CN102584541B - A kind of 1-alkyl-3-methylimidazole acidic ionic liquid prepares the method for Bisphenol F - Google Patents
A kind of 1-alkyl-3-methylimidazole acidic ionic liquid prepares the method for Bisphenol F Download PDFInfo
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- CN102584541B CN102584541B CN201210015375.6A CN201210015375A CN102584541B CN 102584541 B CN102584541 B CN 102584541B CN 201210015375 A CN201210015375 A CN 201210015375A CN 102584541 B CN102584541 B CN 102584541B
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- ionic liquid
- alkyl
- methylimidazole
- bisphenol
- acidic ionic
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- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The present invention relates to a kind of method that 1-alkyl-3-methylimidazole acidic ionic liquid prepares Bisphenol F.The method for raw material with phenol and formaldehyde, doubles as solvent and catalyzer with 1-alkyl-3-methylimidazole acidic ionic liquid, prepares Bisphenol F through condensation reaction.The method does not use other volatile organic solvent, and the long reaction time existed when solving common Protic Acid Catalyzed bisphenol synthesis F, difficulty reclaim, and the shortcomings such as the life-span is short, corrodibility is strong are a kind of Bisphenol F preparation methods of new and effective environmental protection.
Description
Technical field
The present invention relates to a kind of method preparing Bisphenol F.
Background technology
Bisphenol F (BPF) chemical name is dihydroxydiphenyl methane.It is a kind of important chemical intermediate, due to the chemical structure characteristic that it is special, synthesizing epoxy type resin, vibrin and as phenolic resin modified dose and fire retardant time, the heat-moisture resistance of products obtained therefrom, insulativity and processing injection moulding are burnt the performances such as casting and are better than taking dihydroxyphenyl propane as the made like product of raw material.Because of many excellent properties of its finished product, make it be widely used in high coating, electronic-grade epoxy resin, injection moulding and burning admittedly and cast the synthesis with extraordinary low viscosity resin, high-performance polyester resin and poly-carbon resin, and the aspect such as the properties-correcting agent of resol 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. report with the method for the mineral acid such as hydrochloric acid, sulfuric acid for catalyzer bisphenol synthesis F.The method have corrodibility, side reaction many, react violent and unmanageable shortcoming.
It is the method for catalyzer bisphenol synthesis F that patent US4400554 have studied with phosphoric acid.The method is simple, also has 70%, be conducive to the separation of product and the recycling of catalyzer with the Bisphenol F yield that formaldehyde calculates, but long reaction time, the para-isomeride content of the performance the best in product is also lower.
Patent JP08268943, JP08198790 etc. patent reports with the organic acid catalysis such as oxalic acid, acetic acid bisphenol synthesis F, sour aldehyde than 5 ~ 50, temperature 60 ~ 100 DEG C, the method reaction temperature and, also comparatively light to equipment corrosion, but side reaction is a lot, phenol formaldehyde ratio is too high, and productive rate is relatively low.
It is the method for catalyzer bisphenol synthesis F that patent JP11269113 reports with zeolite molecular sieve, patent CN101987812A discloses the method that one take the mesopore molecular sieve class of silica alumina ratio 60: 1 ~ 150: 1 as catalyzer bisphenol synthesis F, this class methods product separation and catalyst recovery ratio are easier to, but phenol formaldehyde ratio and temperature of reaction higher, react restive, raw material consumption is larger.
Patent JP6340565 reports the method by acid catalyst and urea-formaldehyde resin co-catalysis bisphenol synthesis F, the feature of the method is to improve 4, the selectivity of 4 '-isomer, easily reclaims after urea-formaldehyde resin reaction simultaneously, but resin repeat usage is low, and activity decrease is fast.
Reported at present that bisphenol synthesis F method all always exists that phenol formaldehyde ratio is high, productive rate and the shortcoming such as selectivity is low, side reaction is many, long reaction time, corrodibility are strong, catalyst activity reduction is fast, catalyst life is short, thus cause Bisphenol F production cost high, have impact on the sizable application of this product.Therefore, the novel method of the Bisphenol F synthesis of urgent need developing low-cost, environmental protection.
Summary of the invention
The object of this invention is to provide a kind of method that 1-alkyl-3-methylimidazole acidic ionic liquid prepares Bisphenol F.
A kind of 1-alkyl-3-methylimidazole acidic ionic liquid prepares the method for Bisphenol F, it is characterized in that: with 1-alkyl-3-methylimidazole acidic ionic liquid for catalysts and solvents, phenol and formaldehyde condensation bisphenol synthesis F, the steps include: 1-alkyl-3-methylimidazole acidic ionic liquid to join to be equipped with in the container of phenol, strong stirring makes it to mix, the formaldehyde solution processed is added drop-wise in 1-alkyl-3-methylimidazole acidic ionic liquid/phenol mixed solution, nitrogen protection, isothermal reaction, reaction terminates rear cool to room temperature, the recycle of 1-alkyl-3-methylimidazole acid ion ionic liquid is reclaimed in reaction solution washing, remaining organic phase reclaims phenol by underpressure distillation, obtain crude product, Bisphenol F product is obtained after dimethylbenzene recrystallization.
Described a kind of 1-alkyl-3-methylimidazole acidic ionic liquid prepares the method for Bisphenol F, it is characterized in that: the mol ratio of 1-alkyl-3-methylimidazole acidic ionic liquid and formaldehyde is 0.5: 1 ~ 4: 1.
Described a kind of 1-alkyl-3-methylimidazole acidic ionic liquid prepares the method for Bisphenol F, it is characterized in that: the mol ratio of phenol and formaldehyde is 4: 1 ~ 12: 1.
Described a kind of 1-alkyl-3-methylimidazole acidic ionic liquid prepares the method for Bisphenol F, it is characterized in that: temperature of reaction controls at 40 ~ 150 DEG C, and the reaction times is 0.5 ~ 8 hour.
Described a kind of 1-alkyl-3-methylimidazole acidic ionic liquid prepares the method for Bisphenol F, it is characterized in that: described 1-alkyl-3-methylimidazole acidic ionic liquid, structural formula is
Formula cationic is 1-alkyl-3-Methylimidazole ion, when n=0,1,2,3,4,5,6 time corresponding alkyl imidazolium cation be respectively [Hmim]
+, [Emim]
+, [Bmim]
+, [C
6mim]
+, [C
8mim]
+, [C
10mim]
+, [C
12mim]
+; Negatively charged ion x is the one in bisulfate ion, dihydrogen phosphate ions, nitrate ion or fluoro boron acid ion.
Described a kind of 1-alkyl-3-methylimidazole acidic ionic liquid prepares the method for Bisphenol F, it is characterized in that: described 1-alkyl-3-methylimidazole acidic ionic liquid alkyl chain length is the even number chain of 4 ~ 12.
Advantage of the present invention is: (1) has verified the rule that the change of 1-alkyl-3-methylimidazole acidic ionic liquid alkyl chain length and Bisphenol F productive rate change, and when alkyl chain length is the even number chain of 4 ~ 8, Bisphenol F yield can reach more than 85%; (2) improve speed of reaction with 1-alkyl-3-methylimidazole acidic ionic liquid for catalyzer, shorten the reaction times; (3) with the stable 1-alkyl-3-methylimidazole acidic ionic liquid of physicochemical property for catalyzer and reaction solvent, phenol and formaldehyde are raw material condensation bisphenol synthesis F; (4) reaction process does not use extra catalyst and any volatile, poisonous organic solvent; (5) 1-alkyl-3-methylimidazole acidic ionic liquid is catalyzer is also solvent, easy recycling, thus avoids and use volatile organic solvent to be difficult to recycle and the low defect of utilization ratio; (6) long service life of the 1-alkyl-3-methylimidazole acidic ionic liquid used, catalytic activity keeps good, and repeating utilization factor is high; (7) catalyzer used almost without any corrodibility, to reaction and conversion unit without particular requirement; (8) reclaim 1-alkyl-3-methylimidazole acidic ionic liquid and superfluous phenol by simple washing and underpressure distillation, operating simple and easy, is a kind of novel method of preparation Bisphenol F of environmental protection.
Accompanying drawing explanation
Fig. 1 is the comparison diagram that product and Bisphenol F standard specimen infrared chromatography analyze collection of illustrative plates.
Embodiment
Embodiment 1
Get 0.1mol1-alkyl-3-methylimidazole acidic ionic liquid [Hmim] [HSO
4] and 0.6mol phenol add in there-necked flask, be warmed up to 90 DEG C, drip 0.1mol formaldehyde.And respectively react 0.5h, 1h, 2h, 3h, 4h, 5h, 6h time sampling analysis.After reaction terminates, cooling, washing layering.Aqueous phase to be anhydrated part by decompression rotary evaporation, and remaining ionic liquid recycles; Organic phase reclaims phenol by underpressure distillation, obtains crude product, obtains Bisphenol F product after dimethylbenzene recrystallization, and yield is 70.68%.
Embodiment 2
Get 0.1mol1-alkyl-3-methylimidazole acidic ionic liquid [Emim] [HSO
4] and 0.7mol phenol add in there-necked flask, be warmed up to 80 DEG C, drip 0.1mol formaldehyde.And respectively react 0.5h, 1h, 2h, 3h, 4h, 5h, 6h time sampling analysis.After reaction terminates, cooling, washing layering.Aqueous phase to be anhydrated part by decompression rotary evaporation, and remaining ionic liquid recycles; Organic phase reclaims phenol by underpressure distillation, obtains crude product, obtains Bisphenol F product after dimethylbenzene recrystallization, and yield is 65.53%.
Embodiment 3
Get 0.1mol1-alkyl-3-methylimidazole acidic ionic liquid [Bmim] [HSO
4] and 0.8mol phenol add in there-necked flask, be warmed up to 60 DEG C, drip 0.05mol formaldehyde.And respectively react 0.5h, 1h, 2h, 3h, 4h, 5h, 6h time sampling analysis.After reaction terminates, cooling, washing layering.Aqueous phase to be anhydrated part by decompression rotary evaporation, and remaining ionic liquid recycles; Organic phase reclaims phenol by underpressure distillation, obtains crude product, obtains Bisphenol F product after dimethylbenzene recrystallization, and yield is 69.58%.
Embodiment 4
Get 0.1mol1-alkyl-3-methylimidazole acidic ionic liquid [C
6mim] [HSO
4] and 0.6mol phenol add in there-necked flask, be warmed up to 90 DEG C, drip 0.1mol formaldehyde.And respectively react 0.5h, 1h, 2h, 3h, 4h, 5h, 6h time sampling analysis.After reaction terminates, cooling, washing layering.Aqueous phase to be anhydrated part by decompression rotary evaporation, and remaining ionic liquid recycles; Organic phase reclaims phenol by underpressure distillation, obtains crude product, obtains Bisphenol F product after dimethylbenzene recrystallization, and yield is 85.35%.
Embodiment 5
Get 0.1mol1-alkyl-3-methylimidazole acidic ionic liquid [C
12mim] [HSO
4] and 0.7mol phenol add in there-necked flask, be warmed up to 90 DEG C, drip 0.05mol formaldehyde.And respectively react 0.5h, 1h, 2h, 3h, 4h, 5h, 6h time sampling analysis.After reaction terminates, cooling, washing layering.Aqueous phase to be anhydrated part by decompression rotary evaporation, and remaining ionic liquid recycles; Organic phase reclaims phenol by underpressure distillation, obtains crude product, obtains Bisphenol F product after dimethylbenzene recrystallization, and yield is 80.52%.
Embodiment 6
Get 0.1mol1-alkyl-3-methylimidazole acidic ionic liquid [C
12mim] [H
2pO
4] and 0.6mol phenol add in there-necked flask, be warmed up to 90 DEG C, drip 0.05mol formaldehyde.And respectively react 0.5h, 1h, 2h, 3h, 4h, 5h, 6h time sampling analysis.After reaction terminates, cooling, washing layering.Aqueous phase to be anhydrated part by decompression rotary evaporation, and remaining ionic liquid recycles; Organic phase reclaims phenol by underpressure distillation, obtains crude product, obtains Bisphenol F product after dimethylbenzene recrystallization, and yield is 49.67%.
Embodiment 7
Get 0.1mol1-alkyl-3-methylimidazole acidic ionic liquid [Hmim] [NO
3] and 0.6mol phenol add in there-necked flask, be warmed up to 90 DEG C, drip 0.1mol formaldehyde.And respectively react 0.5h, 1h, 2h, 3h, 4h, 5h, 6h time sampling analysis.After reaction terminates, cooling, washing layering.Aqueous phase to be anhydrated part by decompression rotary evaporation, and remaining ionic liquid recycles; Organic phase reclaims phenol by underpressure distillation, obtains crude product, obtains Bisphenol F product after dimethylbenzene recrystallization, and yield is 30.5%.
Embodiment 8
Get 0.1mol1-alkyl-3-methylimidazole acidic ionic liquid [Hmim] [BF
4] and 0.6mol phenol add in there-necked flask, be warmed up to 90 DEG C, drip 0.1mol formaldehyde.And respectively react 0.5h, 1h, 2h, 3h, 4h, 5h, 6h time sampling analysis.After reaction terminates, cooling, washing layering.Aqueous phase to be anhydrated part by decompression rotary evaporation, and remaining ionic liquid recycles; Organic phase reclaims phenol by underpressure distillation, obtains crude product, obtains Bisphenol F product after dimethylbenzene recrystallization, and yield is 30.69%.
Embodiment 9
Get 0.05mol1-alkyl-3-methylimidazole acidic ionic liquid [C
6mim] [HSO
4] and 0.3mol phenol add in there-necked flask, be warmed up to 90 DEG C, drip 0.05mol formaldehyde.And respectively react 0.5h, 1h, 2h, 3h, 4h, 5h, 6h time sampling analysis.After reaction terminates, cooling, washing layering.Aqueous phase to be anhydrated part by decompression rotary evaporation, and remaining ionic liquid recycles; Organic phase reclaims phenol by underpressure distillation, obtains crude product, obtains Bisphenol F product after dimethylbenzene recrystallization, and yield is 82.35%.
As shown in Figure 1, in Fig. 1, upper figure is embodiment product infrared colour spectrogram, figure below is Bisphenol F standard infrared colour spectrogram, by comparative analysis embodiment product infrared colour spectrogram and Bisphenol F standard specimen infrared colour spectrogram basically identical, illustrate that in embodiment, products therefrom is Bisphenol F.
Claims (1)
1. prepare the method for Bisphenol F with 1-alkyl-3-methylimidazole acidic ionic liquid for one kind, it is characterized in that: with 1-alkyl-3-methylimidazole acidic ionic liquid for catalysts and solvents, phenol and formaldehyde condensation bisphenol synthesis F, the steps include: 1-alkyl-3-methylimidazole acidic ionic liquid to add to be equipped with in the container of phenol, strong stirring makes it to mix, formaldehyde solution is added drop-wise in 1-alkyl-3-methylimidazole acidic ionic liquid/phenol mixed solution, nitrogen protection, isothermal reaction, reaction terminates rear cool to room temperature, the recycle of 1-alkyl-3-methylimidazole acidic ionic liquid is reclaimed in reaction solution washing, remaining organic phase reclaims phenol by underpressure distillation, obtain crude product, Bisphenol F product is obtained after dimethylbenzene recrystallization,
Described 1-alkyl-3-methylimidazole acidic ionic liquid is [C
6mim] [HSO
4], [C
12mim] [HSO
4] in a kind of or two kinds, the mol ratio of ionic liquid and formaldehyde is 0.5: 1 ~ 4: 1, and the mol ratio of phenol and formaldehyde is 4: 1 ~ 12: 1, and temperature of reaction controls at 60 ~ 90 DEG C, and the reaction times is 0.5 ~ 6 hour.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103896742B (en) * | 2014-01-21 | 2015-12-02 | 湘潭大学 | A kind of Zeo-karb solid-loaded ionic-liquid catalyzes and synthesizes the method for Bisphenol F |
| CN105016980B (en) * | 2014-04-21 | 2017-02-08 | 湘潭大学 | High-selectivity catalytic synthesis method for 4, 4'-bisphenol F |
| 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 |
| CN105272827B (en) * | 2015-03-20 | 2017-03-15 | 湖南师范大学 | A kind of catalysis process of bisphenol synthesis F |
| CN104876804B (en) * | 2015-06-04 | 2017-03-08 | 湘潭大学 | A kind of preparation method of high 4,4 ' content of 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 |
| CN112574007B (en) * | 2020-12-14 | 2022-03-29 | 江南大学 | Novel cyclohexylimine ionic liquid and method for catalyzing synthesis of butyl citrate and bisphenol F |
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| CN1160704A (en) * | 1996-03-22 | 1997-10-01 | 沈阳化工综合利用研究所 | Synthesis technology of bisphenol F |
| JP2006008634A (en) * | 2004-06-29 | 2006-01-12 | Nippon Steel Chem Co Ltd | Method for producing bisphenols |
| CN101293815A (en) * | 2008-06-17 | 2008-10-29 | 浙江大学 | Method for preparing bisphenol A in acidic ion liquid |
| CN101440022A (en) * | 2008-11-06 | 2009-05-27 | 厦门大学 | Method for synthesizing high content of 4,4'-dihydroxydiphenylmethane by one-step method |
| CN101564662A (en) * | 2009-03-18 | 2009-10-28 | 河北工业大学 | Method for synthesizing alkylphenol-polyethenoxy ether terpolymer surfactant |
| CN101987812A (en) * | 2009-08-02 | 2011-03-23 | 中国石油化工集团公司 | Method for preparing bisphenol F |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19703934C2 (en) * | 1997-02-04 | 1999-05-20 | Degussa | Process for the selective production of 2,2'-bis (4-hydroxyphenyl) propanes |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1160704A (en) * | 1996-03-22 | 1997-10-01 | 沈阳化工综合利用研究所 | Synthesis technology of bisphenol F |
| JP2006008634A (en) * | 2004-06-29 | 2006-01-12 | Nippon Steel Chem Co Ltd | Method for producing bisphenols |
| CN101293815A (en) * | 2008-06-17 | 2008-10-29 | 浙江大学 | Method for preparing bisphenol A in acidic ion liquid |
| CN101440022A (en) * | 2008-11-06 | 2009-05-27 | 厦门大学 | Method for synthesizing high content of 4,4'-dihydroxydiphenylmethane by one-step method |
| CN101564662A (en) * | 2009-03-18 | 2009-10-28 | 河北工业大学 | Method for synthesizing alkylphenol-polyethenoxy ether terpolymer surfactant |
| CN101987812A (en) * | 2009-08-02 | 2011-03-23 | 中国石油化工集团公司 | Method for preparing bisphenol F |
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