CN1986509A - Bisphenol fluorene synthesizing process catalyzed with solid supported heteropolyacid - Google Patents
Bisphenol fluorene synthesizing process catalyzed with solid supported heteropolyacid Download PDFInfo
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- CN1986509A CN1986509A CNA2006101511724A CN200610151172A CN1986509A CN 1986509 A CN1986509 A CN 1986509A CN A2006101511724 A CNA2006101511724 A CN A2006101511724A CN 200610151172 A CN200610151172 A CN 200610151172A CN 1986509 A CN1986509 A CN 1986509A
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- heteropolyacid
- bisphenol fluorene
- fluorenone
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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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The bisphenol fluorine synthesizing process includes mixing phenol, 9-fluorenone, solid supported heteropoly acid and mercapto carboxylic acid, with phenol/9-fluorenone molar ratio of 6-14 to 1, solid supported heteropoly acid accounting for 5.0-20.0 % of total reactant weight, heteropoly acid/solid carrier weight ratio of 0.3-1 to 1 and mercapto carboxylic acid/9-fluorenone weight ratio of 0.02-0.50 to 1, to react at 60-130 deg.c via stirring for 6-14 hr; filtering the reacted product while it is still hot, and recovering the catalyst; washing the catalyst, merging the washed liquid with the filtrate, crystallizing, filtering, drying, recrystallizing in organic solvent and vacuum drying to obtain bisphenol fluorine crystal. The present invention has product purity as high as 99.8 %, simple post-treatment, less metal corrosion and environmental pollution and recovery of catalyst, and may be used widely in the phenol and 9-fluorenone condensation reaction.
Description
(1) technical field
The present invention relates to organic synthesis and material field, be specifically related to a kind of method with the catalyzed with solid supported heteropolyacid bisphenol fluorene synthesizing.
(2) background technology
Bisphenol fluorene is the fluorenyl compounds that a class contains phenolic hydroxyl structure, it is a polycarbonate synthesis, Resins, epoxy, the important monomer of polycondensation products such as polyester or polyethers, with the bisphenol fluorene is raw material synthetic heat resistance Resins, epoxy, materials such as polycarbonate have good thermostability, high transparent, characteristic such as high refractive index and Yi Rong can be used for preparing the transparent conductive film, alignment films, gas separation membrane, the photoreceptor of photoelectric properties, the high-performance poly zoarium, photo-conductor, heat transfer material, the flame retardant resistance thermoplastic resin, CD, radioprotective polymkeric substance with high temperature resistant property, thermoplasticity heat expansion resin, electrical conductor insulated body and high-temperature resistant coating etc.
The synthesis technique of bisphenol fluorene was under the certain reaction temperature in the past, phenol and Fluorenone carry out condensation reaction under sulfuric acid or gas chlorination hydrogen catalyst and an amount of mercaptan carboxylic acid's catalysis, the crude product that reaction generates is again through the bisphenol fluorene product of solvent treatment acquisition more than 98%.The rapids abundant bright novel method that in Chinese patent CN1617845, proposes a kind of bisphenol fluorene synthesizing in village: promptly under the coexistence of thio-alcohol and hydrochloric acid, make Fluorenone and phenols carry out condensation reaction, make fluorene derivatives.The ratio of Fluorenone and thio-alcohol (weight ratio) is a Fluorenone: thio-alcohol=about 1: 0.01～1: 0.5, the ratio (weight ratio) of the hydrochloric acid in thio-alcohol and the salt sour water is a thio-alcohol: hydrochloric acid=about 1: 0.1～1: 3.As thio-alcohol, can use mercaptan carboxylic acid's (β-Qiu Jibingsuan).This method is marked down and make the excellent high purity fluorene derivatives of the transparency easily, and does not use the hydrogen chloride gas that is difficult to handle.Because reaction process uses hydrochloric acid as catalyzer, maximum shortcoming is serious to equipment corrosion, and production equipment needs expensive erosion resistance material, and production process produces a large amount of spent acid, also need carry out neutralizing treatment, and a large amount of waste water of generation also bring harm to environment.
(3) summary of the invention
The object of the present invention is to provide a kind of lowly to metal equipment corrosion, environmental pollution is little, and processing requirement is lower, the bisphenol fluorene synthetic method of good product quality.
The object of the present invention is achieved like this: phenol, 9-Fluorenone, solid-carrying heteropolyacid and mercaptan carboxylic acid are added in the container, stir, wherein the mol ratio of phenol and 9-Fluorenone is 6～14: 1, solid-carrying heteropolyacid accounts for 5.0%～20.0% of reactant total mass, the mass ratio of heteropolyacid and solid carrier is 0.3～1: 1, the mass ratio of mercaptan carboxylic acid and 9-Fluorenone is 0.02～0.50: 1, under the condition of 60～130 ℃ of temperature of reaction, stirred 6～14 hours, after reaction finishes, with the reactant filtered while hot, reclaim catalyzer; With the methanol aqueous solution washing, together merge in the filtrate, separate out crystallization, to filter, drying is used the organic solvent recrystallization, and vacuum-drying gets the bisphenol fluorene crystal.
The present invention also has some technical characterictics like this:
1, described heteropolyacid is a kind of in phospho-molybdic acid, phospho-wolframic acid, silicomolybdic acid or the silicotungstic acid, its structure is a kind of in 2: 18 serial heteropolyacids of 1: 12 serial heteropolyacid of saturated Keggin structure or unsaturated 1: 11 serial heteropolyacid or Dawson structure, and the molecular formula of heteropolyacid is H
3PW
12O
40, H
4SiW
12O
40, H
3PMo
12O
40, H
4SiMo
12O
40, H
8PMo
11O
39, H
8SiW
11O
39Or H
6P
2Mo
18O
62
2, described solid carrier is gac, molecular sieve or silica gel;
3, described molecular sieve is A type molecular sieve, ZSM-5 molecular sieve, Y zeolite, beta molecular sieve or mercerising molecular sieve;
4, described mercaptan carboxylic acid is Thiovanic acid or thiohydracrylic acid;
5, the employed organic solvent of described recrystallization is toluene, acetone, ethanol or Virahol;
6, described container is the there-necked flask that has reflux exchanger and thermometer.
The present invention is a catalyzer with solid-carrying heteropolyacid and mercaptan carboxylic acid, make phenol and Fluorenone carry out condensation reaction, the synthesis technique flow process is rationally feasible, the technological reaction mild condition, aftertreatment is simple, and catalyst recovery is convenient, product purity is up to 99.8%, the product yield height can solve with sulfuric acid and hydrogenchloride again simultaneously and be metallic corrosion problem and the problem of environmental pollution that catalyzer brings, can be widely used in fluorenone condensation reaction.
(4) specific implementation method
Embodiment 1:
2 gram Fluorenones, 10.44 gram phenol, 0.2ml β-Qiu Jibingsuan, 2.19 are restrained immobilized 12-phospho-wolframic acid, and (molecular formula is H
3PW
12O
40) catalyzer joins successively in the there-necked flask that has reflux exchanger and thermometer and stir, carrier is a gac, the mass ratio of 12-phospho-wolframic acid and gac is 0.6: 1, temperature of reaction is 95 ℃, and the reaction times is 12 hours, the reaction mixture filtered while hot, with the methanol aqueous solution washing, separate out crystal, filter, dry, use acetone recrystallization, vacuum-drying gets the bisphenol fluorene crystal, the bisphenol fluorene yield is 72.5%, and purity can reach 99.8%.
Embodiment 2:
Heteropolyacid in the present embodiment solid-carried catalyst is that (molecular formula is H to the 12-phospho-molybdic acid
3PMo
12O
40), other conditions are with embodiment 1, and the bisphenol fluorene yield is 51.5%, and purity reaches 99.4%.
Embodiment 3:
The present embodiment carrier is the ZSM-5 molecular sieve, and other conditions are with embodiment 1, and the bisphenol fluorene yield is 66.8%, and purity reaches 99.5%.
Claims (7)
1, a kind of method of catalyzed with solid supported heteropolyacid bisphenol fluorene synthesizing, it is characterized in that: phenol, 9-Fluorenone, solid-carrying heteropolyacid and mercaptan carboxylic acid are added in the container, stir, wherein the mol ratio of phenol and 9-Fluorenone is 6～14: 1, solid-carrying heteropolyacid accounts for 5.0%～20.0% of reactant total mass, the mass ratio of heteropolyacid and solid carrier is 0.3～1: 1, the mass ratio of mercaptan carboxylic acid and 9-Fluorenone is 0.02～0.50: 1, under the condition of 60～130 ℃ of temperature of reaction, stirred 6～14 hours, after reaction finishes, with the reactant filtered while hot, reclaim catalyzer; With the methanol aqueous solution washing, together merge in the filtrate, separate out crystallization, to filter, drying is used the organic solvent recrystallization, and vacuum-drying gets the bisphenol fluorene crystal.
2, the method for catalyzed with solid supported heteropolyacid bisphenol fluorene synthesizing according to claim 1, the structure that it is characterized in that described heteropolyacid is a kind of in 2: 18 serial heteropolyacids of 1: 12 serial heteropolyacid of saturated Keggin structure or unsaturated 1: 11 serial heteropolyacid or Dawson structure, and the molecular formula of heteropolyacid is H
3PW
12O
40, H
4SiW
12O
40, H
3PMo
12O
40, H
4SiMo
12O
40, H
8PMo
11O
39, H
8SiW
11O
39Or H
6P
2Mo
18O
62
3, the method for catalyzed with solid supported heteropolyacid bisphenol fluorene synthesizing according to claim 1 is characterized in that described solid carrier is gac, molecular sieve or silica gel.
4, the method for catalyzed with solid supported heteropolyacid bisphenol fluorene synthesizing according to claim 3 is characterized in that described molecular sieve is A type molecular sieve, ZSM-5 molecular sieve, Y zeolite, beta molecular sieve or mercerising molecular sieve.
5, the method for catalyzed with solid supported heteropolyacid bisphenol fluorene synthesizing according to claim 1 is characterized in that described mercaptan carboxylic acid is Thiovanic acid or thiohydracrylic acid.
6, the method for catalyzed with solid supported heteropolyacid bisphenol fluorene synthesizing according to claim 1 is characterized in that the employed organic solvent of described recrystallization is toluene, acetone, ethanol or Virahol.
7, the method for catalyzed with solid supported heteropolyacid bisphenol fluorene synthesizing according to claim 1 is characterized in that described container is the there-necked flask that has reflux exchanger and thermometer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101511724A CN1986509A (en) | 2006-12-20 | 2006-12-20 | Bisphenol fluorene synthesizing process catalyzed with solid supported heteropolyacid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101511724A CN1986509A (en) | 2006-12-20 | 2006-12-20 | Bisphenol fluorene synthesizing process catalyzed with solid supported heteropolyacid |
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|---|---|
| CN1986509A true CN1986509A (en) | 2007-06-27 |
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|---|---|---|---|
| CNA2006101511724A Pending CN1986509A (en) | 2006-12-20 | 2006-12-20 | Bisphenol fluorene synthesizing process catalyzed with solid supported heteropolyacid |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659526A (en) * | 2012-04-11 | 2012-09-12 | 哈尔滨工程大学 | Tetraphenolic hydroxyfluorene compound and preparation method thereof |
| CN104437637A (en) * | 2014-10-31 | 2015-03-25 | 常州大学 | Epoxy resin loaded phosphotungstic acid catalyst as well as preparation method and application thereof |
| CN105001027A (en) * | 2015-07-24 | 2015-10-28 | 上虞日月星科技化学有限公司 | Fluorne compound preparing method |
| CN107698429A (en) * | 2017-09-25 | 2018-02-16 | 大连理工大学 | A kind of method of functionalized ion liquid catalytic synthesis of bisphenol fluorene |
-
2006
- 2006-12-20 CN CNA2006101511724A patent/CN1986509A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659526A (en) * | 2012-04-11 | 2012-09-12 | 哈尔滨工程大学 | Tetraphenolic hydroxyfluorene compound and preparation method thereof |
| CN102659526B (en) * | 2012-04-11 | 2014-08-20 | 哈尔滨工程大学 | Tetraphenolic hydroxyfluorene compound and preparation method thereof |
| CN104437637A (en) * | 2014-10-31 | 2015-03-25 | 常州大学 | Epoxy resin loaded phosphotungstic acid catalyst as well as preparation method and application thereof |
| CN105001027A (en) * | 2015-07-24 | 2015-10-28 | 上虞日月星科技化学有限公司 | Fluorne compound preparing method |
| CN107698429A (en) * | 2017-09-25 | 2018-02-16 | 大连理工大学 | A kind of method of functionalized ion liquid catalytic synthesis of bisphenol fluorene |
| CN107698429B (en) * | 2017-09-25 | 2019-11-26 | 大连理工大学 | A kind of method of functionalized ion liquid catalytic synthesis of bisphenol fluorene |
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Open date: 20070627 |