CN105254544A - Preparing method for bisphenol S - Google Patents
Preparing method for bisphenol S Download PDFInfo
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- CN105254544A CN105254544A CN201510773834.0A CN201510773834A CN105254544A CN 105254544 A CN105254544 A CN 105254544A CN 201510773834 A CN201510773834 A CN 201510773834A CN 105254544 A CN105254544 A CN 105254544A
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Abstract
The invention relates to a preparing method for bisphenol S. Phenol and mesitylene are thrown into a flask, stirring is started, temperature rises, the temperature is kept to be 100 DEG C, 98% concentrated sulfuric acid is dripped, after dripping is completed, the temperature rises, back-flowing is carried out for water division, the temperature is kept to be 165 DEG C, the reaction continues to be carried out for 5 h to obtain a crude product bisphenol S, and mesitylene is recovered; organic solvent and activated carbon are sequentially added into the crude product bisphenol S, the temperature is kept to be 65 DEG C, decolorizing is carried out for 1 h, then filtering is carried out with heat, filter liquor is transferred into the flask, the temperature falls slowly, after a crystal is dissolved out, cooling is carried out to the room temperature, finally, a solid is filtered out, a little amount of organic solvent is used for flushing the solid, and the solid is dried to obtain the bisphenol S. The preparing method has the advantages that the bisphenol S content is 99.5% or more, the 2,4 isomer content is smaller than 0.2%, the yield is 92% or more, industrial production is achieved completely, production cost is low, and product purity is high.
Description
Technical field
The invention belongs to organic synthesis field, particularly a kind of preparation method of bisphenol S.
Background technology
More current industrial bisphenol S synthesis adopts phenol, the vitriol oil to react in certain solvent and forms, reaction generates crude product generally between 92%-95%, do not reach derived product requirement, derived product laking agent serial application bisphenol S general requirement content is more than 95%, temperature-sensitive paper series bisphenol S general requirement content is more than 99%, polysulfones ether, polyester and epoxy resin series bisphenol S general requirement content are more than 99.5%, and even requirements at the higher level are more than 99.8%.
Therefore, when preparing polysulfones ether, polyester, poly-carbonic acid vinegar and epoxy resin, bisphenol S requires that its purity is very high.Impurity in bisphenol S is brought very difficult washing in polymkeric substance into and is removed, and directly can affect the mechanical property of polymkeric substance, electrical property and optical property.
Adopting the method for aqueous sodium hydroxide solution purification bisphenol S, is the method that most domestic manufacturing enterprise generally adopts.This purification step is as follows: thick for bisphenol S product is dissolved in alkaline solution by (1); (2) add alkali further and make 4,4 ' isomer is with the form crystallization of single sodium salt; (3) single sodium salt is separated; (4) single sodium salt is dissolved in the water; (5) the bis-phenol s product that acid adding Precipitation is refining.The yield of the bisphenol S that this technique obtains is about 70%, 2, and the content of 4 ' isomer is not more than 0.5%.Alkali-soluble acid analysis method main drawback is that operation is loaded down with trivial details, and yield is lower, and wastewater flow rate is comparatively large, and production cost is higher.
Now also useful phenol makes the process for purification of solvent: mixed with phenol by bisphenol S crude product, heating for dissolving, crystallisation by cooling, the adducts crystal that precipitation 4,4 ' isomer and phenol generate, desolvation, and adducts obtains highly purified bisphenol S through dephenolize; 2,4 ' isomer can be dissolved in solvent phenol completely and be removed, the method utilizes cheap phenol to make solvent, obtain high purity finished product, the phenol simultaneously reclaimed still can be used as the raw material producing bisphenol S, the yield of the bisphenol S that this technique obtains can reach 80%, 2, and the content of 4 ' isomer is not more than 0.5%.The method main drawback is that phenol fusing point is higher, and operation easier is large, and equipment requirements is high, and product purity is difficult to improve, and production cost is large.
Therefore, research and develop and be a kind ofly easy to the low and preparation method of the bisphenol S that product purity is high of suitability for industrialized production, production cost.
Summary of the invention
The technical problem to be solved in the present invention is to provide and is a kind ofly easy to the low and preparation method of the bisphenol S that product purity is high of suitability for industrialized production, production cost, the method adopts the method for organic solvent (as methyl alcohol, ethanol, benzene, ethyl acetate etc.) recrystallization to refine, and its principle mainly utilizes organic solvent optionally to dissolve organic impurity to reach purifying object product.
For solving the problems of the technologies described above, technical scheme of the present invention is: a kind of preparation method of bisphenol S, and its innovative point is: these process for purification concrete steps are as follows:
(1) preparation of bisphenol S crude product: phenol, sym-trimethylbenzene are dropped into respectively in flask, opens and stirs, and heats up, be incubated and drip 98% vitriol oil at 100 DEG C, drip off rear temperature rising reflux and divide water, be incubated 165 DEG C and continue reaction 5 hours, obtain bisphenol S crude product, and reclaim sym-trimethylbenzene;
(2) bisphenol S is refining: in bisphenol S crude product, add organic solvent and gac successively, be incubated 65 DEG C of decolourings 1 hour, then filtered while hot, filtrate proceeds in bottle, then slow cooling, treats that crystal is separated out, be down to room temperature, finally filter out solid, and rinse solid by a small amount of organic solution, then solid is dried to obtain product.
Further, in described step (1), the dripping quantity of 98% vitriol oil is the half of phenol input amount.
Further, the organic solvent in described step (2) is the one in methyl alcohol, ethanol, benzene or ethyl acetate.
The invention has the advantages that: the preparation method of bisphenol S of the present invention, take sym-trimethylbenzene as solvent, and under specific processing condition, can reach 94%, 2 by the bisphenol S content in crude product of condensation, isomerization process synthesis, the content of 4 ' isomer is less than 4%; In addition, waste water is not produced in treating process, solvent can recovery and reuse easily, and rational organic solvent, can make the finished product content reach more than 99.5%, 2, the content of 4 ' isomer is less than 0.2%, and yield reaches more than 92%, meets suitability for industrialized production completely, production cost is low, and product purity is high.
Embodiment
The following examples can make the present invention of professional and technical personnel's comprehend, but therefore do not limit the present invention among described scope of embodiments.
Embodiment
The preparation method of the bisphenol S of the present embodiment, concrete steps are as follows:
(1) preparation of bisphenol S crude product: 100g phenol, 200ml sym-trimethylbenzene are dropped into respectively in flask, opens and stirs, and heats up, be incubated 98% vitriol oil dripping 50g at 100 DEG C, drip off rear temperature rising reflux and divide water, be incubated 165 DEG C and continue reaction 5 hours, obtain bisphenol S crude product, and reclaim sym-trimethylbenzene;
(2) bisphenol S is refining: in bisphenol S crude product, add organic solvent 300ml and gac 3g successively, be incubated 65 DEG C of decolourings 1 hour, then filtered while hot, filtrate proceeds in bottle, then slow cooling, treats that crystal is separated out, be down to room temperature, finally filter out solid, and rinse solid by a small amount of organic solution, then solid is dried to obtain product 116.5g.
comparative example 1
100g phenol, 200ml sym-trimethylbenzene are dropped in 500ml reaction flask respectively, opens and stir, heat up, be incubated 98% vitriol oil dripping 50g at 100 DEG C, drip off rear temperature rising reflux and divide water, be incubated 165 DEG C and continue reaction 5 hours, obtain bisphenol S crude product, reclaim sym-trimethylbenzene;
15% liquid caustic soda adding 300g in bisphenol S crude product dissolves, add gac 3g, control 65 DEG C of decolourings, filter, filtrate adds in 500ml water, with dilute sulphuric acid, pH value is adjusted to 6.5, crystal is had to separate out, 70 DEG C of insulations 1 hour, filtered while hot, solid hot water 100ml washes down 2 times, the mono-sodium salt of solid bisphenol S will enter in 1000ml water, be heated to 80 DEG C, continue to be acidified to pH value about 5.0 with dilute sulphuric acid, crystallize out was 90 DEG C of insulations 1 hour, be cooled to 40 DEG C, leach, rinse with clear water, dry, obtain product 85.5g.
comparative example 2
Dropped into by 250g phenol in 500ml reaction flask, heat up, be incubated at about 100 DEG C, drip 98% vitriol oil of 50g, drip off rear intensification and divide water reflux water-dividing, after point water completes, insulation 165 DEG C continues reaction 5 hours, bisphenol S crude product of lowering the temperature to obtain;
In bisphenol S crude product, add gac 3g at 80 DEG C to decolour 1 hour, filtered while hot, filtrate cooling has crystal to separate out at 50 DEG C, insulation crystallization, solid filtered while hot, and with hot water injection, obtains product 100g.
Following table is the contrast that embodiment and comparative example bisphenol S preparation method are prepared into product:
| Embodiment | Comparative example 1 | Comparative example 2 | |
| Bisphenol S content in thick product | 94.5% | 94.7% | 89.5% |
| Bisphenol S content in product | 99．7% | 99.65% | 99% |
| Isomers In Products content | 0.15% | 0.3% | 0.5% |
| Yield (sulphur acid meter) | 93.2% | 68.4% | 80% |
As can be seen from the above table, the present invention take sym-trimethylbenzene as solvent, under specific processing condition, can reach 94% by the bisphenol S content in crude product of condensation, isomerization process synthesis, refined by the method for organic solvent recrystallization again, the finished product content can be made to reach more than 99.5%, 2, and the content of 4 ' isomer is less than 0.2%, yield reaches more than 92%, meet suitability for industrialized production completely, production cost is low, and product purity is high.
The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (3)
1. a preparation method for bisphenol S, is characterized in that: these process for purification concrete steps are as follows:
(1) preparation of bisphenol S crude product: phenol, sym-trimethylbenzene are dropped into respectively in flask, opens and stirs, and heats up, be incubated and drip 98% vitriol oil at 100 DEG C, drip off rear temperature rising reflux and divide water, be incubated 165 DEG C and continue reaction 5 hours, obtain bisphenol S crude product, and reclaim sym-trimethylbenzene;
(2) bisphenol S is refining: in bisphenol S crude product, add organic solvent and gac successively, be incubated 65 DEG C of decolourings 1 hour, then filtered while hot, filtrate proceeds in bottle, then slow cooling, treats that crystal is separated out, be down to room temperature, finally filter out solid, and rinse solid by a small amount of organic solution, then solid is dried to obtain product.
2. the process for purification of bisphenol S according to claim 1, is characterized in that: in described step (1), the dripping quantity of 98% vitriol oil is the half of phenol input amount.
3. the process for purification of bisphenol S according to claim 1, is characterized in that: the organic solvent in described step (2) is the one in methyl alcohol, ethanol, benzene or ethyl acetate.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108084068A (en) * | 2017-12-29 | 2018-05-29 | 南通波涛化工有限公司 | A kind of method that low content bisphenol S changes into high-content bisphenol S |
| CN110317146A (en) * | 2019-07-10 | 2019-10-11 | 贵阳学院 | A kind of preparation method for the diphenol monomer substituting bisphenol-A |
| 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 |
| CN110467552A (en) * | 2019-08-30 | 2019-11-19 | 山东道可化学有限公司 | A kind of synthetic method of bisphenol S |
| CN113480457A (en) * | 2021-07-23 | 2021-10-08 | 涉县津东经贸有限责任公司 | Production method of high-purity bisphenol S |
| CN113493400A (en) * | 2020-04-03 | 2021-10-12 | 杭州逸翔化工科技有限公司 | Method for producing bisphenol S and co-producing sodium lignosulfonate |
| CN115611786A (en) * | 2022-10-25 | 2023-01-17 | 南通波涛化工有限公司 | Bisphenol S crystal form transformation and precipitation process |
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| US5241121A (en) * | 1989-12-29 | 1993-08-31 | Konishi Chemical Ind. Co., Ltd. | Process for preparation of 4,4'-dihydroxydiphenylsulfone |
| CN1622935A (en) * | 2002-03-20 | 2005-06-01 | 日本曹达株式会社 | Process for producing 4,4'-bisphenol sulfone |
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Patent Citations (3)
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| US5241121A (en) * | 1989-12-29 | 1993-08-31 | Konishi Chemical Ind. Co., Ltd. | Process for preparation of 4,4'-dihydroxydiphenylsulfone |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108084068A (en) * | 2017-12-29 | 2018-05-29 | 南通波涛化工有限公司 | A kind of method that low content bisphenol S changes into high-content bisphenol S |
| CN108084068B (en) * | 2017-12-29 | 2020-09-08 | 南通波涛化工有限公司 | Method for converting low-content bisphenol S into high-content bisphenol S |
| 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 |
| CN110317146A (en) * | 2019-07-10 | 2019-10-11 | 贵阳学院 | A kind of preparation method for the diphenol monomer substituting bisphenol-A |
| CN110467552A (en) * | 2019-08-30 | 2019-11-19 | 山东道可化学有限公司 | A kind of synthetic method of bisphenol S |
| CN110467552B (en) * | 2019-08-30 | 2021-07-09 | 山东道可化学有限公司 | Synthesis method of bisphenol S |
| CN113493400A (en) * | 2020-04-03 | 2021-10-12 | 杭州逸翔化工科技有限公司 | Method for producing bisphenol S and co-producing sodium lignosulfonate |
| CN113493400B (en) * | 2020-04-03 | 2023-07-07 | 杭州逸翔化工科技有限公司 | Method for producing bisphenol S and co-producing sodium lignin sulfonate |
| CN113480457A (en) * | 2021-07-23 | 2021-10-08 | 涉县津东经贸有限责任公司 | Production method of high-purity bisphenol S |
| CN115611786A (en) * | 2022-10-25 | 2023-01-17 | 南通波涛化工有限公司 | Bisphenol S crystal form transformation and precipitation process |
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Effective date of registration: 20160601 Address after: 226500, 2, Xiangjiang Road, Changjiang town (Rugao port area), Nantong, Jiangsu, Rugao Applicant after: NANTONG BOTAO CHEMICAL CO., LTD. Address before: Jiang town Rugao City, Jiangsu province 226500 Nantong City Village Liaison Applicant before: Rugao Jinling Chemical Co., Ltd. |
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Application publication date: 20160120 |