CN105037102A - Method for synthesizing bisphenol F by using amine bisulphate as catalyst - Google Patents
Method for synthesizing bisphenol F by using amine bisulphate as catalyst Download PDFInfo
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- CN105037102A CN105037102A CN201510311750.5A CN201510311750A CN105037102A CN 105037102 A CN105037102 A CN 105037102A CN 201510311750 A CN201510311750 A CN 201510311750A CN 105037102 A CN105037102 A CN 105037102A
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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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- 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
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
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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 by using amine bisulphate as a catalyst. The method comprises the following steps: adding amine bisulphate into a closed reactor filled with molten phenol, and adding a formaldehyde solution, wherein the mole ratio of the phenol to the formaldehyde is (5-10):1, and the mole ratio of the amine bisulphate to the formaldehyde is (0.05-0.5):1; reacting at 50-100 DEG C for 30-180 minutes; after the reaction finishes, cooling to room temperature, and recovering the catalyst for reuse; and carrying out reduced pressure distillation to recover excessive phenol, and recrystallizing the residual concentrate by toluene to obtain the bisphenol F product. The catalyst used by the method has the advantages of simple preparation process, low consumption and high catalytic efficiency, is reusable, and overcomes the defects of high byproduct quantity, severe corrosion and the like when other protonic acid catalysts are used for synthesizing bisphenol F.
Description
Technical field
The present invention relates to a kind of method preparing Bisphenol F.
Background technology
The chemical name of Bisphenol F is dihydroxydiphenyl methane, it is a kind of important Novel chemical raw material that last century, the eighties was developed, come from its special chemical structure characteristic (what connect between two phenyl ring is rotatable methylene radical), bisphenol f type epoxy resin viscosity can be low to moderate 1/4 of bisphenol A epoxide resin.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., and solid-state bisphenol f type epoxy resin can be used as protective system and powder coating.Participate in by Bisphenol F the requirement that obtained product can meet a lot of material property, its product has boundless development and application prospect.
Bisphenol F is generally formed through special process condensation under acid catalyst or Friedel – Crafts type catalyst action by phenol and formaldehyde.React as shown in the formula
Ortho position and contraposition methylolphenol two kinds of intermediates can be generated in reaction process, these two kinds of reaction intermediates continue to react with the ortho position of phenol or contraposition, therefore the Bisphenol F generated is actually the mixture containing 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 (<10%) in the Bisphenol F of technical grade.
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.
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.
In a word, prepare in the method for Bisphenol F 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 low-cost high-efficiency to prepare the method for Bisphenol F, with improve existing protonic acid for catalyst levels in catalyst preparing Bisphenol F method the large and shortcoming that corrodibility is strong.
The method preparing Bisphenol F of the present invention, its key step is:
A, Ammonium hydrogen sulfate catalyzer to be joined in the closed reactor of the phenol that the molten state being heated to certain temperature is housed, then drop into formaldehyde solution or paraformaldehyde.At this temperature, stirring reaction 30 ~ 180 minutes, obtains target product by phenol and formaldehyde condensation reaction.After b, reaction solution are cooled to room temperature, washing, aqueous phase decompression rotary evaporation reclaims catalyzer.Unreacting phenol is reclaimed in c, organic phase underpressure distillation, and its temperature is no more than 120 DEG C, re crystallization from toluene, obtains Bisphenol F product.
Wherein certain temperature described in step a is 50 ~ 90 DEG C, and acid catalyst is Trimethylamine 99 hydrosulfate, triethylamine hydrosulfate, tripropyl amine hydrosulfate or tri-n-butylamine hydrosulfate 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 0.05:1 ~ 0.5:1.
Above-mentioned more excellent scheme is, temperature described in step a is 60 ~ 80 DEG C, and acid catalyst is Trimethylamine 99 hydrosulfate, triethylamine hydrosulfate, tripropyl amine hydrosulfate or tri-n-butylamine hydrosulfate any one or multiple mixture., phenol and formaldehyde mole ratio are 7.5:1 ~ 10:1, and the mol ratio of phenol and Ammonium hydrogen sulfate is 0.1:1 ~ 0.5:1.
Above-mentioned more excellent scheme is, in reclaim under reduced pressure unreacting phenol operation described in step c, its temperature is no more than 120 DEG C.
Described acid catalyst structural formula is:
Formula cationic be respectively [Me3NH]+, [Et3NH]+, [Pr3NH]+, [Bu3NH]+.
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 49% ~ 52%, 2, and 2 '-BPF ratio is the Bisphenol F product of 22% ~ 25%.Advantage of the present invention be that cheaper starting materials is easy to get, catalyst levels is few and recyclable, technological operation relative ease is easy.
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, 15.8g Trimethylamine 99 hydrosulfate, be heated to 60 DEG C, then add 80.1g formaldehyde solution (mass percent is 37.5%).Stirring reaction 3h at 70 DEG C.Stopped reaction, then reaction solution is cooled to room temperature, washing, and aqueous phase decompression rotary evaporation reclaims catalyzer, and organic phase underpressure distillation removing phenol, adds 500mL toluene and carry out recrystallization.Obtain Bisphenol F product.Bisphenol F yield (in formaldehyde) is 88.9%, and Bisphenol F three kinds of isomeric distribution are as follows: 4,4 '-BPF be 25.6%, 2,4 '-BPF be 49.1%, 2,2 '-BPF is 25.3%.
Embodiment 2
One be equipped with thermometer, reflux condensing tube 2000mL there-necked flask in, first add 941.1g molten state phenol, 20.0g triethylamine hydrosulfate, be heated to 60 DEG C, then add 80.1g formaldehyde solution (mass percent is 37.5%).Stirring reaction 3h at 70 DEG C.Stopped reaction, then reaction solution is cooled to room temperature, washing, and aqueous phase decompression rotary evaporation reclaims catalyzer, and organic phase underpressure distillation removing phenol, adds 500mL toluene and carry out recrystallization.Obtain Bisphenol F product.The different Bisphenol F yield (in formaldehyde) of Bisphenol F three kinds is 89.5%, and the distribution of structure body is as follows: 4,4 '-BPF be 25.3%, 2,4 '-BPF be 49.7%, 2,2 '-BPF is 25.0%.
Embodiment 3
One be equipped with thermometer, reflux condensing tube 2000mL there-necked flask in, first add 941.1g molten state phenol, 24.2g Tri-n-Propylamine hydrosulfate, be heated to 60 DEG C, then add 80.1g formaldehyde solution (mass percent is 37.5%).Stirring reaction 3h at 80 DEG C.Stopped reaction, then reaction solution is cooled to room temperature, washing, and aqueous phase decompression rotary evaporation reclaims catalyzer, and organic phase underpressure distillation removing phenol, adds 500mL toluene and carry out recrystallization.Obtain Bisphenol F product.Bisphenol F yield (in formaldehyde) is 89.2%, and Bisphenol F three kinds of isomeric distribution are as follows: 4,4 '-BPF be 24.7%, 2,4 '-BPF be 50.7%, 2,2 '-BPF is 24.6%.
Embodiment 4
One be equipped with thermometer, reflux condensing tube 2000mL there-necked flask in, first add 941.1g molten state phenol, 14.15g tri-n-butylamine hydrosulfate, be heated to 80 DEG C, then add 80.1g formaldehyde solution (mass percent is 37.5%).Stirring reaction 3h at 80 DEG C.Stopped reaction, then reaction solution is cooled to room temperature, washing, and aqueous phase decompression rotary evaporation reclaims catalyst recovery catalyzer, and organic phase underpressure distillation removing phenol, adds 250mL toluene and carry out recrystallization.Obtain Bisphenol F product.Bisphenol F yield (in formaldehyde) is 88.9%, and Bisphenol F three kinds of isomeric distribution are as follows: 4,4 '-BPF be 23.2%, 2,4 '-BPF be 50.6%, 2,2 '-BPF is 26.1%.
Embodiment 5
One be equipped with thermometer, reflux condensing tube 2000mL there-necked flask in, first add 941.1g molten state phenol, 14.15g tri-n-butylamine hydrosulfate and 12.1g triethylamine hydrosulfate, be heated to 80 DEG C, then add 80.1g formaldehyde solution (mass percent is 37.5%).Stirring reaction 3h at 80 DEG C.Stopped reaction, then reaction solution is cooled to room temperature, washing, and aqueous phase decompression rotary evaporation reclaims catalyst recovery catalyzer, and organic phase underpressure distillation removing phenol, adds 200mL toluene and carry out recrystallization.Obtain Bisphenol F product.Bisphenol F yield (in formaldehyde) is 88.9%, and Bisphenol F three kinds of isomeric distribution are as follows: 4,4 '-BPF be 22.6%, 2,4 '-BPF be 51.1%, 2,2 '-BPF is 26.3%.
Claims (6)
1. one kind take Ammonium hydrogen sulfate as the method for catalyzer bisphenol synthesis F, the steps include: first Ammonium hydrogen sulfate to be added in the closed reactor that the phenol being heated to certain temperature is housed, drop into formaldehyde solution again, the mol ratio of added phenol and formaldehyde is 5 ~ 10:1, the mol ratio of added Ammonium hydrogen sulfate and formaldehyde is 0.05 ~ 0.5:1, temperature of reaction 50 ~ 100 DEG C, stirring reaction 30 ~ 180 minutes at this temperature, target product is obtained by phenol and formaldehyde condensation reaction, reaction terminates rear cool to room temperature, recovery catalyzer 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 take Ammonium hydrogen sulfate as the method for catalyzer bisphenol synthesis F, it is characterized in that: described Ammonium hydrogen sulfate catalyst structure formula is:
R1 in formula, 2,3=Me, Et, Pr, Bu.
3. according to method described in claim 1, it is characterized in that: the mol ratio of added phenol and formaldehyde is 7.5 ~ 10:1.
4. according to the method described in claim 1, it is characterized in that: the mol ratio of added Ammonium hydrogen sulfate and formaldehyde is 0.1 ~ 0.5:1.
5. according to the method described in claim 1, it is characterized in that: temperature of reaction is 60 ~ 80 DEG C.
6. according to the method described in claim 1, it is characterized in that: the reaction times is 60 ~ 120 minutes.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0889819A (en) * | 1994-09-20 | 1996-04-09 | Mitsubishi Chem Corp | Ion exchange resin |
| CN101293815A (en) * | 2008-06-17 | 2008-10-29 | 浙江大学 | Method for preparing bisphenol A in acidic ion liquid |
| 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 |
-
2015
- 2015-06-10 CN CN201510311750.5A patent/CN105037102A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0889819A (en) * | 1994-09-20 | 1996-04-09 | Mitsubishi Chem Corp | Ion exchange resin |
| CN101293815A (en) * | 2008-06-17 | 2008-10-29 | 浙江大学 | Method for preparing bisphenol A in acidic ion liquid |
| 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》 * |
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