CN101696179A - Method for synthesizing and refining 2,4'-dihydroxy diphenyl sulfone - Google Patents
Method for synthesizing and refining 2,4'-dihydroxy diphenyl sulfone Download PDFInfo
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- CN101696179A CN101696179A CN200910188206A CN200910188206A CN101696179A CN 101696179 A CN101696179 A CN 101696179A CN 200910188206 A CN200910188206 A CN 200910188206A CN 200910188206 A CN200910188206 A CN 200910188206A CN 101696179 A CN101696179 A CN 101696179A
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Abstract
The invention belongs to the field of synthesizing new chemical products, and relates to a method for synthesizing a fine chemical product, in particular to a method for synthesizing and refining 2,4'-dihydroxy diphenyl sulfone. The method is characterized by comprising the following steps: using phenol and sulfuric acid as raw materials; stirring, refluxing, filtering, crystallizing and drying the raw materials in an aromatic solvent in the presence of an acid catalyst to obtain a crude product containing an isomeride of the 2,4'-dihydroxy diphenyl sulfone and 4,4'-dihydroxy diphenyl sulfone; and refining the crude product by a mixed solvent method to obtain a refined sample of which the maximum content of the 2,4'-dihydroxy diphenyl sulfone can reach 98 percent. The method has the advantages of solving the problems of high manufacturing cost, serious pollution, low product purity and the like in the commonly used reduced pressure method and solvent method.
Description
Technical field
The present invention relates to a kind of 2, the synthetic and process for purification of 4 '-dihydroxy diphenylsulphone.Particularly, involved in the present invention a kind of 2, the method for synthesizing and refining of 4 '-dihydroxy diphenylsulphone is for containing 2 with the solvent method preparation, 4 '-dihydroxy diphenylsulphone and 4, the mixture of 4 '-dihydroxy diphenylsulphone, and from then on isolate in the mixture content reach 2,4 more than 92% '-dihydroxy diphenylsulphone.
Background technology
2,4 '-dihydroxy diphenylsulphone (be called for short 2,4 '-BPS) be white crystal, 187～188 ℃ of fusing points.Its purposes is very extensive, can substitute dihydroxyphenyl propane and prepare plastics such as polyester, polycarbonate and Resins, epoxy, also can be as lubricant, the sterilization antiseptic-germicide of the material of mixing, metal processing.In addition, also be used for the developer of electrothermal sensitive recording paper in a large number, its color developing than traditional developer 4,4 '-dihydroxy diphenylsulphone (be called for short 4,4 '-BPS) good, therefore in recent years on the market to 2,4 '-demand of BPS rapidly increases.
2,4 '-BPS normally obtains by phenol and vitriolic dehydrating condensation in the presence of certain catalyzer.Reaction can be carried out in reduced pressure atmosphere or ebullient solvent, and these two kinds of different condition synthetic methods are called decompression method and solvent method respectively.Though the decompression method can reduce temperature of reaction, need not introduce extra organic solvent, reduced the discharging of the three wastes and follow-up separating step; Keep system and under low pressure environment, operate but will consume lot of energy in process of production, also will consider the good recovery of phenol.Therefore the cost of product high (Ji Yehao etc., preparation 2,4 '-method of dihydroxy diphenylsulphone, CN1620428A.).According to the literature, the current Synthetic 2 that is used for, 4 '-the reasonable solvent of BPS effect is 1 (being sym-trimethylbenzene), it removes the moisture of by-product in the product as entrainer in reaction process, improves the transformation efficiency of reactant and the yield of product; But the expensive of sym-trimethylbenzene is not suitable for suitability for industrialized production (Qiu Mingyan etc., the progress of dihydroxy diphenylsulphone, dyestuff and dyeing, 2005,42 (5): 35-37.).Therefore need find other suitable solvent.
Obtaining in the reaction process of dihydroxy diphenylsulphone with phenol and sulfuric acid dehydrating condensation, owing to thermodynamic (al) reason, can obtain 2,4 in the product simultaneously '-BPS and 4,4 '-two kinds of isomerss of BPS.4,4 '-BPS also is a kind of important chemical product, the thermotolerance monomer that can be used to prepare the raw material of polyethersulfone and improve polycarbonate.Therefore, must find suitable separation method that they are separated effectively so that obtain can commercialization and the product of industrial applications.It is reported, can be used for separating 2,4 '-BPS and 4,4 '-method of BPS mainly contains alkali fusion and mixed solvent method (Masaske H., et al., Process for producing a high purity2,4 '-dihydroxydiphenylsufone, EP 0755920B1; Ogata E., et al., Purification of2,4 '-dihydroxyphenylsulfone, JP 10139756.).These two kinds of methods respectively have advantage separately, and alkali fusion is not because not with an organic solvent, so environmental pollution is little, cost is low, is reasonable method; Mixed solvent method does not produce a large amount of waste water in treating process, be expected to repeatedly recycle solvent, is reasonable method therefore yet.But, the mixed solvent method of reported in literature mainly be used for from 2,4 '-isolate 4,4 in the mixture of BPS and 4,4 '-BPS '-BPS, and at 2,4 '-BPS is that target carries out isolatingly directly not being described in detail.Await further research.
Summary of the invention
The objective of the invention is to adopt aromatic solvent method Synthetic 2,4 '-BPS, adopt mixed solvent method that product is separated purification, obtain purity be higher than 92% 2,4 '-BPS.
The present invention realizes above-mentioned purpose by the following method: with phenol and sulfuric acid, carry out dehydration reaction in the presence of the acid catalyst in aromatic solvent.After steps such as distilling off solvent, thin up, neutralization and filtration, contained 2,4 simultaneously '-filter cake of BPS and 4,4 '-BPS mixture, i.e. crude product.Crude product again through obtain 2,4 after the steps such as mixed solvent dissolving, recrystallization, filtration '-the higher highly finished product of BPS content.
The object of the present invention is achieved like this:
(1) be that 2.1: 1～2.6: 1 phenol and sulfuric acid mix with mol ratio, in aromatic solvent, acid catalyst carries out reflux dewatering reaction 2～7 hours under 130～180 ℃, obtains suspension.After the process normal pressure steams solvent, be cooled to 100～150 ℃, thin up, the water yield is 1～3 times of solvent for use amount, stir, being neutralized to pH value with alkali (as NaOH or KOH) is 4～6, is cooled to room temperature after-filtration, drying, obtain containing 2,4 '-the crude product powder of BPS and 4,4 '-BPS mixture.Wherein 2,4 '-content of BPS is 30～45wt%.
(2) with the dissolving crude product that obtains described in the technique scheme (1) in mixed solvent, 80～95 ℃ of following stirring and refluxing 0.5～3 hour drop to 30～40 ℃ and be incubated 5～45 minutes after-filtration.Filtrate is added the dilution of deionized water or tap water, fully stir, cool to 10～20 ℃ and separate out a large amount of white solids, filter, drying, promptly mainly contained 2,4 '-white or the lightpink pressed powder of BPS.Wherein 2,4 '-content of BPS is 80～95wt%.
(3) get an one-step refining sample that obtains described in the technique scheme (2), be dissolved in the mixed solvent, 80～95 ℃ of following stirring and refluxing 0.5～3 hour drop to 30～40 ℃ and be incubated 5～45 minutes after-filtration.Filtrate is added the dilution of deionized water or tap water, fully stirs, cool to 10～20 ℃ and separate out a large amount of white solids, filter, drying, get final product content better contain 2,4 '-white or the lightpink pressed powder of BPS.Wherein 2,4 '-content of BPS is 92～99wt%.
The invention has the beneficial effects as follows:
(1) propose with aromatic series kind solvent Synthetic 2, the method for 4 '-dihydroxy diphenylsulphone, the aromatic series kind solvent of employing has 1,3, the 5-trimethylbenzene, 1,2, the 4-trimethylbenzene, 1,2-orthodichlorobenzene, benzene, dimethylbenzene, chlorobenzene etc., particularly 1,2,4-trimethylbenzene, 1, the 2-orthodichlorobenzene has lower price, has reduced by 2, the production cost of 4 '-dihydroxy diphenylsulphone.
(2) proposed the employing mixed solvent prepare high-content 2,4 '-process for purification of BPS.By mixed solvent, as methyl alcohol-orthodichlorobenzene or ethanol-orthodichlorobenzene or acetone-orthodichlorobenzene, can make 2,4 '-BPS and 4,2 in 4 '-BPS crude mixture, 4 '-BPS content is from the disposable 80～95wt% that brings up to of 30～45wt%.By twice continuous solvent method that adopts, can be with 2,4 '-BPS and 4,2 in 4 '-BPS crude mixture, 4 '-BPS content reaches 92～99wt%.
(3) adopt mixed solvent method to 2,4 '-BPS and 4,2 in 4 '-BPS crude mixture, 4 '-BPS purifies.Show that through test of many times mixed solvent can be repeatedly used, after applying mechanically through 5 times, find solvent to 2, the purity of 4 '-BPS and yield be obviously influence not, thereby has significantly reduced the cost of product purification process and the quantity discharged of the three wastes.
Embodiment
Be described in detail most preferred embodiment of the present invention below in conjunction with technical scheme.
Embodiment 1
The phenol and the sulfuric acid mixing adding that will have mol ratio have in the four-hole bottle of water trap, put into aromatic solvent and acid catalyst again, and dehydration reaction is carried out in heating, and reflux water-dividing obtained suspension after 2～7 hours.After normal pressure steams solvent, be cooled to 100～150 ℃, add deionized water or tap water (be solvent load 1～3 times).Stir on one side, with NaOH neutralization solution to pH value be 4～6 on one side.Solution is cooled to room temperature after-filtration, drying, obtains containing 2,4 '-BPS and 4, the crude product powder of 4 '-BPS mixture.The index of concrete reaction conditions and product the results are shown in Table 1.
Table 1 reaction conditions is in the product 2, the influence of 4 '-BPS
| Sequence number | Phenol/sulfuric acid consumption (g) | Solvent species/consumption (ml) | Catalyst type/consumption (g) | Temperature of reaction (℃)/time (h) | Product yield/2,4 '-BPS content (wt%) |
| ??1 | ??71.8/36 | 1,2,4-trimethylbenzene/78.7 | Phosphorous acid/4 | ??130/2 | ??80/45 |
| ??2 | ??71.8/33 | 1,2,4-trimethylbenzene/108.2 | Hypophosporous Acid, 50/5 | ??180/7 | ??85/36 |
| ??3 | ??71.8/29.2 | 1,3,5-trimethylbenzene/79.8 | Phosphoric acid/6 | ??165/5 | ??87/40 |
| ??4 | ??71.8/31 | 1,2-orthodichlorobenzene/84.7 | Phosphorous acid/6 | ??155/5 | ??89/39 |
| ??5 | ??71.8/36 | 1,2,4-trimethylbenzene/78.7 | A type zeolite molecular sieve | ??160/3 | ??88/43 |
| ??6 | ??71.8/36 | 1,2,4-trimethylbenzene/78.7 | The ZSM-5 zeolite molecular sieve | ??160/3 | ??90/44 |
Embodiment 2
The crude product or the one-step refining sample that obtain among the embodiment 1 are put into four-hole bottle, add mixed solvent (as methyl alcohol-orthodichlorobenzene or ethanol-orthodichlorobenzene or acetone-orthodichlorobenzene).80～95 ℃ of following stirring and refluxing 0.5～3 hour, cool to 30～40 ℃ and be incubated 5～60 minutes after-filtration.The filtrate that obtains is added deionized water or tap water dilution, fully stir, cool to 10～20 ℃ and separate out a large amount of white solids, filtration, drying promptly get and mainly contain 2, the white of 4 '-BPS or lightpink pressed powder.The index of concrete reaction conditions and product the results are shown in Table 2.
Table 2 purification condition is in the product 2, the influence of 4 '-BPS
| Sequence number | Crude product consumption (g)/2,4 '-BPS content (wt%) | Mixed solvent kind/concentration (wt%)/consumption (g) | Reflux temperature (℃)/time (h) | Soaking time (min) | 2,4 '-BPS yield (%)/content (wt%) |
| ??1 | ??50/33.9 | Methyl alcohol-orthodichlorobenzene/2/450 | ??95/1 | ?30 | ??21.3/84.5 |
| Sequence number | Crude product consumption (g)/2,4 '-BPS content (wt%) | Mixed solvent kind/concentration (wt%)/consumption (g) | Reflux temperature (℃)/time (h) | Soaking time (min) | 2,4 '-BPS yield (%)/content (wt%) |
| ??2 | ??30/36.4 | Methyl alcohol-orthodichlorobenzene/2/175 | ??85/2 | ?45 | ??24.7/83.2 |
| ??3 | ??30/36.3 | Methyl alcohol-orthodichlorobenzene/1/283.2 | ??90/0.5 | ?5 | ??24.4/91.3 |
| ??4 | ??30/34.5 | Ethanol-orthodichlorobenzene/1/265.6 | ??95/1 | ?30 | ??22.2/88.4 |
| ??5 | ??30/35.7 | Acetone-orthodichlorobenzene/1/280.8 | ??80/1.5 | ??20 | ??23.5/86.6 |
| ??6 | ??50/90 | Methyl alcohol-orthodichlorobenzene/0.5/1620 | ??95/3 | ??40 | ??88.1/99.0 |
Claims (5)
1. one kind 2, the method for synthesizing and refining of 4 '-dihydroxy diphenylsulphone, be with solvent method preparation 2,4 '-dihydroxy diphenylsulphone (2,4 '-BPS) and isomers 4,4 '-dihydroxy diphenylsulphone (4,4 '-BPS) mixture, and from then on isolate 2,4 in the mixture '-dihydroxy diphenylsulphone, it is characterized in that:
(1) phenol and sulfuric acid are mixed, in aromatic solvent, phosphoric acid class material is as catalyzer, under 130 ℃-180 ℃, reflux, dehydration reaction 2-7 hour, obtain suspension, after the process normal pressure steams solvent, be cooled to 100～150 ℃, add water and stir, being neutralized to pH value with alkali is 4～6, is cooled to the room temperature after-filtration, drying, obtain containing 2,4 '-the crude product powder of BPS and 4,4 '-BPS mixture, wherein 2,4 '-content of BPS is 30～45wt%;
(2) will contain 2,4 '-BPS is that the dissolving crude product of 30～45wt% is in mixed solvent, after 80～95 ℃ of stirring and refluxing, cool to 30～40 ℃ and be incubated 5～45 minutes after-filtration, the filtrate that obtains is added deionized water or tap water dilution, fully stir, cool to 10～20 ℃ and separate out a large amount of white solids, filter, after the drying, mainly contained 2,4 '-white of BPS or an one-step refining pressed powder of lightpink, wherein 2,4 '-content of BPS is 80～95wt%;
(3) get contain 2,4 '-BPS is the exquisite sample of 80～95wt%, be dissolved in the mixed solvent, 80～95 ℃ following stirring and refluxing 0.5-3 hour, cool to 30～40 ℃ and be incubated 5～45 minutes after-filtration, the filtrate that obtains is added deionized water or tap water dilution, fully stir, cool to 10～20 ℃ and separate out a large amount of white solids, filter, drying, get final product 2, white that 4 '-BPS content is higher or lightpink are made with extra care pressed powder, wherein 2,4 '-content of BPS is 92～99wt%.
2. described a kind of 2 according to claim 1, the method for synthesizing and refining of 4 '-dihydroxy diphenylsulphone is characterized in that phenol and vitriolic mol ratio are 2.1: 1 or 2.2: 1 or 2.3: 1 or 2.4: 1 or 2.5: 1 or 2.6: 1 in the reactant feed; Used aromatic solvent is 1,3, and 5-trimethylbenzene or 1,2,4-trimethylbenzene or 1,2-orthodichlorobenzene, consumption are 4 times or 5 times or 6 times of the used volume of sulfuric acid; Catalyzer is phosphoric acid or phosphorous acid or Hypophosporous Acid, 50; The reflux dewatering temperature of reaction is 130 ℃ or 140 ℃ or 150 ℃ or 160 ℃ or 170 ℃ or 180 ℃, and the reaction times is 2h or 3h or 4h or 5h or 6h or 7h; The reaction back amount of water that finishes is 1 times or 2 times or 3 times of solvent volume; Used alkali is NaOH or KOH, and the pH value after the neutralization is 4 or 5 or 6.
3. according to claim 1 described a kind of 2, the method for synthesizing and refining of 4 '-dihydroxy diphenylsulphone, it is characterized in that used mixed solvent is methyl alcohol-orthodichlorobenzene or ethanol-orthodichlorobenzene or acetone-orthodichlorobenzene in the refining sample process, the concentration of methyl alcohol or ethanol or acetone is 0.5% or 1% or 2% in the mixed solvent.
4. described a kind of 2 according to claim 1, the synthetic and process for purification of 4 '-dihydroxy diphenylsulphone is characterized in that the stirring and refluxing temperature is 80 ℃ or 85 ℃ or 90 ℃ or 95 ℃ in the refining sample process, and the time is 0.5h or 1h or 1.5h or 2h or 2.5h or 3h; Lower the temperature afterwards and be incubated, soaking time is 5 minutes or 10 minutes or 15 minutes or 20 minutes or 25 minutes or 30 minutes or 35 minutes or 40 minutes or 45 minutes.
5. according to claim 1 described a kind of 2, synthetic and the process for purification of 4 '-dihydroxy diphenylsulphone, it is characterized in that crude product in the mixed solvent method treating process through stirring and refluxing, insulation, filter, add water, crystallization, refilter with the exsiccant step after, obtain containing 2 behind one one-step refining, 4 '-concentration of BPS is 80～95wt%, through obtain containing 2,4 after for the second time refining '-concentration of BPS is white or the lightpink powder of 92～99wt%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104693081A (en) * | 2015-02-10 | 2015-06-10 | 科迈化工股份有限公司 | Method for refining bisphenol S by using mixed solvent |
| CN106986798A (en) * | 2017-03-30 | 2017-07-28 | 南通沃兰化工有限公司 | One kind synthesis 2, the technique of 4 '-dihydroxydiphenylsulisomer |
| CN110330448A (en) * | 2019-06-19 | 2019-10-15 | 江阴长盛化工有限公司 | A kind of heat-sensitive paper bisphenol S production system |
-
2009
- 2009-10-27 CN CN200910188206A patent/CN101696179A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104693081A (en) * | 2015-02-10 | 2015-06-10 | 科迈化工股份有限公司 | Method for refining bisphenol S by using mixed solvent |
| CN106986798A (en) * | 2017-03-30 | 2017-07-28 | 南通沃兰化工有限公司 | One kind synthesis 2, the technique of 4 '-dihydroxydiphenylsulisomer |
| CN110330448A (en) * | 2019-06-19 | 2019-10-15 | 江阴长盛化工有限公司 | A kind of heat-sensitive paper bisphenol S production system |
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Application publication date: 20100421 |