speed of the gas of 100L～200L to purge), preferred 150L/Kg.H～200L/Kg.H.Pressure is excessive or gas is fast excessive, all can cause product yield to descend; Reverse pressure is too small or gas is fast too small, all can influence product gas purity.Aromatic solvent according to the invention can be any mixing of chlorobenzene, toluene, m-xylene, p-Xylol or above-mentioned two or more solvent.The above-mentioned amount that in the residue solid substances, adds entry is 1～2 times of a solid substances quality.Sulphonating agent is preferably sulfuric acid.
In the aforesaid method; Can also in the solid substances after removing residual aromatic solvent, add the alcohol of 1～3.5 times of solid substances quality or the mixing solutions of ketone and water; Add gac again, heating up makes solid substances dissolving, decolouring, and filtered while hot, filtrating are reduced to room temperature and separated out, filters, dries; Obtain purity up to 99.99% 4,4 '-dihydroxy diphenylsulphone.
The mass concentration of the mixing solutions of alcohol or ketone and water is 20%～50%, and preferred mass concentration is 30%; Described alcohol is preferably methyl alcohol, ethanol, and ketone is preferably acetone.Wherein, the mixing solutions consumption of alcohol or ketone and water is excessive or concentration is excessive, can cause product yield to descend; Consumption is too small or concentration is too small, can cause material dissolution incomplete, is difficult to carry out heat filtering.
Separation liquid form mixt of the present invention is to provide power that liquid form mixt is extruded through micropore by vacuum or pressurized gas (comprising: water vapor, air, nitrogen, organic vapor etc.) etc., keeps solid substances.The present invention also can be realized separating by the reactor drum that inside is provided with microporous filter.Liquid form mixt comprises: phenol, sulfuric acid, sulfocarbolic acid, trihydroxy-triphen two sulfones and not transposition 2,4 '-impurity such as dihydroxy diphenylsulphone, can apply mechanically in that the secondary response relaying is continuous down.
Principle of the present invention is: phenol and sulphonating agent carry out heating reflux reaction in the presence of aromatic solvent, after reaction is reached home, continue to be warming up to 160～210 ℃; Impurity and small number of materials that reaction generates exist with liquid state, and 4,4 '-dihydroxy diphenylsulphone (bisphenol S) exists with solid state; After the solid-liquid separation, feed 160～210 ℃ aromatic solvent steaming in the bisphenol S bullion after separating, a small amount of liquid form mixt impurity that contains in the solid substances is purged out; Add entry then; Distill, aromatic solvent residual in the reactor drum is steamed, obtain the bisphenol S bullion behind the purifying; Add the alcohol of specified proportion or the mixed solvent of ketone and water again, heating up makes material dissolution, through activated carbon decolorizing, cooling separate out, filter, after the operation such as oven dry, obtain content up to 99.99% 4,4 '-dihydroxy diphenylsulphone.
With prior art beneficial effect more of the present invention:
(1) the present invention 4,4 '-treating process of dihydroxy diphenylsulphone in used aromatic solvent seldom, and this method can adopt reactor drum with the solvent cycle utilization, is a kind of clean preparation method;
(2) the present invention can obtain purity and yield all very high 4,4 '-dihydroxy diphenylsulphone, purity can reach more than 99.8%, yield can reach (with sulphur acid meter) more than 90%;
(3) the present invention will purify 4,4 '-isolated liquid form mixt turns back to down in the secondary response and goes during dihydroxy diphenylsulphone, can improve next reaction yield, thereby reduce the generation of residue.
Description of drawings
The reactor drum that Fig. 1 is adopted for embodiment of the invention reaction.
Among the figure, 1 is cylindrical shell, and 2 are the heating medium outlet, and 3 is the heating medium import, and 4 is whisking appliance, and 5 is opening for feed, and 6 is filter stick, and 7 is discharge port, and 8 is liquid outlet, and 9 is filter screen or filter cloth, and 10 for hanging the angle.
Embodiment
Below through specific embodiment the present invention is done further elaboration, should not be construed as qualification to the total technical scheme of the present invention.
The reactor drum that embodiment 1-4 is adopted is as shown in Figure 1: a kind of heated closed reactor with stirring, comprise cylindrical shell 1, and cylindrical shell 1 top is provided with opening for feed 5, and cylindrical shell 1 bottom is provided with discharge port 7; Cylindrical shell 1 sidewall below is provided with heating medium import 3, and cylindrical shell 1 another sidewall top is provided with heating medium outlet 2, and cylindrical shell 1 top is provided with whisking appliance 4, and whisking appliance 4 stretches into cylindrical shell 1 inside and do not contact with 1 end of cylindrical shell; Cylindrical shell 1 both sides are respectively equipped with 1 and hang angle 10; Cylindrical shell 1 sidewall bottom transverse is provided with the paddle that filter stick 6 and filter stick 6 are higher than whisking appliance; Cylindrical shell 1 bottom is provided with discharge port 7 and liquid outlet 8, and liquid outlet 8 outer one deck conventional filter screen or the filter clothes 9 (200～500 order) of covering are so that hold back residue.
During concrete operations, material gets into reactor drum by opening for feed 5, and each outlet of off-response device is simultaneously opened whisking appliance 4 and stirred; Can heat as required simultaneously, reaction is opened filter stick 6 after finishing, and the micropore filter material through wherein carries out millipore filtration; Liquid material is extruded by filter stick 6, and press filtration is opened liquid outlet 8 after finishing; Extrude a little remaining feed liquid again, feed gas through opening for feed 5 and purge, the liquid material that purges out flows out through filter stick 6 and/or liquid outlet 8; Each outlet of off-response device adds water and adds thermal distillation in reactor drum, after giving vent to anger through the production well on the reactor drum, in reactor drum, add the mixing solutions and the gac of alcohol or ketone and water again, heats up to make solid substances dissolving and decolouring, is discharged by discharge port 7.
Embodiment 1:
In reactor drum, drop into 1.02mol phenol, 0.5mol sulfuric acid and the reaction of 15g chlorobenzene temperature rising reflux; After reaction is reached home, continue to be warming up to 180～190 ℃, through micropore filter material the liquid form mixt in the reactor drum is extruded reactor drum with nitrogen and do not go out to there being liquid mixture flow, pressure is 1.5Kgf/cm
2～3Kgf/cm
2Pressed the back in reactor drum, to feed chlorobenzene steam and purged, pressure is 4Kgf/cm
2, gas speed is 150L/Kg.H, no liquid mixture leaches behind the purging 10min; In reactor drum, adding the intensification of 100g water steams wherein residual chlorobenzene; Record 4,4 this moment '-dihydroxy diphenylsulphone content is 99.5%, in reactor drum, adds the 339g mass percentage concentration then and be 30% aqueous ethanolic solution and 5.6g gac; Temperature rising reflux; The solid substances dissolving, decolouring is discharged by the discharge port of reactor drum; With the material filtered while hot of discharging, filtrating is reduced to room temperature and is separated out, and filters, and oven dry obtains 113g 4,4 '-dihydroxy diphenylsulphone after the weighing, and content is 99.99%, and yield is 90.4% (with sulphur acid meter).
Embodiment 2:
In reactor drum, drop into 1.01mol phenol, 0.5mol sulfuric acid and the reaction of 15g toluene solvant temperature rising reflux; After reaction is reached home, continue to be warming up to 170～180 ℃, through micropore filter material the liquid form mixt in the reactor drum is extruded reactor drum with nitrogen and do not go out to there being liquid mixture flow, pressure is 1.5Kgf/cm
2～3Kgf/cm
2Pressed the back in reactor drum, to feed toluene vapor and purged, pressure is 2Kgf/cm
2, gas speed is 160L/Kg.H, no liquid mixture leaches behind the purging 10min; In reactor drum, adding the intensification of 100g water steams wherein residual toluene; Record 4,4 this moment '-dihydroxy diphenylsulphone content is 99.5%, in reactor drum, adds the 339g mass percentage concentration then and be 30% aqueous acetone solution and 5.6g gac; Temperature rising reflux; The solid substances dissolving, decolouring is discharged by the discharge port of reactor drum; With the material filtered while hot of discharging, filtrating is reduced to room temperature and is separated out, and filters, and oven dry obtains 114.2g 4,4 '-dihydroxy diphenylsulphone after the weighing, and content is 99.98%, and yield is 91.4% (with sulphur acid meter).
Embodiment 3:
The liquid material that 180～190 ℃ are shifted out in the instance 1 is dropped into reactor drum, drop into 1.02mol phenol, 0.5mol sulfuric acid and the reaction of 15g chlorobenzene solvent temperature rising reflux then; After reaction is reached home, continue to be warming up to 180～190 ℃, through micropore filter material the liquid form mixt in the reactor drum is extruded reactor drum with nitrogen and do not go out to there being liquid mixture flow, pressure is 1.5Kgf/cm
2～3Kgf/cm
2, to have pressed the back in reactor drum, to feed chlorobenzene steam and purged, pressure is 6Kgf/cm
2, gas speed is 100L/Kg.H, no liquid mixture leaches behind the purging 10min; In reactor drum, adding the intensification of 100g water steams wherein residual chlorobenzene; Record 4,4 this moment '-dihydroxy diphenylsulphone content is 99.5%, in reactor drum, adds the 339g mass percentage concentration then and be 30% aqueous ethanolic solution and 5.6g gac; Temperature rising reflux; The solid substances dissolving, decolouring is discharged by the discharge port of reactor drum; With the material filtered while hot of discharging, filtrating is reduced to room temperature and is separated out, and filters, and oven dry obtains 115.2g4 after the weighing, 4 '-dihydroxy diphenylsulphone, content is 99.98%, yield is 92.2% (with sulphur acid meter).
Embodiment 4:
The liquid material that 170～180 ℃ are shifted out in the instance 2 is dropped into reactor drum, drop into 1.01mol phenol, 0.5mol sulfuric acid and 15g toluene solvant then, the temperature rising reflux reaction; After reaction is reached home, continue to be warming up to 170～180 ℃, through micropore filter material the liquid form mixt in the reactor drum is extruded reactor drum with nitrogen and do not go out to there being liquid mixture flow; Pressure is 1.5Kgf/cm
2～3Kgf/cm
2, to have pressed the back in reactor drum, to feed long-pending toluene and chlorobenzene mixing steam and purged than 1: 1, pressure is 2Kgf/cm
2, gas speed is 200L/Kg.H, no liquid mixture leaches behind the purging 10min; In reactor drum, add 100g water, heating up steams wherein residual toluene and chlorobenzene, and record 4 this moment; 4 '-dihydroxy diphenylsulphone content is 99.5%; In reactor drum, add the 115g mass percentage concentration then and be 50% aqueous ethanolic solution and 5.6g gac, temperature rising reflux, solid substances dissolves; Decolouring is discharged by the discharge port of reactor drum; With the material filtered while hot of discharging, filtrating is reduced to room temperature and is separated out, and filters, and oven dry obtains 115.6g 4,4 '-dihydroxy diphenylsulphone after the weighing, and content is 99.98%, and yield is 92.5% (with sulphur acid meter).
Embodiment of the invention employing HPLC detection 4,4 '-dihydroxy diphenylsulphone content.Chromatographic condition: with the octadecylsilane chemically bonded silica is weighting agent; With volume ratio is that acetonitrile-water-Glacial acetic acid min. 99.5 of 30: 70: 0.1 is a moving phase; Flow velocity is 1.2ml/min; The detection wavelength is 254nm.Number of theoretical plate by 4,4 '-dihydroxy diphenylsulphone reference substance peak calculates and should be not less than 2000.
The inventive method can adopt other the outer any experimental installations that can realize step of the present invention of said reactor drum, is not limited to the reactor drum that the present invention puts down in writing.
Claims (10)
- A high purity 4,4 '-separating and purifying method of dihydroxy diphenylsulphone, comprise that phenol and sulphonating agent carry out heating reflux reaction in the presence of aromatic solvent; After it is characterized in that reaction is reached home; Continue to be warming up to 160～210 ℃, separate liquid form mixt, do not go out to there being liquid mixture flow with aromatic solvent steaming out residue solid substances; In the residue solid substances, add water, component distillation is removed residual aromatic solvent; Wherein, the pressure that purges used aromatic solvent steam is 1～10Kgf/cm 2, gas speed is 100L/Kg.H～200L/Kg.H.
- 2. a kind of high purity 4,4 according to claim 1 '-separating and purifying method of dihydroxy diphenylsulphone, it is characterized in that reaction is reached home after, continue to be warming up to 180～200 ℃.
- 3. a kind of high purity 4,4 according to claim 1 '-separating and purifying method of dihydroxy diphenylsulphone, the pressure that it is characterized in that purging used aromatic solvent steam is 2～5Kgf/cm 2
- 4. a kind of high purity 4,4 according to claim 1 '-separating and purifying method of dihydroxy diphenylsulphone, it is characterized in that said aromatic solvent is any mixing of chlorobenzene, toluene, m-xylene, p-Xylol or above-mentioned two or more solvent.
- 5. a kind of high purity 4,4 according to claim 1 '-separating and purifying method of dihydroxy diphenylsulphone, it is characterized in that the described water that in the residue solid substances, adds 1～2 times of amount of solid substances quality.
- 6. a kind of high purity 4,4 according to claim 1 '-separating and purifying method of dihydroxy diphenylsulphone, it is characterized in that described separation liquid form mixt extrudes liquid form mixt for power is provided with vacuum or pressurized gas through micropore, keep solid substances.
- 7. high purity 4,4 according to claim 1 '-separating and purifying method of dihydroxy diphenylsulphone, it is characterized in that described sulphonating agent is a sulfuric acid.
- 8. high purity 4 according to claim 1; 4 '-separating and purifying method of dihydroxy diphenylsulphone; It is characterized in that adding the alcohol of 1～3.5 times of solid substances quality or the mixing solutions of ketone and water in the solid substances after removing residual aromatic solvent; Add gac again, heating up makes solid substances dissolving, decolouring, and filtered while hot, filtrating are reduced to room temperature and separated out, filters, dries.
- 9. a kind of high purity 4,4 according to claim 8 '-separating and purifying method of dihydroxy diphenylsulphone, the mass concentration that it is characterized in that the mixing solutions of described alcohol or ketone and water is 20%～50%.
- 10. high purity 4,4 according to claim 8 '-separating and purifying method of dihydroxy diphenylsulphone, it is characterized in that described alcohol is methyl alcohol or ethanol, described ketone is acetone.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105732448A (en) * | 2016-03-31 | 2016-07-06 | 苏州华道生物药业股份有限公司 | Purification method of diphenylsulfone |
| CN105968357A (en) * | 2016-06-29 | 2016-09-28 | 江苏傲伦达科技实业股份有限公司 | Preparation method of polyether sulphone |
| CN106758415A (en) * | 2016-12-12 | 2017-05-31 | 郑州艾莫弗信息技术有限公司 | A kind of active dye fixing agent and preparation method thereof |
Citations (1)
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| CN1508127A (en) * | 2002-12-13 | 2004-06-30 | 上海群力化工有限公司 | High-purity 4,4'-dihydroxy diphenyl sulfone preparing method |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1508127A (en) * | 2002-12-13 | 2004-06-30 | 上海群力化工有限公司 | High-purity 4,4'-dihydroxy diphenyl sulfone preparing method |
Non-Patent Citations (1)
| Title |
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| 《技术进展》 20011231 马海洪等 制备双酚S研究的新进展 , 第8期 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105732448A (en) * | 2016-03-31 | 2016-07-06 | 苏州华道生物药业股份有限公司 | Purification method of diphenylsulfone |
| CN105968357A (en) * | 2016-06-29 | 2016-09-28 | 江苏傲伦达科技实业股份有限公司 | Preparation method of polyether sulphone |
| CN106758415A (en) * | 2016-12-12 | 2017-05-31 | 郑州艾莫弗信息技术有限公司 | A kind of active dye fixing agent and preparation method thereof |
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