CN105272827A - Catalysis method for synthesizing bisphenol F - Google Patents
Catalysis method for synthesizing bisphenol F Download PDFInfo
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- CN105272827A CN105272827A CN201510121995.1A CN201510121995A CN105272827A CN 105272827 A CN105272827 A CN 105272827A CN 201510121995 A CN201510121995 A CN 201510121995A CN 105272827 A CN105272827 A CN 105272827A
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- phenol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a method for synthesizing bisphenol F with alkali metal bisulfate as a catalyst. Firstly, alkali metal bisulfate is dissolved in a formaldehyde solution, the mixture is added in an enclosed reactor with molten state phenol, the mol ratio of phenol to formaldehyde is 5-10:1, and the mol ratio of alkali metal bisulfate to formaldehyde is 0.005-0.05:1. The reaction temperature is 40-100 DEG C, the reaction time is 30-240min, cooling to the room temperature is carried out after the reaction is finished, the catalyst precipitates automatically, and the catalyst is filtered, recovered and reused. The filtrate is subjected to reduced pressure distillation, excess phenol is recovered, the residual concentrate is subjected to crystallization through toluene, xylene or a mixture with any ratio and bisphenol F is obtained. The employed catalyst is any one or a mixture of some selected from potassium hydrogen sulfate, sodium hydrogen sulfate or lithium hydrogen sulfate. The employed catalyst is cheap and easily available, has advantages of small dosage, high catalysis efficiency and repeated usage, and overcomes defects of many byproducts, large catalyst dosage and the like in synthesis of bisphenol F through other catalysts.
Description
Technical field
The present invention relates to a kind of method preparing Bisphenol F.
Background technology
Bisphenol F (BisphenylF, conventional abbreviation BPF represents) be the Novel chemical raw material that last century, the eighties was developed, as a kind of important chemical intermediate, because of the chemical structure characteristic that it is special, synthetic epoxy resin, vibrin, polycarbonate and as phenolic resin modified dose and fire retardant time, the processing of products obtained therefrom and mechanical property are all better than taking dihydroxyphenyl propane as the like product that raw material is made.In use can add less or not solubilizing agent and reactive thinner, thus reduce environmental pollution and reduce costs.Liquid bisphenol F type epoxy resin can be used for solventless coatings, tackiness agent, casting material, glass reinforced plastic and carbon fiber-based composite material etc.Solid-state bisphenol f type epoxy resin can be used as protective system and powder coating.Generally speaking, participate in by Bisphenol F the requirement that obtained product can meet a lot of property material, its product has boundless development and application prospect.
The chemical name of Bisphenol F is dihydroxydiphenyl methane, is generally formed through special process condensation under acid catalyst or Friedel – Crafts type catalyst action by phenol and formaldehyde.Based on the characteristic of reaction raw materials, ortho position and contraposition methylolphenol can be generated in reaction process, the Bisphenol F that reaction generates is the mixture containing following three isomer: 4,4 '-dihydroxydiphenyl methane is (hereinafter referred to as 4,4 '-BPF), 2,4 '-dihydroxydiphenyl methane (hereinafter referred to as 2,4 '-BPF), 2,2 '-dihydroxydiphenyl methane (hereinafter referred to as 2,2 '-BPF).In addition, also likely containing a small amount of polymer in the Bisphenol F of technical grade.
Patent CN102070409A discloses a kind of with the preparation method of the Bisphenol F of two step synthesis height ortho isomer content.In two steps, the first step is that phenol and formaldehyde are reacted under the condition of slightly acidic (being regulated reaction solution pH to be 2 ~ 3 by phosphoric acid) to the method; Second step is then in the first step reaction solution, add a large amount of catalyzer phosphoric acid and formaldehyde (mass ratio of phosphoric acid and phenol is 9 ~ 18:50), makes formaldehyde complete reaction, thereby is achieved the Bisphenol F of high ortho isomer content.But the method still also exists, and phosphoric acid catalyst consumption is large, phenol usage is excessive, recovery energy consumption is high, the defect of complicated operation.
Patent CN1075723A discloses the method simultaneously preparing high-purity bisphenols F and novolak phenol resins, the method adopts phenol: formaldehyde=6 ~ 30:1, under Catalyzed by Oxalic Acid agent effect, condensation generates thick Bisphenol F, then under utilizing high temperature, high vacuum, large multiple phenol circulating and evaporating is applied mechanically the water in technique removing acid catalyst, unreacted phenol and reaction system thus obtains highly purified Bisphenol F, and this method energy consumption is high, complex process.
Patent CN102992964A then discloses a kind of Bisphenol F production method, the method is 2:1 ~ 10:1 at phenol formaldehyde ratio, organic phosphoric acid catalyst reacts the mixture that 1 ~ 8h obtains acid catalyst and Bisphenol F and phenol under accounting for the condition of 2% ~ 60%, 40 ~ 50 DEG C of phenol weight, after acid catalyst is isolated in separatory operation, inert ion fluidized bed processing, deep bed filter and cyclonic separator is adopted to reclaim rough Bisphenol F product, improve the purity of Bisphenol F by means re-crystallization refinement treatment, the method still also exists that catalyst levels is large, the problem of complex manufacturing.
Patent CN102584541A discloses a kind of method that 1-alkyl-3-methylimidazole acidic ionic liquid prepares Bisphenol F, the method does catalysts and solvents so that 1-alkyl-3-methylimidazole acidic ionic liquid is double, and phenol formaldehyde ratio is no more than 12:1, acid catalyst formaldehyde mole ratio is obtain Bisphenol F under the condition of 0.5:1 ~ 4:1.This catalyst levels is large and need wash reprocessing and could reclaim.Add energy consumption, unfavorable for realizing large-scale industrial production.
In a word, prepare in the method for BPF at present, there is the defect that catalyst levels is large, reclaim the large and complex process of unreacting phenol energy consumption etc.
Summary of the invention
The object of the present invention is to provide a kind of high-level efficiency to generate the preparation method of Bisphenol F, to improve in existing Bisphenol F preparation method, catalyst levels is large, by product is many and the shortcoming of complex process.
The method preparing Bisphenol F of the present invention, its key step is:
Alkali metal sulphuric acid hydrogen salt catalyzer is dissolved in formaldehyde solution, then joins the phenol of the molten state being heated to certain temperature together, at this temperature, stirring reaction 30 ~ 300 minutes, obtains target product by phenol and formaldehyde condensation reaction.After reaction solution is cooled to room temperature, filters, isolate catalyzer.Reclaim under reduced pressure unreacting phenol, its temperature is no more than 150 DEG C.The mixture recrystallization of toluene and dimethylbenzene, obtains Bisphenol F product.
Wherein said certain temperature is 50 ~ 90 DEG C, and acid catalyst is sodium pyrosulfate, sal enixum or lithium hydrogen sulfate any one or multiple mixture.The mol ratio of described phenol and formaldehyde is 5:1 ~ 10:1, and the mol ratio of catalyzer and formaldehyde is 0.005:1 ~ 0.05:1.
Above-mentioned more excellent scheme is, described temperature is 60 ~ 80 DEG C, acid catalyst is sodium pyrosulfate, sal enixum or lithium hydrogen sulfate any one or multiple mixture, and phenol and formaldehyde mole ratio are 8:1 ~ 10:1, and the mol ratio of phenol and hydrosulfate is 0.01:1 ~ 0.05:1.
Above-mentioned more excellent scheme is, in described reclaim under reduced pressure unreacting phenol operation, its temperature is no more than 120 DEG C.Bisphenol F prepared by the present invention is with three kind of two nuclear isomer (4,4 '-BPF, 2,4 '-BPF, 2,2 '-BPF) be main component, wherein 2,4 '-BPF, 2,2 '-BPF comparision contents is high, can stablize and obtain 2,4 '-BPF ratio is 42.% ~ 52.5%, 2, and 2 '-BPF ratio is the Bisphenol F product of 19% ~ 25%.Cheaper starting materials of the present invention is easy to get, catalyst levels is few and recyclable, technological operation relative ease is easy, be easy to realize industrialization scale operation.
embodiment
Example of the present invention can not limit the present invention to of the present invention further illustrating, and is any change in the implication that the present invention is suitable and scope and adjustment, all should thinks within the scope of the invention.
Embodiment 1
One be equipped with thermometer, reflux condensing tube 2000mL there-necked flask in, first add 941.1g molten state phenol, be heated to 60 DEG C, then add the 80.1g formaldehyde solution (mass percent is 37.5%) of the LiHSO4 being dissolved with 5.0g.Stirring reaction 3h at 70 DEG C.Stopped reaction, then by reacting liquid filtering, isolates catalyzer, and underpressure distillation removing phenol, adds 500mL toluene and carry out recrystallization.Obtain Bisphenol F product.Bisphenol F three kinds of isomeric distribution are as follows: 4,4 '-BPF be 28.6%, 2,4 '-BPF be 46.3%, 2,2 '-BPF is 25.1%.
Embodiment 2
One be equipped with thermometer, reflux condensing tube 2000mL there-necked flask in, first add 941.1g molten state phenol, be heated to 60 DEG C, then add the 80.1g formaldehyde solution (mass percent is 37.5%) of the NaHSO4 being dissolved with 1.0g.Stirring reaction 3h at 70 DEG C.Stopped reaction, then by reacting liquid filtering, isolates catalyzer, and underpressure distillation removing phenol, adds 250mL toluene and carry out recrystallization.Obtain Bisphenol F product.Bisphenol F three kinds of isomeric distribution are as follows: 4,4 '-BPF be 29.9%, 2,4 '-BPF be 44.5%, 2,2 '-BPF is 25.6%.
Embodiment 3
One be equipped with thermometer, reflux condensing tube 2000mL there-necked flask in, first add 941.1g molten state phenol, be heated to 60 DEG C, then add the 160.2g formaldehyde solution (mass percent is 37.5%) of the KHSO4 being dissolved with 10.0g.Stirring reaction 3h at 70 DEG C.Stopped reaction, then by reacting liquid filtering, isolates catalyzer, and underpressure distillation removing phenol, adds 500mL toluene and carry out recrystallization.Obtain Bisphenol F product.Bisphenol F three kinds of isomeric distribution are as follows: 4,4 '-BPF be 26.7%, 2,4 '-BPF be 47.4%, 2,2 '-BPF is 25.9%.
Embodiment 4
One be equipped with thermometer, reflux condensing tube 2000mL there-necked flask in, first add 941.1g molten state phenol, be heated to 60 DEG C, then add LiHSO4,0.5gNAHSO of being dissolved with 0.5g
480.1g formaldehyde solution (mass percent is 37.5%).Stirring reaction 3h at 90 DEG C.Stopped reaction, then by reacting liquid filtering, isolates catalyzer, and underpressure distillation removing phenol, adds 100mL dimethylbenzene and carry out recrystallization and obtain Bisphenol F product.Bisphenol F three kinds of isomeric distribution are as follows: 4,4 '-BPF be 29.5%, 2,4 '-BPF be 45.3%, 2,2 '-BPF is 25.2%.
Embodiment 5
One be equipped with thermometer, reflux condensing tube 500mL there-necked flask in, first add 941.1g molten state phenol, be heated to 60 DEG C, then add the 80.1g formaldehyde solution (mass percent is 37.5%) of NaHSO4,2.5gKHSO4 of being dissolved with 2.5g.Stirring reaction 2h at 90 DEG C.Stopped reaction, then by reacting liquid filtering, isolates catalyzer, and underpressure distillation removing phenol, the mixed solution adding 200mL toluene and dimethylbenzene carries out recrystallization.Obtain Bisphenol F product.Bisphenol F three kinds of isomeric distribution are as follows: 4,4 '-BPF be 29.6%, 2,4 '-BPF be 45.3%, 2,2 '-BPF is 25.1%.
Claims (6)
1. one kind with the method for alkali metal sulphuric acid hydrogen salt for catalyzer bisphenol synthesis F, alkali metal sulphuric acid hydrogen salt catalyzer is the steps include: to be dissolved in formaldehyde solution, join together again to molten state phenol, the mol ratio of added phenol and formaldehyde is 5 ~ 10:1, the mol ratio of added alkali metal sulphuric acid hydrogen salt and formaldehyde is 0.005 ~ 0.05:1, temperature of reaction 40 ~ 100 DEG C, stirring reaction 30 ~ 300 minutes at this temperature, target product is obtained by phenol and formaldehyde condensation reaction, reaction terminates rear cool to room temperature, catalyzer is separated out voluntarily, filtering recovering catalyst is reused, filtrate reclaims excessive phenol through underpressure distillation, residue enriched material is through toluene, namely the crystalline mixture of dimethylbenzene or its arbitrary proportion obtains Bisphenol F.
2. according to claim 1 a kind of with the method for alkali metal sulphuric acid hydrogen salt for catalyzer bisphenol synthesis F, it is characterized in that: described alkali metal sulphuric acid hydrogen salt catalyzer is sal enixum, sodium pyrosulfate or lithium hydrogen sulfate wherein any one or multiple mixture.
3. according to the method described in claim 1, it is characterized in that: the mol ratio of added phenol and formaldehyde is 8 ~ 10:1.
4. according to the method described in claim 1, it is characterized in that: the mol ratio of added alkali metal sulphuric acid hydrogen salt and formaldehyde is 0.01 ~ 0.05:1.
5. according to the method described in claim 1, it is characterized in that: temperature of reaction is 60 ~ 90 DEG C.
6. according to the method described in claim 1, it is characterized in that: the reaction times is 30 ~ 300 minutes.
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| CN201510121995.1A CN105272827B (en) | 2015-03-20 | 2015-03-20 | A kind of catalysis process of bisphenol synthesis F |
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| CN201510121995.1A CN105272827B (en) | 2015-03-20 | 2015-03-20 | A kind of catalysis process of bisphenol synthesis F |
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| CN105272827A true CN105272827A (en) | 2016-01-27 |
| CN105272827B CN105272827B (en) | 2017-03-15 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114671740A (en) * | 2022-01-27 | 2022-06-28 | 濮阳市恩赢高分子材料有限公司 | Synthesis method of bisphenol F |
| CN114835559A (en) * | 2022-07-04 | 2022-08-02 | 山东亿科化学有限责任公司 | Catalytic method for synthesizing bisphenol F |
| CN117209362A (en) * | 2023-11-09 | 2023-12-12 | 山东富宇石化有限公司 | Preparation method of bisphenol F with chelating agent |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584541A (en) * | 2012-01-18 | 2012-07-18 | 湘潭大学 | Method for preparing bisphenol F by using 1-alkyl-3-methylimidazole acidic ionic liquid |
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- 2015-03-20 CN CN201510121995.1A patent/CN105272827B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584541A (en) * | 2012-01-18 | 2012-07-18 | 湘潭大学 | Method for preparing bisphenol F by using 1-alkyl-3-methylimidazole acidic ionic liquid |
Non-Patent Citations (1)
| Title |
|---|
| QING WANG 等: "The efficient hydroxyalkylation of phenol with formaldehyde to bisphenol F over a thermoregulated phase-separable reaction system containing a water-soluble Brønsted acidic ionic liquid", 《RSC ADVANCES》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114671740A (en) * | 2022-01-27 | 2022-06-28 | 濮阳市恩赢高分子材料有限公司 | Synthesis method of bisphenol F |
| CN114671740B (en) * | 2022-01-27 | 2024-03-12 | 濮阳市恩赢高分子材料有限公司 | Bisphenol F synthesis method |
| CN114835559A (en) * | 2022-07-04 | 2022-08-02 | 山东亿科化学有限责任公司 | Catalytic method for synthesizing bisphenol F |
| CN114835559B (en) * | 2022-07-04 | 2022-09-09 | 山东亿科化学有限责任公司 | Catalytic method for synthesizing bisphenol F |
| CN117209362A (en) * | 2023-11-09 | 2023-12-12 | 山东富宇石化有限公司 | Preparation method of bisphenol F with chelating agent |
| CN117209362B (en) * | 2023-11-09 | 2024-01-30 | 山东富宇石化有限公司 | Preparation method of bisphenol F with chelating agent |
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