CN105272827B - A kind of catalysis process of bisphenol synthesis F - Google Patents
A kind of catalysis process of bisphenol synthesis F Download PDFInfo
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- CN105272827B CN105272827B CN201510121995.1A CN201510121995A CN105272827B CN 105272827 B CN105272827 B CN 105272827B CN 201510121995 A CN201510121995 A CN 201510121995A CN 105272827 B CN105272827 B CN 105272827B
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- bisphenol
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- sulphuric acid
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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
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- 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 kind of method with alkali metal sulphuric acid hydrogen salt as catalyst bisphenol synthesis F.Alkali metal sulphuric acid hydrogen salt is first dissolved in formalin by the method, and another rising adds the closed reactor that molten state phenol is extremely housed, and added phenol is 5～10 with the mol ratio of formaldehyde:1, added alkali metal sulphuric acid hydrogen salt is 0.005～0.05 with the mol ratio of formaldehyde:1.40～100 DEG C of reaction temperature, 30～240 minutes response time, reaction are cooled to room temperature after terminating, and catalyst is voluntarily separated out, and catalyst reuse is recovered by filtration.Filtrate reclaims excessive phenol through vacuum distillation, and remaining concentrate obtains final product Bisphenol F through the crystalline mixture of toluene, dimethylbenzene or its arbitrary proportion.The catalyst for being adopted is potassium acid sulfate, sodium bisulfate or lithium hydrogen sulfate any of which or multiple mixture.Catalyst used by the method is cheap and easy to get, with consumption is few, high catalytic efficiency and reusable advantage, the shortcomings of when overcoming other catalyst bisphenol synthesis F, by-product is more, catalyst amount is big.
Description
Technical field
The present invention relates to a kind of method for preparing Bisphenol F.
Background technology
Bisphenol F（Bisphenyl F, commonly use abbreviation BPF to represent）Be that last century the eighties are developed one
Novel chemical raw material, as a kind of important chemical intermediate, because of its special chemical structure characteristic, synthetic epoxy resin,
Polyester resin, polycarbonate and during as phenolic resin modified dose and fire retardant, the processing of products obtained therefrom and mechanical property are equal
Better than the like product that is made as raw material with bisphenol-A.Can add less in use or not solubilizer and activity dilution
Agent, so that reduce environmental pollution and reduces cost.Liquid bisphenol F type epoxy resin can be used for solventless coatings, adhesive, casting
Material, fiberglass and carbon fiber-based composite material etc..Solid-state bisphenol f type epoxy resin can be used as anticorrosive paint and powdery paints.Always
For it, product obtained in Bisphenol F is participated in can meet the requirement of a lot of property materials, and its product has boundless
Development and application prospect.
The chemical name of Bisphenol F is dihydroxydiphenyl methane, typically by phenol and formaldehyde in acid catalyst or
Form through special process condensation under Friedel Crafts type catalyst actions.Based on the characteristic of reaction raw materials, in course of reaction
Ortho position and para-position hydroxymethylphenol can be generated, it is the mixture containing three below isomer to react the Bisphenol F for generating：4,4’-
Dihydroxydiphenyl methane（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）.Additionally, it is also possible to containing a small amount of in the Bisphenol F of technical grade
Polymer.
Patent CN102070409A discloses a kind of preparation side of the Bisphenol F for synthesizing high ortho isomer content with two-step method
Method.In two steps, the first step is phenol with formaldehyde in faintly acid to the method（It is 2～3 that reactant liquor pH is adjusted by phosphoric acid）Condition
Lower reaction；Second step be then to first step reactant liquor in add substantial amounts of catalyst phosphoric acid and formaldehyde（Phosphoric acid and the quality of phenol
Than for 9～18:50）, formaldehyde is reacted completely, thereby is achieved the Bisphenol F of high ortho isomer content.But the method is still deposited
Phosphoric acid catalyst consumption big, phenol usage is excessive, reclaim high energy consumption, complex operation defect.
1075723 A of patent CN discloses the method while preparing high-purity bisphenols F and novolak phenol resins, the party
Method adopts phenol：Formaldehyde=6～30:1, the lower condensation of Catalyzed by Oxalic Acid agent effect generates thick Bisphenol F, then using high temperature, fine vacuum under
Big multiple phenol circulating and evaporating applies mechanically water that technique removed in acid catalyst, unreacted phenol and reaction system so as to obtaining height
The Bisphenol F of purity, the method high energy consumption, complex process.
Patent CN102992964 A then discloses a kind of Bisphenol F production method, and the method is 2 in phenol formaldehyde ratio:1～10:
1, organic phosphoric acid catalyst account for the 2%～60% of phenol weight, 40～50 DEG C under conditions of react 1～8h obtained acid catalyst and
Bisphenol F and the mixture of phenol, after acid catalyst is isolated in a point liquid operation, using inert ion fluidized bed processing, bag type filtering
Device and cyclone separator reclaim rough Bisphenol F product, the purity that improve Bisphenol F with means re-crystallization refinement treatment, the method
Remain that catalyst amount is big, the problem of complex manufacturing.
Patent CN102584541 A discloses a kind of 1- alkyl-3-methylimidazole acidic ionic liquids and prepares Bisphenol F
Method, the method also serve as catalysts and solvents with 1- alkyl-3-methylimidazole acidic ionic liquids, and phenol formaldehyde ratio is less than 12:
1st, acid catalyst formaldehyde mole ratio is 0.5：1～4：Bisphenol F is obtained under conditions of 1.The catalyst amount is big and need to wash again
Process and could reclaim.Energy consumption is increased, unfavorable for large-scale industrial production is realized.
In a word, prepares at present in the method for BPF, exist that catalyst amount is big, reclaim unreacting phenol energy consumption greatly and work
The defect of skill complexity etc..
Content of the invention
It is an object of the invention to provide a kind of high efficiency generates the preparation method of Bisphenol F, prepared with improving existing Bisphenol F
In method, catalyst amount is big, by-product is more and the shortcoming of complex process.
The method for preparing Bisphenol F of the present invention, which has main steps that：
Alkali metal sulphuric acid hydrogen salt catalyst is dissolved in formalin, then is added to the molten for being heated to uniform temperature together
The phenol of state, stirring reaction 30～300 minutes, obtain target product by phenol and formaldehyde condensation reaction at this temperature.Reactant liquor
After being cooled to room temperature, filter, isolate catalyst.Recovered under reduced pressure unreacting phenol, its temperature are less than 150 DEG C.Toluene and two
The mixture recrystallization of toluene, obtains Bisphenol F product.
Wherein described uniform temperature is 50～90 DEG C, and acid catalyst is that sodium bisulfate, potassium acid sulfate or lithium hydrogen sulfate are any
One or more mixture.The phenol is 5 with the mol ratio of formaldehyde:1～10:1, catalyst with the mol ratio of formaldehyde is
0.005:1～0.05:1.
Above-mentioned more excellent scheme is that the temperature is 60～80 DEG C, and acid catalyst is sodium bisulfate, potassium acid sulfate or hydrogen sulfate
Lithium any one or more mixture, phenol are 8 with formaldehyde mole ratio:1～10:1, phenol with the mol ratio of disulfate is
0.01:1～0.05:1.
Above-mentioned more excellent scheme is that, in the recovered under reduced pressure unreacting phenol operation, its temperature is less than 120 DEG C.The present invention
Prepared Bisphenol F is with three kind of two nuclear isomer（4,4’-BPF、2,4’-BPF、2,2’-BPF）For main component, wherein 2,
4 '-BPF, 2,2 '-BPF comparision contents are high, can stably obtain 2,4 '-BPF ratios for 42.%～52.5%, 2,2 '-BPF ratios
For 19%～25% Bisphenol F product.Raw material of the present invention is cheap and easy to get, catalyst amount is few and recyclable, technological operation is relatively simple
Easy row, it is easily achieved industrialization large-scale production.
Specific embodiment
Example of the present invention is can not to limit the present invention to further illustrating for the present invention, is of the invention suitable
Implication and scope in any change and adjustment, be all considered as within the scope of the invention.
Embodiment 1
It is equipped with thermometer, the there-necked flask of the 2000mL of reflux condensing tube one, is initially charged 941.1g molten state phenol,
60 DEG C are heated to, the 80.1g formalins of the LiHSO4 dissolved with 5.0g are added（Mass percent is 37.5%）.70℃
Lower stirring reaction 3h.Stopped reaction, then by reacting liquid filtering, isolates catalyst, and vacuum distillation removes phenol, adds
500mL toluene carries out recrystallization.Obtain Bisphenol F product.Three kinds of isomer distributions of Bisphenol F are as follows：4,4 '-BPF are 28.6%, 2,
It is 25.1% that 4 '-BPF are 46.3%, 2,2 '-BPF.
Embodiment 2
It is equipped with thermometer, the there-necked flask of the 2000mL of reflux condensing tube one, is initially charged 941.1g molten state phenol,
60 DEG C are heated to, the 80.1g formalins of the NaHSO4 dissolved with 1.0g are added（Mass percent is 37.5%）.70℃
Lower stirring reaction 3h.Stopped reaction, then by reacting liquid filtering, isolates catalyst, and vacuum distillation removes phenol, adds
250mL toluene carries out recrystallization.Obtain Bisphenol F product.Three kinds of isomer distributions of Bisphenol F are as follows：4,4 '-BPF are 29.9%, 2,
It is 25.6% that 4 '-BPF are 44.5%, 2,2 '-BPF.
Embodiment 3
It is equipped with thermometer, the there-necked flask of the 2000mL of reflux condensing tube one, is initially charged 941.1g molten state phenol,
60 DEG C are heated to, the 160.2 g formalins of the KHSO4 dissolved with 10.0g are added（Mass percent is 37.5%）.70
Stirring reaction 3h at DEG C.Stopped reaction, then by reacting liquid filtering, isolates catalyst, and vacuum distillation removes phenol, adds
500mL toluene carries out recrystallization.Obtain Bisphenol F product.Three kinds of isomer distributions of Bisphenol F are as follows：4,4 '-BPF are 26.7%, 2,
It is 25.9% that 4 '-BPF are 47.4%, 2,2 '-BPF.
Embodiment 4
It is equipped with thermometer, the there-necked flask of the 2000mL of reflux condensing tube one, is initially charged 941.1g molten state phenol,
60 DEG C are heated to, LiHSO4,0.5gNAHSO dissolved with 0.5g is added480.1g formalins（Mass percent is
37.5%）.Stirring reaction 3h at 90 DEG C.Stopped reaction, then by reacting liquid filtering, isolates catalyst, and vacuum distillation removes benzene
Phenol, adds 100mL dimethylbenzene to carry out being recrystallized to give Bisphenol F product.Three kinds of isomer distributions of Bisphenol F are as follows：4,4 '-BPF are
29.5%, 2,4 '-BPF are 45.3%, 2, and 2 '-BPF are 25.2%.
Embodiment 5
It is equipped with thermometer, the there-necked flask of the 500mL of reflux condensing tube one, is initially charged 941.1g molten state phenol,
60 DEG C are heated to, the 80.1 g formalins of NaHSO4, the 2.5gKHSO4 dissolved with 2.5g are added（Mass percent is
37.5%）.Stirring reaction 2h at 90 DEG C.Stopped reaction, then by reacting liquid filtering, isolates catalyst, and vacuum distillation removes benzene
Phenol, adds 200mL toluene and the mixed liquor of dimethylbenzene to carry out recrystallization.Obtain Bisphenol F product.Three kinds of isomer distributions of Bisphenol F
As follows：4,4 '-BPF are 29.6%, 2, and 4 '-BPF are 45.3%, 2, and 2 '-BPF are 25.1%.
Claims (6)
1. a kind of method with alkali metal sulphuric acid hydrogen salt as catalyst bisphenol synthesis F, its step is：Alkali metal sulphuric acid hydrogen salt is urged
Agent is dissolved in formalin, then is added to molten state phenol together, and added phenol is 5～10 with the mol ratio of formaldehyde:1, institute
Plus alkali metal sulphuric acid hydrogen salt is 0.005～0.05 with the mol ratio of formaldehyde:1,40～100 DEG C of reaction temperature is stirred at this temperature
Reaction 30～300 minutes, obtains target product by phenol and formaldehyde condensation reaction, and reaction is cooled to room temperature, catalyst after terminating
Voluntarily separate out, be recovered by filtration catalyst reuse, filtrate through vacuum distillation reclaim excessive phenol, remaining concentrate through toluene,
The crystalline mixture of dimethylbenzene or its arbitrary proportion obtains final product Bisphenol F.
2. a kind of method with alkali metal sulphuric acid hydrogen salt as catalyst bisphenol synthesis F according to claim 1, its feature exist
In：The alkali metal sulphuric acid hydrogen salt catalyst is potassium acid sulfate, sodium bisulfate or lithium hydrogen sulfate any of which or multiple
Mixture.
3. according to the method described in claim 1, it is characterised in that：Added phenol is 8～10 with the mol ratio of formaldehyde:1.
4. according to the method described in claim 1, it is characterised in that：Added alkali metal sulphuric acid hydrogen salt with the mol ratio of formaldehyde is
0.01～0.05:1.
5. according to the method described in claim 1, it is characterised in that：Reaction temperature is 60～90 DEG C.
6. according to the method described in claim 1, it is characterised in that：Response time 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 CN105272827A (en) | 2016-01-27 |
| CN105272827B true CN105272827B (en) | 2017-03-15 |
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| 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 |
| 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 |
| 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 |
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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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 (3)
| Title |
|---|
| cient hydroxyalkylation of phenol with formaldehyde to bisphenol F over a thermoregulated phase-separable reaction system containing a water-soluble Brø * |
| nsted acidic ionic liquid.《RSC Advances》.2014,第4卷(第63期), * |
| Qing Wang 等.The effi * |
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