CN1332945C - Process for producing 4,4'-bisphenol sulphone - Google Patents
Process for producing 4,4'-bisphenol sulphone Download PDFInfo
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- CN1332945C CN1332945C CNB2006100033778A CN200610003377A CN1332945C CN 1332945 C CN1332945 C CN 1332945C CN B2006100033778 A CNB2006100033778 A CN B2006100033778A CN 200610003377 A CN200610003377 A CN 200610003377A CN 1332945 C CN1332945 C CN 1332945C
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Abstract
The present invention relates to a method for preparing 4, 4'-bisphenol sulphone. When phenol reacts with sulfuric acid in the process of preparing the 4, 4'-bisphenol sulphone, the dehydration reaction is carried out in a mixed solvent prepared from aliphatic saturated hydrocarbon and mesitylene, and the boiling point of the aliphatic saturated hydrocarbon is 175 DEG C or more than 175 DEG C. The mesitylene is finally distilled from a reaction system. The reaction can also be carried out in a solvent containing aliphatic saturated hydrocarbon or in a reaction container with a rectifying device. The 4, 4'-bisphenol sulphone with excellent operability and high yield can be prepared. Moreover, after the reaction is carried out in the solvent containing aliphatic saturated hydrocarbon, alcohol with the carbon number of 1 to 3 is added to the reaction solution. The 4, 4'-bisphenol sulphone is recrystallized in an alcohol layer whose solution is separated. As a result, the 4, 4'-bisphenol sulphone with high purity can be obtained conveniently.
Description
The application is to be dividing an application of March 20, application number in 2002 Chinese patent application that is 02828560.3 (international application no is PCT/JP02/02702) the applying date.
Technical field
The present invention relates to make phenol and sulfuric acid to react making 4, and 4 '-bisphenol sulphone (perhaps 4,4 '-dihydroxy-diphenyl sulfone, hereinafter referred to as 4,4 '-BPS) method.
Background technology
4,4 '-BPS is a kind of usually as the useful compound of the raw material of polysulfones (PSF) and polyethersulfone engineering plastics such as (PES) etc.For make this 4,4 '-BPS is although research in the past often makes the method for phenol and sulfuric acid reaction, but the problem of this technology mainly is, how to carry out the removal of water effectively and how to reduce isomer 2 as by product, 4 '-BPS is to improve 4, these two aspects of the yield of 4 '-BPS.
Disclose a kind of 4 in the Te Kaiping 3-101656 communique, the manufacture method of 4 '-BPS, the feature of this method is, with mesitylene as reaction solvent, under refluxad phenol and sulphonating agent etc. are reacted while removing water, make 4 of generation, 4 '-BPS reacts when suspending.Mesitylene has the advantage that does not react and dissolve phenol etc. well with sulfonic acid etc.But because mesitylene dissolves the by product 2 in this reaction, 4 '-BPS exists down with about about 2 one-tenth significant quantity so be difficult in this by product, improves the yield of 4,4 '-BPS.
Te Kaiping 3-206073 communique has been put down in writing a kind of method in order to improve the problems referred to above, and the feature of this method is, use mesitylene especially as reaction solvent, Yi Bian under the acid catalyst condition, make 2,4 '-BPS and 4,4 '-BPS suspends and heats up in a steamer and desolvate, Yi Bian make it carry out isomerization reaction.In this case, because the solid phase that can not obtain piece to be in loose state, thereby operation easily.But in order to make it carry out isomerization, must similarly heat up in a steamer and desolvate, thereby need management to be used to adjust the reaction conditions of the removal speed and the isomerization speed of solvent.In addition, desolvate, also need reliever in order fully to heat up in a steamer, and, in case after solvent heats up in a steamer, under solid state, make resultant continue at high temperature to heat the state of resultant, then cause easily painted, so not preferred.
Put down in writing by phenol and sulfuric acid are reacted in dichlorobenzene or trichlorobenzene in the special fair 4-74347 communique, optionally made 4,4 '-BPS crystallization, finally obtain crystalline 4,2 of 4 '-BPS and solution state, 4 '-BPS.In this case, do not desolvate owing to do not heat up in a steamer, thus there is no need to adjust miscellaneous reaction of accompanying with it, but owing to 2 of residual solution state, 4 '-BPS, so the result causes 4, the yield of 4 '-BPS descends.
The spy opens and has put down in writing in the clear 51-98239 communique when phenol and sulfuric acid are reacted, and finally will heat up in a steamer whole solvents and make 4, the method for 4 '-BPS.In the method, desolvate by heating up in a steamer from reaction system, can make to be dissolved in 2 of solvent, 4 '-BPS is to 4, and isomerization reaction takes place 4 '-BPS.But the problem of existence is that the resultant of reaction that obtains after solvent heats up in a steamer will be formed on industrial reluctant solid block, and needs management to be used to adjust the reaction conditions of the removal speed and the isomerization speed of solvent.
In using the method for solvent, except that aforesaid method, use the method No. the 4th, 996,367, clear 64-9970, United States Patent (USP) (spy open etc.) of aliphatic hydrocarbon solvent in addition.
Using under the situation of aliphatic hydrocarbon solvent, its advantage is, because 4,4 '-BPS, 2,4 '-BPS is dissolved in this solvent hardly, even thereby do not heat up in a steamer and desolvate, also can make 2,4 '-BPS is to 4, and 4 '-BPS resets, and obtains the resultant at industrial easy to handle pulpous state.
For example United States Patent (USP) the 4th, 996, the high boiling hydrocarbon that discloses the low boiling hydrocarbon that uses 70-140 ℃ of boiling point and boiling point 160-220 ℃ for No. 367 is as solvent, make it to distill condensation with low boiling hydrocarbon as entrainer, make phenol layer at least 2 layers the liquid layer that obtains thus turn back to the method for reaction system.The heaviest formation bottom of this phenol layer makes its easy backflow.Preferred solvent for example has the combination of ア イ ソ パ-(registered trademark of エ Network ソ Application chemistry (strain)) E (115 ℃ of initial boiling points) and ア イ ソ パ-H (176 ℃ of initial boiling points).When in the reaction system of having used this solvent, refluxing,, and be difficult to when removing water layer, phenol and aliphatic hydrocarbon solvent be turned back in the responding layer usually because phlegma is separated into 3 layers in phenol/water/aliphatic hydrocarbon.In addition, in this invention, it is indispensable using suspension agent (for example ア イ ソ パ-(registered trademark of エ Network ソ Application chemistry (strain)) H, initial boiling point are 176 ℃) and 2 kinds of solvents of entrainer (for example ア イ ソ パ-E, initial boiling point are 115 ℃), but when using the different solvent of rerum natura as mentioned above, its problem is, in the occasion of utilizing solvent again, will encounter difficulties at the management aspect of boiling point etc., also will cause manufacturing cost to rise simultaneously.
Therefore, in above-mentioned prior art, also not to reacted post-processing operation advantageous method.
The spy opens that disclosed method is that the resultant of reaction of the phenol and the vitriol oil is dissolved in the methanol aqueous solution among the clear 50-106937, in this methanol aqueous solution, make 4,4 '-BPS recrystallize, improve 2, the separation efficiency of 4 '-BPS, but this method is characterised in that, is a kind of manufacture method in solvent-free reaction system, has used the quite low methanol aqueous solution of concentration.
Although disclose among special (patent application) 2000-273084 of hope utilize phenol and sulfuric acid are reacted after, the alcohol that adds carbon number 1-3 to this reaction solution, from liquid separation obtain alcohol layer recrystallize 4, the method of 4 '-BPS, easy and make 4,4 '-BPS with high yield.But need further improve reaction efficiency.
The objective of the invention is to, provide a kind of make under refluxad in the sturated aliphatic hydrocarbon solvent that phenol and sulfuric acid reacts 4, the manufacture method of 4 '-BPS, in the method, bring 4 by using in reaction process and operation thereafter, the suitable mixed solvent of the high yield of 4 '-BPS can be removed the water that side reaction generates effectively, and can improve 4, the yield of 4 '-BPS.
Other purpose is, with sturated aliphatic hydrocarbon as under the situation of solvent, by cooperating the appropriate postprocessing operation, easy and make 4,4 ' BPS with high yield.
And then the object of the invention is, provides a kind of and is using sturated aliphatic hydrocarbon as solvent, phenol and sulfuric acid are reacted make 4, under the situation of 4 '-BPS, remove water effectively while heating up in a steamer to anhydrate, suppress the quantity of distillate of phenol, thereby further improve the means of the reaction efficiency of BPS.
Summary of the invention
The present invention is a kind of 4, the manufacture method of 4 '-bisphenol sulphone, wherein, be that sturated aliphatic hydrocarbon more than 175 ℃ or 175 ℃ and the boiling point that dissolves phenol are in the mixed solvent of the solvent composition below 170 ℃ or 170 ℃ by boiling point, under refluxing, phenol and sulfuric acid are reacted while removing water, heat up in a steamer from reaction system and dissolve this phenol, boiling point is the solvent below 170 ℃ or 170 ℃.The solvent that particularly dissolves phenol, boiling point and be below 170 ℃ or 170 ℃ is 4 of a mesitylene, the manufacture method of 4 '-bisphenol sulphone.
In addition, preferably after reaction finishes, dissolving phenol and the solvent of boiling point below 170 ℃ or 170 ℃ are heated up in a steamer from reaction system.
The solvent that the present invention uses be a kind of be the mixed solvent that aliphatic hydrocarbon more than a kind or 2 kinds more than 175 ℃ or 175 ℃ and mesitylene are formed by boiling point.
At sturated aliphatic hydrocarbon is under the situation of mixed solvent, and the recovered temperature of this mixed solvent is more than 175 ℃ or 175 ℃.This solvent for example has ア イ ソ パ-(registered trademark of エ Network ソ Application chemistry (strain)) H, ア イ ソ パ-L, ア イ ソ パ-M.Wherein, preferred ア イ ソ パ-H (176 ℃ of initial boiling points).
Dissolving phenol of the present invention and boiling point are the solvent below 170 ℃ or 170 ℃, and mesitylene and chlorobenzene etc. are for example arranged, but preferred mesitylene.By using the solvent of such dissolving phenol, distilled water, phenol and solvent form 2 layers when dehydration, and the removal of its operation and water is very easy to.
In this mixed solvent, the ratio of sturated aliphatic hydrocarbon and mesitylene is not particularly limited, and with respect to sturated aliphatic hydrocarbon 1 weight part, can use the mesitylene of 0.1-10 weight part, the mesitylene of preferred 0.5-12 weight part.
Usually people know in that phenol and sulfuric acid are reacted and make 4, during 4 '-BPS, be effective as entrainer to removing water with mesitylene particularly.When using mesitylene as solvent, owing to dissolve phenol etc. well, when in this dehydration reaction, utilizing necessary distillation to remove water, distilled phenol and mesitylene form 1 layer, and because proportion is lighter than water, remove the water layer of heavy bottom on one side, on one side light phenol and mesitylene as the upper strata are turned back in the reaction system, this operation is very easy to.
But in the occasion of only using mesitylene as reaction solvent, because mesitylene has dissolving 2, the character of 4 '-BPS does not take place to 4, and the problem that yield reduces appears in the rearrangement reaction of 4 '-BPS.
On the other hand, the sturated aliphatic hydrocarbon solvent dissolves 2 hardly, and 4 '-isomer, thereby can promote 2,4 '-isomer be to 4, the transformation of 4 '-isomer, obtain more 4,4 '-isomer.
When under refluxad carrying out dehydration reaction, under the situation of only using lower boiling aliphatic hydrocarbon solvent, because phlegma is separated into 3 layers from following order by phenol/water/hydrocarbon, while thereby be difficult to remove water and carry out reflux operation, still, when using solvent of the present invention, because phlegma is separated into these 2 layers of water/phenol and mesitylenes from below, thereby in dehydration reaction, can remove water effectively, the result can produce 4,4 '-BPS effectively.In addition, after the dehydration reaction, by heating up in a steamer mesitylene, quicken rearrangement reaction, can obtain being suspended in highly purified 4 in the sturated aliphatic hydrocarbon, 4 '-BPS from reaction system.
According to the present invention, in the dehydration reaction of forebody, there is the lower solvent of boiling point of mesitylene etc. by a side, can promotes the removal of water and can carry out reflux operation easily, in latter half of rearrangement reaction at mixed solvent, by heating up in a steamer this low-boiling solvent, the solvent that formation is made of sturated aliphatic hydrocarbon can promote to change into 4, the rearrangement reaction of 4 '-BPS, improve 4, the output of 4 '-BPS.The mixed solvent of the application of the invention can be eliminated the problem that existing solvent exists, and brings into play a plurality of advantages simultaneously.
Fig. 1 represents from 2, and 4 '-isomer is to 4, the transformation of 4 '-isomer and the relation of temperature.Wherein be to make (4,4 '-BPS) 2,20: 1 mixture of the weight ratio of 4 '-BPS and sulfocarbolic acid is suspended in ア イ ソ パ-series solvent, measures 4 with high performance liquid chromatography (HPLC) under each temperature-time condition, the generation ratio of 4 '-isomer.As known in the figure, between 150 ℃ and 160 ℃, conversion rate is significantly different, have a large amount of 4, the generation of 4 '-isomer.That is, by reacting, can improve 4, the yield of 4 '-isomer in this temperature more than temperature.
Consider above-mentioned situation, the boiling point of sturated aliphatic hydrocarbon solvent be this more than temperature, preferably be higher than the boiling point (162 ℃) of mesitylene significantly, be preferably about more than 175 ℃ or 175 ℃ especially.
In this invention, 4, the formation reaction of 4 '-BPS is generally carried out as follows.
Dissolving phenol and the boiling point prepared by sturated aliphatic hydrocarbon and mesitylene etc. in reaction vessel are the mixed solvent of the solvent composition below 170 ℃ or 170 ℃.To wherein adding phenol and sulfuric acid lentamente, can add simultaneously, add sulfuric acid lentamente after also can adding the necessary amounts of phenol.The amount of phenol finally reaches phenol and vitriolic mol ratio and is 2～3: 1 scope, preferably roughly reaches 2: 1.On the other hand, the ratio of the solvent in the reaction solution is 1～3 times of weight of sulfuric acid weight, especially preferably reaches roughly 2 times of sulfuric acid weight.
Being reflected at about 145 carries out to about 175 ℃ temperature range.
In this reaction, forebody is a dehydration reaction, makes the water and the mesitylene component distillation that generate under above-mentioned temperature of reaction, and making the dissolving phenol of water, mesitylene etc. and distillating boiling point is that solvent and phenol below 170 ℃ or 170 ℃ distillates.When making its condensation, then be separated into 2 layers of the dissolving layers of water layer and phenol.In the occasion of using mesitylene, this phenol dissolving layer is because light, and water layer forms bottom, can easily remove water from the bottom.Distilled phenol can turn back in the reaction system continuously as the solution with solvent formation.
This backflow till confirming that dehydration reaction ends, thereafter, stops this backflow by distillating the water of theoretical amount, heats up in a steamer the solvent of lower boilings such as mesitylene (below 170 ℃ or 170 ℃) from reaction system.Can easily heat up in a steamer solvent with this scope boiling point.
At this moment, also can further add sturated aliphatic hydrocarbon solvent with the roughly the same amount of mesitylene of heating up in a steamer.
As mentioned above, begin from solvent, to remove lower boiling solvents such as mesitylene owing to autoreaction is latter half of, so solvent substantially all forms sturated aliphatic hydrocarbon.In this solvent, promote 2,4 '-BPS is to 4, and the conversion reaction of 4 '-BPS finally improves 4, the yield of 4 '-BPS.
By above operation, the resultant that can obtain crystallization is suspended in the slurries in the hydrocarbon system solvent.For from this solvent layer, recrystallize 4,4 '-BPS also can use any known method.
In addition, the present invention also is a kind of 4, the manufacture method of 4 '-bisphenol sulphone, wherein, in containing the solvent of sturated aliphatic hydrocarbon, make phenol and sulfuric acid reaction after, add the alcohol of carbon number 1-3 to this reaction solution, the alcohol layer recrystallize 4 after the liquid separation, 4 '-bisphenol sulphone.
The present invention is a kind of 4, and the manufacture method of 4 '-bisphenol sulphone is wherein in the solvent that contains the sturated aliphatic hydrocarbon more than a kind or 2 kinds or 2 kinds, after making phenol and sulfuric acid reaction, add the alcohol of carbon number 1-3 to this reaction solution, the alcohol layer recrystallize 4 after the liquid separation, 4 '-bisphenol sulphone.Aforementioned solvents can be a kind of sturated aliphatic hydrocarbon, and, the preferred 155-175 of the boiling point of aforementioned sturated aliphatic hydrocarbon ℃.
According to the present invention, use the sturated aliphatic hydrocarbon solvent to obtain 4, behind 4 '-BPS, add alcohol immediately to this reaction solution, can access the alcoholic solution that is dissolved with resultant by the liquid separation operation thus, can transfer to the recrystallize operation effectively.In addition, the sturated aliphatic hydrocarbon after the ethanol-extracted operation can easily carry out recycling.
In the present invention, the sturated aliphatic hydrocarbon of use more than a kind or 2 kinds or 2 kinds is as reaction solvent.The boiling point of this sturated aliphatic hydrocarbon series solvent is preferably more than 155 ℃ or 155 ℃, and the occasion of only being made up of sturated aliphatic hydrocarbon at solvent is more preferably in 155 ℃-175 ℃ scope.At this, sturated aliphatic hydrocarbon is the occasion of mixed solvent, and the recovered temperature of mixed solvent is more than 155 ℃ or 155 ℃ or 155-175 ℃ scope.
The 1st figure represents 2, and 4 '-isomer is to 4, the conversion of 4 '-isomer and the relation of temperature.At this, with 2,20: 1 mixture of the weight ratio of 4 '-BPS and sulfocarbolic acid is suspended in ア イ ソ パ-series solvent, under each temperature-time condition, utilizes high performance liquid chromatography (HPLC) to measure 4, the generation ratio of 4 '-isomer.By this figure also as can be known, 150 ℃ with 160 ℃ between conversion rate significantly different, generate 4,4 '-isomer is many.That is, by reacting, can improve 4, the yield of 4 '-isomer in this temperature more than temperature.From this situation, the boiling point of solvent is this temperature or this is more than temperature preferably.
On the other hand, the boiling point of phenol is 182 ℃, so when use has the solvent of this temperature or the above boiling point of this temperature, under this temperature or this situation of reacting more than the temperature, for example in rectifier unit, reflux solvent not, and phenol is refluxed, be inappropriate.
Solvent of the present invention is the solvent that contains the sturated aliphatic hydrocarbon more than a kind or 2 kinds or 2 kinds, it can be a kind of sturated aliphatic hydrocarbon, also can be the mixed solvent of the sturated aliphatic hydrocarbon more than 2 kinds or 2 kinds, but also can be on the sturated aliphatic hydrocarbon basis with aromatic hydrocarbons series solvent etc. beyond the mixed solvent that forms of solvent.
Under the situation of using the solvent that only constitutes by the sturated aliphatic hydrocarbon series solvent, the sturated aliphatic hydrocarbon series solvent can, use for example nonane, decane, undecane, dodecane, ア イ ソ パ-(registered trademark of エ Network ソ Application chemistry (strain)) G, ア イ ソ パ-H, ア イ ソ パ-L, ア イ ソ パ-M or their mixture.The preferred a kind of solvent that has only wherein that uses.This ア イ ソ パ-solvent is a mixed solvent, owing to,, just can handle equally with single solvent from the viewpoint of utilizing again as long as keep specific composition, so in this manual as the solvent treatment of single kind.
And preferably more than 155 ℃ or 155 ℃, particularly in 155-175 ℃ scope, the solvent with this boiling point for example specifically has nonane, decane, ア イ ソ パ-G etc. to the boiling point of this solvent.Wherein, preferred ア イ ソ パ-G.When use has a kind of solvent of this boiling point, then do not need to use entrainer, in addition because solvent is single composition, thereby help the utilization again of solvent.
On the other hand, in the occasion of the mixed solvent that uses sturated aliphatic hydrocarbon and aromatic hydrocarbons series solvent and solvent, the boiling point of sturated aliphatic hydrocarbon is preferably high than described aromatic hydrocarbons series solvent.In addition, usually when the aromatic hydrocarbons series solvent remains in the reaction system, do not carry out rearrangement reaction, thereby after the water of having confirmed theoretical amount is removed in the reaction system, preferably heat up in a steamer the aromatic hydrocarbons series solvent that adds as far as possible.This sturated aliphatic hydrocarbon series solvent for example has, nonane, decane, undecane, dodecane, ア イ ソ パ-G, ア イ ソ パ-H, ア イ ソ パ-L, ア イ ソ パ-M, the aromatic hydrocarbons series solvent for example has mesitylene, chlorobenzene, dichlorobenzene, trichlorobenzene, toluene(mono)chloride, diethylbenzene, dimethylbenzene etc.
The alcohol that is used for carbon number 1-3 of the present invention for example has methyl alcohol, ethanol, propyl alcohol, the special particular methanol of Virahol.This alcohol can be that pure product also can be the aqueous solution.
In this invention, 4, the formation reaction of 4 '-BPS is generally carried out in the following manner.
In reaction vessel, prepare sturated aliphatic hydrocarbon, to wherein adding phenol and sulfuric acid lentamente as reaction solvent.At this moment, can side by side add phenol and sulfuric acid, also can after the necessary amounts of adding phenol, add sulfuric acid more lentamente.Phenol and vitriolic mol ratio are 2～3: 1 scope, preferably roughly reach 2: 1.
The ratio of the reaction solvent in the reaction solution is 1～2 times of weight of sulfuric acid weight, especially preferably reaches roughly 1.5 times of sulfuric acid weight.
Reaction is about 140 to the temperature of about 175 ℃ of scopes, carries out while under refluxad stir.
This reaction is a dehydration reaction, and its dewatering if within the scope of the invention, can use any known method.In entire reaction, dewater constantly.Concrete easy method is, thereby devices such as use デ ィ Application ス -Network separate the water of removing component distillation.
After dehydration reaction finishes, in order to promote rearrangement reaction, the temperature in the time of also can temporarily keeping dehydration reaction.
Above reaction process makes reaction solution be cooled to about about 80 ℃ after finishing.In this stage, 4,4 '-BPS and 2,2 in the mixture of 4 '-BPS, 4 '-BPS are below about 5% or 5%.
Next adds the alcohol of the 0.5-2 volume ratio doubly of reaction solvent, the preferred alcohol of roughly measuring together in cooled reaction solution, adopted about about 1 hour at about about 65 ℃, makes resultant, and 4,4 '-BPS and 2, the mixture dissolving of 4 '-BPS.Reaction solvent of the present invention is owing to being separated into 2 layers with the intermiscibility of alcohol is little.Because resultant is dissolved in the alcohol layer, so can easily obtain the alcoholic solution of resultant by this operation.This alcoholic solution can be used for the recrystallize operation immediately.
The alcohol that uses is the occasion of pure product, also can add entry again.In addition, consider extraction efficiency, preferably adopt pure water to carry out liquid separation, about the preferred 30-70 weight of the determining alcohol % in the pure water in this stage.
In order to remove impurity and to adjust pH, also can add gac and caustic soda etc. to the alcohol layer.
Add processing such as water in the alcohol layer after liquid separation as required again, near the cool to room temperature, make BPS recrystallize drying, can obtain 4,4 ' BPS.
Determining alcohol in the pure water when carrying out recrystallize is 10-50 weight %, preferred 20-40%, can add alcohol and water so that finally become the pure water of this concentration.2,4 '-BPS more is soluble in alcohol than 4,4 '-BPS, thereby 4 in the crystal, and the ratio of 4 '-BPS reaches more than 99% or 90%.
The solvent layer that sturated aliphatic hydrocarbon after the liquid separation constitutes is not owing to containing resultant and impurity, so can easily utilize again.
In addition, the present invention also is a kind of 4, the manufacture method of 4 '-bisphenol sulphone, in containing the solvent of sturated aliphatic hydrocarbon, in being provided with the reaction vessel of rectifier unit, make phenol and sulfuric acid reaction make 4, the method for 4 '-bisphenol sulphone, also be a kind of after reaction, add the alcohol of carbon number 1-3 to this reaction solution, the alcohol layer recrystallize 4 after separating from separating liquid, 4 '-bisphenol sulphone.
According to this manufacture method, in phenol and sulfuric acid reaction, increase the quantity of distillate of water and the quantity of distillate of inhibition phenol, can improve the reaction efficiency of BPS.And, use the sturated aliphatic hydrocarbon solvent to obtain 4, behind 4 '-BPS,, utilize the liquid separation operation can obtain being dissolved with the alcoholic solution of resultant by adding alcohol immediately to this reaction solution, can be transferred to the recrystallize operation effectively.In addition, the sturated aliphatic hydrocarbon behind the pure extracting operation can easily reclaim again and utilize.
In the present invention, the sturated aliphatic hydrocarbon of use more than a kind or 2 kinds or 2 kinds is as reaction solvent.The boiling point of this sturated aliphatic hydrocarbon series solvent is preferably more than 155 ℃, and the occasion that only is made of sturated aliphatic hydrocarbon at solvent is more preferably in 155 ℃-175 ℃ scope.Here, be the occasion of mixed solvent at sturated aliphatic hydrocarbon, the recovered temperature of mixed solvent is more than 155 ℃ or 155 ℃ or 155-175 ℃ scope.
In phenol and vitriolic reaction, between 150 ℃ and 160 ℃, 2,4 '-isomer is to 4, and the conversion rate of 4 '-isomer is widely different, 4 of generation, 4 '-isomer is many.That is,, can improve 4, the yield of 4 '-isomer by under this temperature or this temperature more than temperature, reacting.From this situation, the boiling point of solvent is this temperature or this is more than temperature preferably.On the other hand, because the boiling point of phenol is 182 ℃, therefore when use has the solvent of this temperature or the above boiling point of this temperature, when reacting under this temperature or this condition more than temperature, for example in rectifier unit, solvent does not reflux, and phenol refluxes, and is inappropriate.
Solvent of the present invention is the solvent that contains the sturated aliphatic hydrocarbon more than a kind or 2 kinds or 2 kinds, it can be a kind of sturated aliphatic hydrocarbon, it also can be the mixed solvent of the sturated aliphatic hydrocarbon more than 2 kinds or 2 kinds, and, can also be on the sturated aliphatic hydrocarbon basis with aromatic hydrocarbons series solvent etc. outside the mixed solvent that forms of other solvents.
In the occasion of only using the solvent that constitutes by the sturated aliphatic hydrocarbon series solvent, the sturated aliphatic hydrocarbon series solvent for example can use nonane, decane, undecane, dodecane, ア イ ソ パ-(registered trademark of エ Network ソ Application chemistry (strain)) G, ア イ ソ パ-H, ア イ ソ パ-L, ア イ ソ パ-M or their mixture.Preferred a kind the solvent of having only that uses wherein.This ア イ ソ パ-solvent is a mixed solvent because as long as keep constant composition, from the viewpoint of utilizing again, can similarly handle with single solvent, therefore in this manual as the solvent treatment of single kind.
And the boiling point of this solvent is preferably more than 155 ℃ or 155 ℃, particularly in 155-175 ℃ scope.Solvent with this boiling point for example specifically has nonane, decane, Isop (ア イ ソ パ)-G etc.Wherein, preferred Isop (ア イ ソ パ)-G.When use has a kind of solvent of this boiling point, do not need to use entrainer, in addition because solvent is single composition, so favourable to utilizing again of solvent.
On the other hand, under the situation of the mixed solvent that uses sturated aliphatic hydrocarbon and aromatic hydrocarbons series solvent and solvent, the boiling point of preferred aliphat stable hydrocarbon is than these aromatic hydrocarbons series solvent height.In addition, owing to usually when the aromatic hydrocarbons series solvent remains in the reaction system, do not carry out rearrangement reaction, so preferably after the water of having confirmed theoretical amount is removed, heat up in a steamer the aromatic hydrocarbons series solvent that adds in reaction system as far as possible.This sturated aliphatic hydrocarbon series solvent for example has nonane, decane, undecane, dodecane, Isop (ア イ ソ パ)-G, Isop (ア イ ソ パ)-H, Isop (ア イ ソ パ)-L, Isop (ア イ ソ パ)-M; The aromatic hydrocarbons series solvent for example has mesitylene, chlorobenzene, dichlorobenzene, trichlorobenzene, toluene(mono)chloride, diethylbenzene, dimethylbenzene etc.
The alcohol that is used for carbon number 1-3 of the present invention for example has methyl alcohol, ethanol, propyl alcohol, Virahol, special particular methanol.This alcohol can be that pure product also can be the aqueous solution.
In this invention, 4, the formation reaction of 4 '-BPS is generally carried out in the following manner.
In reaction vessel, prepare sturated aliphatic hydrocarbon, to wherein adding phenol and sulfuric acid lentamente as reaction solvent.At this moment, both can side by side add phenol and sulfuric acid, also can after the necessary amounts of adding phenol, add sulfuric acid lentamente.Phenol and vitriolic mol ratio are 2～3: 1 scope, preferably roughly reach 2: 1.
The ratio of the reaction solvent in the reaction solution is 1～2 times of weight of sulfuric acid weight, especially preferably reaches roughly 1.5 times of sulfuric acid weight.
Be reflected at about 140 to the temperature of about 175 ℃ of scopes, carry out while under refluxad stir.
This reaction is a dehydration reaction, and its dewatering is so long as just can use any known method within the scope of the invention.In entire reaction, dewater constantly.Concrete easy method is that devices such as use デ ィ Application ス -Network separate the water behind the removal component distillation.
In the present invention, by be provided with rectifier unit in reaction vessel, can suppress as the distillating of the phenol of raw material, and remove water effectively from reaction system, the result can produce 4,4 '-BPS effectively.The example of this rectifier unit for example has Wei Demen type rectifying column, Buiglur (ヴ ィ グ リ ュ)-type rectifying column, Snyder (ス ニ-ダ) type rectifying column, Hempel type rectifying column etc.
After dehydration reaction finishes, in order to promote rearrangement reaction, the temperature in the time of also can temporarily keeping dehydration reaction again.
After above reaction process is finished, make reaction solution be cooled to about about 80 ℃.In this stage 4,4 '-BPS and 2,2 in the mixture of 4 '-BPS, 4 '-BPS are below about 5% or 5%.
Next at random adds the alcohol of the 0.5-2 volume ratio doubly of reaction solvent, the preferred alcohol of roughly measuring together to the refrigerative reaction solution, at about about 65 ℃, makes resultant 4,4 '-BPS and 2, the mixture dissolving of 4 '-BPS with about about 1 hour.Reaction solvent of the present invention is owing to being separated into 2 layers with the intermiscibility of alcohol is little.Because resultant is dissolved in the alcohol layer,, can easily obtain the alcoholic solution of resultant by this operation.This alcoholic solution can be used for the recrystallize operation immediately.
The alcohol that uses is the occasion of pure product, also can add entry again.Consider extraction efficiency in addition, adopt pure water to carry out liquid separation, about the preferred 30-70 weight of the determining alcohol % in the pure water in this stage.
In order to remove impurity and to adjust pH, also can add gac and caustic soda etc. to the alcohol layer.
Add water treatment etc. as required again in the alcohol layer after liquid separation, near the cool to room temperature, make BPS recrystallize drying, can obtain 4,4 '-BPS.
Determining alcohol in the pure water when carrying out recrystallize is 10-50 weight %, 20-40% preferably, can add alcohol and water so that finally form the pure water of this concentration.2,4 '-BPS more is soluble in alcohol than 4,4 '-BPS, thereby 4 in the crystal, and the ratio of 4 '-BPS reaches more than 99% or 99%.
The solvent layer that sturated aliphatic hydrocarbon after the liquid separation constitutes is not owing to comprising resultant and impurity, so utilize easily again.
Under situation about making with technical scale, separate separately in the operation of object at the refining reaction mixture, make the liquid color of reaction mixture sometimes, it enters into crystal, thereafter, also is difficult to decolour fully even make with extra care repeatedly.
Under such situation, be in the liquid of reaction mixture, to add the operation of decolouring such as gac in the past, added process of active carbon but use, though can decolour to a certain degree, decolouring is difficult fully, in addition, must filter the gac that adds, operate miscellaneous.Probe in manufacture method the operation of refining reaction mixture in the painted reason of reaction mixture, the result thinks, in the operation of refining reaction mixture, metal ions such as the iron ion that from the reactive tank of SUS system, dissolves or in being used as the process water of solvent, comprise, nickel ion, chromium ion, with the oxybenzene compound formation coordination compound that reacts, this is to cause painted material.And also find to separate separately in the operation of object,, catch metal ion, can prevent painted effectively with sequestrant by adding sequestrant to reaction mixture at the refining reaction mixture.
The sequestrant that uses, so long as the compound that generates inner complex with the metal ion bonding just can, be not particularly limited.
Relevant sequestrant for example can be to make ammonia, polyamines, amino acid etc. contain reaction such as amino compound and dithiocarbonic anhydride, halogenated carboxylic acid, halohydrin and the compound that obtains; And their salt; Dithiocar-bamate; Dimethyl glyoxime; Dithizone; Bipyridine; Phenanthroline etc.
Aforementioned polyamines for example has quadrol, N-methyl ethylenediamine, N, N '-dimethyl-ethylenediamine, 1,1,3-diaminopropanes, diethylenetriamine, Triethylenetetramine (TETA), tetramethylene pentamine, pentamethylene hexamine or the like.
Halogenated carboxylic acid for example has monochloroacetic acid, monobromo acetic acid, monoiodo-acetic acid, 1-chloropropionic acid, 2-chloropropionic acid, 1-bromo-propionic acid, 2 bromopropionic acid etc.
In addition, halohydrin for example has 1-chloroethanol, ethylene chlorhydrin, 1-bromoethanol, ethylene bromohyrin, 1-propylene chlorohydrin, 2-propylene chlorohydrin, 2-chloro isopropanol, 3-propylene chlorohydrin, 1-bromopropyl alcohol, 2-bromopropyl alcohol, 2-bromine Virahol, 3-bromopropyl alcohol etc.
The concrete example of sequestrant for example has dithiocar-bamate such as nabam, dithiocarbamic acid potassium; The acetogenin of ethylenediamine tetraacetic acid (EDTA) (EDTA), hydroxyethyl iminodiethanoic acid (HIDA), nitrilotriacetic acid(NTA) (NTA), Oxyethylethylenediaminetriacetic acid (HEDTA), diethylene triaminepentaacetic acid(DTPA) (DTHA), triethylenetetraaminehexaacetic acid amines such as (TTHA) and the salt of these acetogenins (an alkali metal salt of sodium, potassium etc. for example; The alkali earth metal salt of calcium, magnesium etc.; Ammonium salt etc.); Thanomin, N, N '-two (2-hydroxyethyl) quadrol, N, N ', N "-three (2-hydroxyethyl) quadrol, dihydroxyethylglycin ethanolamines such as (DHEG); N, N '-two (dithiocarboxy) quadrol sodium salt, N, N '-two (dithiocarboxy) quadrol sylvite, N, N '-two (dithiocarboxy) trimethylene diamines sodium salt, N, N '-two (dithiocarboxy) trimethylene diamines sylvite, N, N '-two (dithiocarboxy) diethylenetriamine sodium salt, N, N '-two (dithiocarboxy) diethylenetriamine sylvite, N, N '; N "-three (dithiocarboxy) diethylenetriamine sodium salt, N, N '; N "-three (dithiocarboxy) diethylenetriamine sylvite, N, N '-two (dithiocarboxy) Triethylenetetramine (TETA) sodium salt, N, N '-two (dithiocarboxy) Triethylenetetramine (TETA) sylvite, N, N ', N "-three (dithiocarboxy) Triethylenetetramine (TETA) sodium salt; N; N ', N " salt of dithiocarbamic acid derivative of polyamines such as-three (dithiocarboxy) Triethylenetetramine (TETA) sylvite; Dimethyl glyoxime, dithizone, bipyridine, phenanthroline or the like.
Among these sequestrants, preferably make the reaction of halogenated carboxylic acid and/or halohydrin and ammonia or polyamines and the sequestrant that obtains; And the sequestrant (water-soluble chelator) of the formation water soluble chelate compound of their salt etc., be easy to get calmly, viewpoint such as operability sets out and especially preferably use EDTA or its salt.
The salt of EDTA for example has EDTA disodium salt, EDTA trisodium salt, EDTA tetra-na salt, EDTA di-potassium, EDTA tripotassium salt, EDTA four sylvite, EDTA calcium salt, EDTA tripotassium salt, EDTA di-ammonium salts, EDTA magnesium two calcium salts or the like.Adding under the situation of water-soluble chelator in reaction mixture, the inner complex of generation is water-soluble, can not enter into 4, in the crystal of 4 '-bisphenol sulphone, can access the object of decolouring fully.
Add the time of sequestrant, can add sequestrant in 1. following～4. any 1 time: wherein 1. heat up in a steamer from reaction mixture anhydrate and phenol after, add before the alcohol and water or with it simultaneously; 2. add after the alcohol and water, separate and get before the alcohol water layer; 3. separate and get after the alcohol water layer, before the alcohol water layer adds alkali adjustment pH; After perhaps 4. pH adjusts; But preferably 4. adjust the back and add sequestrant at pH.
The method of adding sequestrant for example has the method for adding sequestrant with solid state in reaction mixture; Make sequestrant be dissolved in the water equal solvent, add the method for solution etc. to reaction mixture.
The addition of sequestrant can suitably be determined according to the concentration of metal ions such as the iron ion that is contained in the reaction mixture, nickel ion, chromium ion.When the addition of sequestrant is very few, prevent that by what the interpolation sequestrant brought coloring effect is insufficient.On the other hand, when the addition of sequestrant is too much, prevent coloring effect fully though can access, it is final 4 to worry that also superfluous sequestrant is blended into as impurity, in 4 '-bisphenol sulphone.Thereby preferably before adding sequestrant,, afterwards, add the sequestrant of the resultant that conforms to concentration of metal ions with contained concentration of metal ions in the known method assaying reaction mixture.The addition of sequestrant is generally the 0.0001-0.5 weight part with respect to reaction mixture 100 weight parts, the scope of preferred 0.001-0.1 weight part.
Description of drawings
Fig. 1 be expression from 2,4 '-isomer is to 4, the transformation of 4 '-isomer and the graph of a relation of temperature.
Fig. 2 is expression when using rectifying tower and when not using rectifying tower, from the figure of the quantity of distillate time to time change of the phenol of reaction solution and water.
Embodiment
Illustrate in greater detail the present invention by the following examples.
Phenol 98.7g (1.05 moles), ア イ ソ パ-H 75ml, mesitylene 50ml pack in the four-hole boiling flask of the 500ml that is provided with stirrer, thermometer, water sepn pipe, under agitation condition, in its mixture, drip 95% sulfuric acid 51.6g (0.50 mole) at 50 ℃, heat up afterwards.
Near distillating 148 ℃ of reaction solution, this overhead product are condensed in and are separated into 2 layers in the water sepn pipe, and the organic layer on upper strata turns back in the reaction system continuously.Begin to reach 170 ℃ through the temperature of about 4 hours reaction systems from intensification, the generation of water stops, and the isolating water yield is 20.5g in the water sepn pipe.Thereafter, add ア イ ソ パ-H50ml, the temperature of reaction system need reach 175 ℃ in 3 hours and heat up in a steamer mesitylene.Utilize high speed effect liquid phase chromatogram method (HPLC) to analyze the composition of this reactant, the result with relative area than (measure wavelength: 231nm) be expressed as: 4,4 '-BPS 94.7%, 2,4 '-BPS 2.8%, sulfocarbolic acid 1.2%.
Comparative example 1
In the four-hole boiling flask of the 500ml that is provided with stirrer, thermometer, water sepn pipe, pack into phenol 98.7g (1.05 moles), ア イ ソ パ-G 100ml, under agitation condition, 50 ℃ after its mixture drips 95% sulfuric acid 51.6g (0.50 mole), heat up.Near distillating 144 ℃ of reaction solution, this overhead product is condensed, and is separated into 3 layers in the water sepn pipe, and the upper strata is that solvent layer, middle layer are that water layer, bottom are the phenol layer.The upper strata solvent layer turns back in the reaction system continuously, and bottom phenol layer extracted and turned back in the reaction system every 15 minutes.Reach 167 ℃ from the beginning that heats up through the temperature of about 7 hours reaction systems, the generation of water stops, and is 21.2g in the isolating water yield of water sepn pipe, and the phenol that turns back in the reaction system adds up to 68.0g.Analyze the composition of this reactant with high performance liquid chromatography (HPLC), the result is with relatively and long-pending than (measure wavelength: 231nm) be expressed as: 4,4 '-BPS 94.0%, 2,4 '-BPS 3.1%, sulfocarbolic acid 1.6%.
Phenol 98.7g (1.05 moles), ア イ ソ パ-G 100ml pack in the four-hole boiling flask of the 500ml that is provided with stirrer, thermometer, water sepn pipe, under agitation condition, behind the dropping 95% sulfuric acid 51.6g (0.50 mole), heat up in its mixture at 50 ℃.
Near distillating 144 ℃ of reaction solution, this overhead product is condensed, and is separated into 3 layers at the water sepn pipe, and the upper strata is that solvent layer, middle layer are that water layer, bottom are the phenol layer.The solvent layer on upper strata is turned back in the reaction system continuously, and the phenol layer of bottom extracted and turned back in the reaction system every 15 minutes.Reach 167 ℃ from the beginning that heats up through the temperature of about 7 hours reaction systems, the generation of water stops, and the isolating water yield is 21.2g in the water sepn pipe.The phenol that turns back in the reaction system adds up to 68.0g.Analyze the composition of this reactant with high performance liquid chromatography (HPLC), the result with relative area than (measure wavelength: 231nm) be expressed as: 4,4 '-BPS 94.0%, 2,4 '-BPS 3.1%, sulfocarbolic acid 1.6%.
Add methyl alcohol 132ml and water 103ml in this reactant, heating for dissolving is separated solvent layer (ア イ ソ パ-G) by liquid separation.Dissolve with methanol liquid adds the 10% caustic soda aqueous solution, makes it to be pH=5, after gac 2.6g decolouring, adds water 103ml, and crystal is separated out, and obtains 100.1g (recovery rate: white crystal 80.1%).
Analyze this crystalline with high performance liquid chromatography (HPLC) and form, the result with relative area than (measure wavelength: 231nm) be expressed as: 4,4 '-BPS 99.7%, 2,4 '-BPS 0.3%.
Phenol 117.5g (1.25 moles), ア イ ソ パ-G 100ml pack in the four-hole boiling flask of the 500ml that is provided with stirrer, thermometer, water sepn pipe, Wei Demen type rectifying column, under agitation condition, behind the dropping 95% sulfuric acid 51.6g (0.50 mole), heat up in its mixture at 50 ℃.
Near distillating 144 ℃ of reaction solution, this overhead product is condensed, and is separated into 3 layers in the water sepn pipe, and the upper strata is that solvent layer, middle layer are that water layer, bottom are the phenol layer.The upper strata solvent layer is turned back in the reaction system continuously, and bottom phenol layer does not turn back in the reaction system and reacts.Reach 167 ℃ from the beginning that heats up through the temperature of about 10 hours reaction systems, the generation of water stops, and the isolating water yield is 20.5g in the water sepn pipe, and the phenol amount is 21.2g.Analyze the composition of this reactant with high performance liquid chromatography (HPLC), the result with relative area than (measure wavelength: 231nm) be expressed as: 4,4 '-BPS 95.5%, 2,4 '-BPS 3.0%, sulfocarbolic acid 0.7%.
Handle this reactant similarly to Example 2, obtain 103.2g (yield: white crystal 82.5%).Analyze this crystalline with high performance liquid chromatography (HPLC) and form, the result is with amassing than (measure wavelength: 231nm) be expressed as: 4,4 '-BPS 99.6%, 2, and 4 '-BPS 0.4% relatively.
Pack in the four-hole boiling flask of the 300ml that is provided with stirrer, thermometer, water sepn pipe, Wei Demen type rectifying column phenol 42g, ア イ ソ パ-G 42ml heat up drip 95% sulfuric acid 22g in this mixture after at 50 ℃ under agitation condition.
Near distillating 144 ℃ of reaction solution, this overhead product is condensed, and is separated into 3 layers in the water sepn pipe, and the upper strata is that solvent layer, middle layer are that water layer, bottom are the phenol layer.The upper strata solvent layer is turned back in the reaction system continuously, and bottom phenol layer extracted and turned back in the reaction system every 15 minutes.Reach 167 ℃ from the beginning that heats up through the temperature of about 6 hours reaction systems, the generation of water stops.The scale of distilled water and phenol in this reaction is shown among Fig. 2.The phenol accumulative total that distillates before reaction stops and turning back in the reaction system is 2.2ml, and the water of removing from reaction system is 9.1ml.Analyze the composition of this reactant with high performance liquid chromatography (HPLC), the result with relative area than (measure wavelength: 231nm) be expressed as: 4,4 '-BPS 90.8%, 2,4 '-BPS 3.4%, sulfocarbolic acid 1.3%, trimer 2.1%.
Add methyl alcohol 56ml and water 44ml to this reactant, heating for dissolving is separated solvent layer (ア イ ソ パ-G) by liquid separation.Dissolve with methanol liquid adds the 10% caustic soda aqueous solution, makes it to be pH=5, after gac 1.1g decolouring, adds water 60ml, and crystal is separated out, and obtains the white crystal (yield: 86.8%) of 46.2g.
Analyze this crystalline with high performance liquid chromatography (HPLC) and form, the result with relative area than (measure wavelength: 231nm) be expressed as: 4,4 '-BPS 99.5%, 2,4 '-BPS 0.4%.
Comparative example 2
4 mouthfuls of flasks are not except that being provided with Wei Demen type rectifying column, and other and embodiment 4 carry out same operation, and the scale of distilled water and phenol is shown among Fig. 2 in the building-up reactions of BPS.The phenol accumulative total that distillates before reaction stops and turning back in the reaction system is 30ml, and the water of removing from reaction system is 9.0ml.In this reactant, add the first alcohol and water, carry out processing similarly to Example 4, obtain the white crystal (yield: 77.4%) of 41.2g.Analyze this crystalline with high performance liquid chromatography (HPLC) and form, the result with relative area than (measure wavelength: 231nm) be expressed as: 4,4 '-BPS 99.5%, 2,4 '-BPS 0.4%.
Reference example
The ア イ ソ パ-G 70ml solution of phenol 131.6g (1.4 moles) of in the four-hole boiling flask of the 500ml that is provided with stirrer, thermometer, water sepn pipe, packing into, Yi Bian stir this solution, Yi Bian drip 95% sulfuric acid 72.2g (0.7 mole) at 50 ℃.After dripping end, on one side stirred reaction mixture, temperature reaction system lentamente on one side.Near distillating 144 ℃ of reaction solution, the condensation in the water sepn pipe of this cut is separated into 3 layers, and the upper strata is that solvent layer, middle layer are that water layer, bottom are the phenol layer.The upper strata solvent layer turns back in the reaction solution continuously, and bottom phenol layer extracted and turned back in the reaction system every 15 minutes.Reach 165 ℃ from the beginning that heats up through the temperature of about 7 hours reaction systems, distillating of water stops, and water and unreacted phenol almost entirely distillate from reaction solution.
Then, reaction mixture is cooled to 80 ℃ after, add methyl alcohol 185ml again, stirred 1 hour at 65 ℃.Add entry 144ml to this solution, carry out liquid separation, separate and take out the alcohol water layer.
Then, add 10% aqueous sodium hydroxide solution, after adjustment becomes pH=5, drip 5% aqueous solution 1ml of EDTA disodium salt.After stirring this alcohol water layer fully, be cooled to 30 ℃, make it crystallization.Crystal is separated out in leaching, and drying obtains object 4 thus, 4 '-dihydroxy-diphenyl sulfone powder 140.2g.Yield: 80%.
Obtain 4, the purity of 4 '-dihydroxy-diphenyl sulfone is more than 99.5%.In addition, (Japanese electric look industry (strain) system, pattern: 1001DP) measure this material, drawing the b value is below 2.5, does not see painted with colour-difference meter.
Industrial applicibility
As mentioned above, method for making of the present invention is characterised in that, uses mixed solvent, and this mixed solvent is 175 by boiling point ℃ or the dissolving benzene of the sturated aliphatic hydrocarbon more than a kind or 2 kinds or 2 kinds more than 175 ℃ and mesitylene etc. Phenol and boiling point be the solvent composition below 170 ℃ or 170 ℃, and the low boiling point solvents such as mesitylene have entrainer Function, and this solvent is forming 2 layers owing to dissolve the layer that distillates when phenol dewaters, so in the dehydration To water electrode effectively remove easily, thereby its reflux operation will be easy. After dehydration finishes, owing to heat up in a steamer Remove the low boiling point solvents such as mesitylene, in the sturated aliphatic hydrocarbon solvent, accelerate rearrangement reaction, can improve thus 4, the yield of 4 '-BPS. By using a kind of mixed solvent, can easily realize at one stroke above-mentioned a lot in the present invention Advantage.
In addition, can not need to heat up in a steamer desolventizing from reaction system, with high yield the pulpous state of processing easy to manufacture 4,4 '-BPS. Therefore sturated aliphatic hydrocarbon solvent of the present invention can utilize methyl alcohol from reaction owing to immiscible with methyl alcohol Liquid extracts product effectively, then can effectively go in the recrystallization operation that methanol-water carries out. And, liquid Solvent layer after the separation can recycle. In addition, when a kind of solvent of the boiling point that uses particular range of the present invention, Do not need to use entrainer, can easily carry out the recycling of solvent yet.
In addition, in the occasion of using rectifying column, the quantity of distillate of phenol reduces significantly, the water energy that side reaction generates Enough effectively removals also can improve reaction efficiency.
Claims (1)
1, a kind of 4, the manufacture method of 4 '-bisphenol sulphone wherein, makes phenol and sulfuric acid react in containing the solvent of sturated aliphatic hydrocarbon, adds the alcohol of carbon number 1-3 afterwards in this reaction solution, recrystallize 4 the alcohol layer after liquid separation, 4 '-bisphenol sulphone.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4996367A (en) * | 1989-12-20 | 1991-02-26 | Amoco Corporation | Process for making 4,4'-dihydroxydiphenyl sulfone |
| WO1992002493A1 (en) * | 1990-08-06 | 1992-02-20 | Aristech Chemical Corporation | Preparation of relatively pure p, p-bisphenol s |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4996367A (en) * | 1989-12-20 | 1991-02-26 | Amoco Corporation | Process for making 4,4'-dihydroxydiphenyl sulfone |
| WO1992002493A1 (en) * | 1990-08-06 | 1992-02-20 | Aristech Chemical Corporation | Preparation of relatively pure p, p-bisphenol s |
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