CN102584541A - Method for preparing bisphenol F by using 1-alkyl-3-methylimidazole acidic ionic liquid - Google Patents
Method for preparing bisphenol F by using 1-alkyl-3-methylimidazole acidic ionic liquid Download PDFInfo
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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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Abstract
The invention relates to a method for preparing bisphenol F by using a 1-alkyl-3-methylimidazole acidic ionic liquid. According to the invention, phenol and formaldehyde are used as raw materials, and the 1-alkyl-3-methylimidazole acidic ionic liquid is used as a solvent and a catalyst, and bisphenol F can be prepared by condensation reaction. As for the method, other organic solvents easy to volatilize are not used, the defects that the reaction time is long, recovery is difficult, the service life is short, the corrosivity is strong and the like when the bisphenol F is subjected to catalytic synthesis by common bronsted acid can be solved, and the method provided by the invention is a novel bisphenol F preparing method which is efficient and environment-friendly.
Description
Technical field
The present invention relates to a kind of method for preparing Bisphenol F.
Background technology
Bisphenol F (BPF) chemical name is the dihydroxyl ditan.It is a kind of important chemical intermediate; Because its particular chemical structural performance; During at synthesizing epoxy type resin, vibrin and as phenolic resin modified dose and fire retardant, it is the made like product of raw material that the heat-moisture resistance of products obtained therefrom, insulativity and processing injection moulding burn that performance such as casting is superior to the dihydroxyphenyl propane.Many excellent properties because of its finished product; Make it be widely used in high solid coating, electronic-grade epoxy resin, injection moulding and burning casting with extraordinary low viscosity resin, high-performance polyester resin with gather synthesizing of carbon resin, and aspects such as STUDY ON THE MODIFICATION OF PENOLIC RESIN agent and high-performance refractory agent.
Catalyzer is the key condition of bisphenol synthesis F.At present, the catalyzer of bisphenol synthesis F has inorganic acids, organic acid, molecular sieve, ion exchange resin and heteropolyacid etc.
Patent JP58177928 etc. have reported with mineral acids such as hydrochloric acid, sulfuric acid to be the method for catalyzer bisphenol synthesis F.This method has corrodibility, many, the violent and unmanageable shortcoming of reaction of side reaction.
It is the method for catalyzer bisphenol synthesis F that patent US4400554 has studied with phosphoric acid.This method is simple, and the Bisphenol F yield that calculates with formaldehyde also has 70%, helps the separation of product and the recycling of catalyzer, but long reaction time, the para-isomeride content of the performance the best in the product is also lower.
Patent report such as patent JP08268943, JP08198790 with organic acid catalysis bisphenol synthesis F such as oxalic acid, acetate, sour aldehyde is than 5～50,60～100 ℃ of temperature; This method reaction temperature with, also lighter to equipment corrosion, but side reaction is a lot; Phenol formaldehyde ratio is too high, and productive rate is relatively low.
Patent JP11269113 has reported with the zeolite molecular sieve to be the method for catalyzer bisphenol synthesis F; It is the method for catalyzer bisphenol synthesis F with 60: 1～150: 1 mesopore molecular sieve class of silica alumina ratio that patent CN101987812A discloses a kind of; This class methods product separates and the catalyst recovery ratio is easier to; But phenol formaldehyde ratio and temperature of reaction are higher, react restive, and raw material consumption is bigger.
Patent JP 6340565 has reported the method with acid catalyst and the common catalysis bisphenol synthesis of urea-formaldehyde resin F; The characteristics of this method are to improve 4,4 '-selectivity of isomer, easy recovery after the urea-formaldehyde resin reaction simultaneously; But the resin repeat usage is low, active decline soon.
Reported that at present bisphenol synthesis F method all always exists phenol formaldehyde ratio height, productive rate and shortcomings such as selectivity is low, side reaction is many, long reaction time, corrodibility is strong, catalyst activity reduction is fast, catalyst life is short; Thereby cause the Bisphenol F production cost high, influenced the sizable application of this product.Therefore, be badly in need of the Bisphenol F synthetic novel method of developing low-cost, environmental protection.
Summary of the invention
The purpose of this invention is to provide and a kind ofly prepare the method for Bisphenol F with 1-alkyl-3-Methylimidazole class acidic ion liquid.
A kind ofly prepare the method for Bisphenol F, it is characterized in that with 1-alkyl-3-Methylimidazole class acidic ion liquid: with 1-alkyl-3-Methylimidazole class acidic ion liquid is catalyzer and solvent, phenol and formaldehyde condensation bisphenol synthesis F; The steps include: 1-alkyl-3-Methylimidazole class acidic ion liquid is joined in the container that phenol is housed; The powerful stirring makes it to mix, and the formaldehyde solution of handling is added drop-wise in 1-alkyl-3-Methylimidazole class acidic ion liquid/phenol mixed solution nitrogen protection; Isothermal reaction; Reaction finishes postcooling to room temperature, and 1-alkyl-3-Methylimidazole class acid ion ionic liquid recycle is reclaimed in the reaction solution washing, and remaining organic phase reclaims phenol through underpressure distillation; Obtain crude product, behind the YLENE recrystallization, obtain the Bisphenol F product.
Describedly a kind ofly prepare the method for Bisphenol F, it is characterized in that with 1-alkyl-3-Methylimidazole class acidic ion liquid: the mol ratio of 1-alkyl-3-Methylimidazole class acidic ion liquid and formaldehyde is 0.5: 1～4: 1.
Describedly a kind ofly prepare the method for Bisphenol F, it is characterized in that with 1-alkyl-3-Methylimidazole class acidic ion liquid: the mol ratio of phenol and formaldehyde is 4: 1～12: 1.
Describedly a kind ofly prepare the method for Bisphenol F, it is characterized in that with 1-alkyl-3-Methylimidazole class acidic ion liquid: temperature of reaction is controlled at 40～150 ℃, and the reaction times is 0.5～8 hour.
Saidly a kind ofly prepare the method for Bisphenol F, it is characterized in that with 1-alkyl-3-Methylimidazole class acidic ion liquid: described 1-alkyl-3-Methylimidazole class acidic ion liquid, structural formula does
Positively charged ion is 1-alkyl-3-Methylimidazole ion in the formula, as n=0,1,2,3,4,5, pairing imidazoles positively charged ion is respectively [Hmin] 6 the time
+, [Emin]
+, [Bmin]
+, [C
6Min]
+, [C
8Min]
+, [C
10Min]
+, [C
12Min]
+Negatively charged ion x is a kind of in bisulfate ion, dihydrogen phosphate ions, nitrate ion or the fluoro boron acid ion.
Saidly a kind ofly prepare the method for Bisphenol F, it is characterized in that with 1-alkyl-3-Methylimidazole class acidic ion liquid: described 1-alkyl-3-Methylimidazole class acidic ion liquid alkyl chain length is 4～12 even number chain.
Advantage of the present invention is: the change of 1-alkyl-3-Methylimidazole class acidic ion liquid alkyl chain length and the rule that the Bisphenol F productive rate changes have been verified in (1), and the Bisphenol F yield can reach more than 85% when alkyl chain length is 4～8 even number chain; (2) be that catalyzer has improved speed of reaction with 1-alkyl-3-Methylimidazole class acidic ion liquid, shortened the reaction times; (3) be catalyzer and reaction solvent with the stable 1-alkyl of physicochemical property-3-Methylimidazole class acidic ion liquid, phenol and formaldehyde are raw material condensation bisphenol synthesis F; (4) reaction process is not used extra catalyst and any volatile, deleterious organic solvent; (5) 1-alkyl-3-Methylimidazole class acidic ion liquid be catalyzer also be solvent, easy recovery is utilized again, thereby has avoided using volatile organic solvent to be difficult to recycle the defective low with utilization ratio; (6) long service life of employed 1-alkyl-3-Methylimidazole class acidic ion liquid, catalytic activity keep good, and repeating utilization factor is high; (7) employed catalyzer almost has no corrodibility, and reaction and conversion unit are not had particular requirement; (8) reclaiming the phenol of 1-alkyl-3-Methylimidazole class acidic ion liquid and surplus through simple washing and underpressure distillation, operate simple and easyly, is a kind of novel method of preparation Bisphenol F of environmental protection.
Description of drawings
Fig. 1 is the comparison diagram that product and Bisphenol F standard specimen infrared chromatography are analyzed collection of illustrative plates.
Embodiment
Embodiment 1
Get 0.1mol 1-alkyl-3-Methylimidazole class acidic ion liquid [Hmin] [HSO
4] and 0.6mol phenol add in the there-necked flask, be warmed up to 90 ℃, drip 0.1mol formaldehyde.And sampling analysis when reaction 0.5h, 1h, 2h, 3h, 4h, 5h, 6h respectively.After reaction finishes, cooling, washing layering.Water is crossed the decompression rotary evaporation part of anhydrating, and last ionic liquid recycles; Organic phase reclaims phenol through underpressure distillation, obtains crude product, behind the YLENE recrystallization, obtains the Bisphenol F product, and yield is 70.68%.
Embodiment 2
Get 0.1mol 1-alkyl-3-Methylimidazole class acidic ion liquid [Emin] [HSO
4] and 0.7mol phenol add in the there-necked flask, be warmed up to 80 ℃, drip 0.1mol formaldehyde.And sampling analysis when reaction 0.5h, 1h, 2h, 3h, 4h, 5h, 6h respectively.After reaction finishes, cooling, washing layering.Water is crossed the decompression rotary evaporation part of anhydrating, and last ionic liquid recycles; Organic phase reclaims phenol through underpressure distillation, obtains crude product, behind the YLENE recrystallization, obtains the Bisphenol F product, and yield is 65.53%.
Embodiment 3
Get 0.1mol 1-alkyl-3-Methylimidazole class acidic ion liquid [Bmin] [HSO
4] and 0.8mol phenol add in the there-necked flask, be warmed up to 60 ℃, drip 0.05mol formaldehyde.And sampling analysis when reaction 0.5h, 1h, 2h, 3h, 4h, 5h, 6h respectively.After reaction finishes, cooling, washing layering.Water is crossed the decompression rotary evaporation part of anhydrating, and last ionic liquid recycles; Organic phase reclaims phenol through underpressure distillation, obtains crude product, behind the YLENE recrystallization, obtains the Bisphenol F product, and yield is 69.58%.
Embodiment 4
Get 0.1mol 1-alkyl-3-Methylimidazole class acidic ion liquid [C
6Min] [HSO
4] and 0.6mol phenol add in the there-necked flask, be warmed up to 90 ℃, drip 0.1mol formaldehyde.And sampling analysis when reaction 0.5h, 1h, 2h, 3h, 4h, 5h, 6h respectively.After reaction finishes, cooling, washing layering.Water is crossed the decompression rotary evaporation part of anhydrating, and last ionic liquid recycles; Organic phase reclaims phenol through underpressure distillation, obtains crude product, behind the YLENE recrystallization, obtains the Bisphenol F product, and yield is 85.35%.
Embodiment 5
Get 0.1mol 1-alkyl-3-Methylimidazole class acidic ion liquid [C
12Min] [HSO
4] and 0.7mol phenol add in the there-necked flask, be warmed up to 90 ℃, drip 0.05mol formaldehyde.And sampling analysis when reaction 0.5h, 1h, 2h, 3h, 4h, 5h, 6h respectively.After reaction finishes, cooling, washing layering.Water is crossed the decompression rotary evaporation part of anhydrating, and last ionic liquid recycles; Organic phase reclaims phenol through underpressure distillation, obtains crude product, behind the YLENE recrystallization, obtains the Bisphenol F product, and yield is 80.52%.
Embodiment 6
Get 0.1mol 1-alkyl-3-Methylimidazole class acidic ion liquid [C
12Min] [H
2PO
4] and 0.6mol phenol add in the there-necked flask, be warmed up to 90 ℃, drip 0.05mol formaldehyde.And sampling analysis when reaction 0.5h, 1h, 2h, 3h, 4h, 5h, 6h respectively.After reaction finishes, cooling, washing layering.Water is crossed the decompression rotary evaporation part of anhydrating, and last ionic liquid recycles; Organic phase reclaims phenol through underpressure distillation, obtains crude product, behind the YLENE recrystallization, obtains the Bisphenol F product, and yield is 49.67%.
Embodiment 7
Get 0.1mol 1-alkyl-3-Methylimidazole class acidic ion liquid [Hmin] [NO
3] and 0.6mol phenol add in the there-necked flask, be warmed up to 90 ℃, drip 0.1mol formaldehyde.And sampling analysis when reaction 0.5h, 1h, 2h, 3h, 4h, 5h, 6h respectively.After reaction finishes, cooling, washing layering.Water is crossed the decompression rotary evaporation part of anhydrating, and last ionic liquid recycles; Organic phase reclaims phenol through underpressure distillation, obtains crude product, behind the YLENE recrystallization, obtains the Bisphenol F product, and yield is 30.5%.
Embodiment 8
Get 0.1mol 1-alkyl-3-Methylimidazole class acidic ion liquid [Hmin] [BF
4] and 0.6mol phenol add in the there-necked flask, be warmed up to 90 ℃, drip 0.1mol formaldehyde.And sampling analysis when reaction 0.5h, 1h, 2h, 3h, 4h, 5h, 6h respectively.After reaction finishes, cooling, washing layering.Water is crossed the decompression rotary evaporation part of anhydrating, and last ionic liquid recycles; Organic phase reclaims phenol through underpressure distillation, obtains crude product, behind the YLENE recrystallization, obtains the Bisphenol F product, and yield is 30.69%.
Embodiment 9
Get 0.05mol 1-alkyl-3-Methylimidazole class acidic ion liquid [C
6Min] [HSO
4] and 0.3mol phenol add in the there-necked flask, be warmed up to 90 ℃, drip 0.05mol formaldehyde.And sampling analysis when reaction 0.5h, 1h, 2h, 3h, 4h, 5h, 6h respectively.After reaction finishes, cooling, washing layering.Water is crossed the decompression rotary evaporation part of anhydrating, and last ionic liquid recycles; Organic phase reclaims phenol through underpressure distillation, obtains crude product, behind the YLENE recrystallization, obtains the Bisphenol F product, and yield is 82.35%.
As shown in Figure 1; Last figure is an embodiment product infrared colour spectrogram among Fig. 1; Figure below is a Bisphenol F standard infrared colour spectrogram, and through comparative analysis embodiment product infrared colour spectrogram and Bisphenol F standard specimen infrared colour spectrogram basically identical, products therefrom is a Bisphenol F in the illustrative embodiment.
Claims (6)
1. one kind prepares the method for Bisphenol F, it is characterized in that with 1-alkyl-3-Methylimidazole class acidic ion liquid: with 1-alkyl-3-Methylimidazole class acidic ion liquid is catalyzer and solvent, phenol and formaldehyde condensation bisphenol synthesis F; The steps include: 1-alkyl-3-Methylimidazole class acidic ion liquid adding is equipped with in the container of phenol; The powerful stirring makes it to mix, and the formaldehyde solution of handling is added drop-wise in 1-alkyl-3-Methylimidazole class acidic ion liquid/phenol mixed solution nitrogen protection; Isothermal reaction; Reaction finishes postcooling to room temperature, and 1-alkyl-3-Methylimidazole class acidic ion liquid recycle is reclaimed in the reaction solution washing, and remaining organic phase reclaims phenol through underpressure distillation; Obtain crude product, behind the YLENE recrystallization, obtain the Bisphenol F product.
2. according to claim 1ly a kind ofly prepare the method for Bisphenol F, it is characterized in that with 1-alkyl-3-Methylimidazole class acidic ion liquid: the mol ratio of 1-alkyl-3-Methylimidazole class acidic ion liquid and formaldehyde is 0.5: 1～4: 1.
3. according to claim 1ly a kind ofly prepare the method for Bisphenol F, it is characterized in that with 1-alkyl-3-Methylimidazole class acidic ion liquid: the mol ratio of phenol and formaldehyde is 4: 1～12: 1.
4. according to claim 1ly a kind ofly prepare the method for Bisphenol F, it is characterized in that with 1-alkyl-3-Methylimidazole class acidic ion liquid: temperature of reaction is controlled at 40～150 ℃, and the reaction times is 0.5～8 hour.
5. a kind ofly prepare the method for Bisphenol F, it is characterized in that according to claim 1 is said with 1-alkyl-3-Methylimidazole class acidic ion liquid: described 1-alkyl-3-Methylimidazole class acidic ion liquid, structural formula is:
Positively charged ion is 1-alkyl-3-Methylimidazole ion in the formula, and pairing imidazoles positively charged ion is respectively [Hmin] when n is respectively 0,1,2,3,4,5,6
+, [Emin]
+, [Bmin]
+, [C
6Min]
+, [C
8Min]
+, [C
10Min]
+, [C
12Min]
+Negatively charged ion x is a kind of in bisulfate ion, dihydrogen phosphate ions, nitrate ion or the fluoro boron acid ion.
6. a kind ofly prepare the method for Bisphenol F, it is characterized in that with 1-alkyl-3-Methylimidazole class acidic ion liquid according to claim 5 is said: described 1-alkyl-3-Methylimidazole class acidic ion liquid alkyl chain length is 4～12 even number chain.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103896742A (en) * | 2014-01-21 | 2014-07-02 | 湘潭大学 | Method for catalytic synthesis of bisphenol F by using cation exchange resin immobilized ionic liquid |
| CN104140361A (en) * | 2014-06-30 | 2014-11-12 | 湘潭大学 | Method for synthesizing bisphenol F under catalysis of phosphotungstic acid imidazolium salt |
| CN104876804A (en) * | 2015-06-04 | 2015-09-02 | 湘潭大学 | Preparation method of high-content 4, 4 minute-isomer bisphenol F |
| CN105016980A (en) * | 2014-04-21 | 2015-11-04 | 湘潭大学 | High-selectivity catalytic synthesis method for 4, 4'-bisphenol F |
| CN105037102A (en) * | 2015-06-10 | 2015-11-11 | 湖南师范大学 | Method for synthesizing bisphenol F by using amine bisulphate as catalyst |
| CN105272827A (en) * | 2015-03-20 | 2016-01-27 | 湖南师范大学 | Catalysis method for synthesizing bisphenol F |
| CN105884584A (en) * | 2014-12-25 | 2016-08-24 | 江南大学 | Novel fluoro bisphenol F and preparing method thereof |
| CN112574007A (en) * | 2020-12-14 | 2021-03-30 | 江南大学 | Novel cyclohexylimine ionic liquid and method for catalyzing synthesis of butyl citrate and bisphenol F |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103896742A (en) * | 2014-01-21 | 2014-07-02 | 湘潭大学 | Method for catalytic synthesis of bisphenol F by using cation exchange resin immobilized ionic liquid |
| CN105016980A (en) * | 2014-04-21 | 2015-11-04 | 湘潭大学 | High-selectivity catalytic synthesis method for 4, 4'-bisphenol F |
| CN105016980B (en) * | 2014-04-21 | 2017-02-08 | 湘潭大学 | High-selectivity catalytic synthesis method for 4, 4'-bisphenol F |
| CN104140361A (en) * | 2014-06-30 | 2014-11-12 | 湘潭大学 | Method for synthesizing bisphenol F under catalysis of phosphotungstic acid imidazolium salt |
| CN104140361B (en) * | 2014-06-30 | 2015-09-23 | 湘潭大学 | A kind of phospho-wolframic acid imidazole salts catalyzes and synthesizes the method for Bisphenol F |
| CN105884584A (en) * | 2014-12-25 | 2016-08-24 | 江南大学 | Novel fluoro bisphenol F and preparing method thereof |
| CN105272827A (en) * | 2015-03-20 | 2016-01-27 | 湖南师范大学 | Catalysis method for synthesizing bisphenol F |
| CN105272827B (en) * | 2015-03-20 | 2017-03-15 | 湖南师范大学 | A kind of catalysis process of bisphenol synthesis F |
| CN104876804A (en) * | 2015-06-04 | 2015-09-02 | 湘潭大学 | Preparation method of high-content 4, 4 minute-isomer bisphenol F |
| CN105037102A (en) * | 2015-06-10 | 2015-11-11 | 湖南师范大学 | Method for synthesizing bisphenol F by using amine bisulphate as catalyst |
| CN112574007A (en) * | 2020-12-14 | 2021-03-30 | 江南大学 | Novel cyclohexylimine ionic liquid and method for catalyzing synthesis of butyl citrate and bisphenol F |
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