CN104370669B - A kind of synthetic method of diaryl hexafluoropropane compound - Google Patents
A kind of synthetic method of diaryl hexafluoropropane compound Download PDFInfo
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- CN104370669B CN104370669B CN201410696994.5A CN201410696994A CN104370669B CN 104370669 B CN104370669 B CN 104370669B CN 201410696994 A CN201410696994 A CN 201410696994A CN 104370669 B CN104370669 B CN 104370669B
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Abstract
The invention provides a kind of synthetic method of diaryl hexafluoropropane compound, it is characterized in that, aromatic hydrocarbon is first mixed in the reactor with anhydrous hydrogen fluoride, then adds catalyzer, then add Propylene oxide hexafluoride, carry out afterwards stirring and heating; After reaction terminates, removed by hydrogen fluoride, the remaining product of institute is refined, and obtains diaryl hexafluoropropane compound product; Wherein, described catalyzer is one or more in antimony halides and halogenated titanium series catalysts.Method of the present invention makes Propylene oxide hexafluoride isomerization and is merged in an operation stage with the condensation reaction of aromatic hydrocarbon to realize, and decreases the processing step of synthesis, decreases production cost and by product generation, and improves the yield of product greatly.
Description
Technical field
The present invention relates to a kind of new synthetic method of diaryl hexafluoropropane compound.
Background technology
Diaryl hexafluoropropane compound refers to 2, the hexafluoropropane compound that 2-diaryl replaces, as 2,2-phenylbenzene-HFC-236fa, 2,2-bis-(4-hydroxy phenyl)-HFC-236fa (being commonly called as bisphenol AF or BPAF), 2,2-bis-(3,4-3,5-dimethylphenyl)-HFC-236fa (is commonly called as 6FXY; Or BoxAF), 2,2-bis-(4-aminomethyl phenyl)-HFC-236fa (being commonly called as BTAF or BIS-T-AF).These compounds are products very with practical value in special fluorine-containing chemical industry, such as 2,2-bis-(4-hydroxy phenyl)-HFC-236fa is 26 class viton vulcanizing agents used, 2,2-bis-(3,4-3,5-dimethylphenyl)-HFC-236fa is the raw material of the principal monomer 6FDA of synthesis fluorinated polyimide.
The synthetic method that this compounds is traditional is by specific aromatic hydrocarbon, with Perfluoroacetone trihydrate, in anhydrous hydrogen fluoride, reacts under certain temperature and pressure.
Reaction formula is as follows:
2ArH+CF
3COCF
3-3H
2O-------→Ar-C(CF
3)
2-Ar+4H
2O
React because the mechanism of this reaction is Fu-Ke, so require that the specific aromatic hydrocarbon as reaction raw materials is the aromatic hydrocarbon with one or more electron donating group, such aromatic hydrocarbon just has enough reactive behavioies of carrying out Fu-Ke and reacting.Specific aromatic hydrocarbon is like this as phenol, and the benzene that alkyl replaces is as toluene, o-Xylol, and the benzene that alkoxyl group replaces is as anisole, phenetole, and dialkyl amido benzene is as diethylaniline etc.
Russian patent USSR117491 describes and uses phenol and Perfluoroacetone trihydrate under anhydrous hydrogen fluoride exists in the reaction of 100 DEG C of synthesis of bisphenol A F.
In US Patent No. P3310573, this traditional technology is expanded to multiple aromatic hydrocarbon in E.I.Du Pont Company and Perfluoroacetone trihydrate reacts, such as, toluene mixes with Perfluoroacetone trihydrate and anhydrous hydrogen fluoride, 160 DEG C of reactions, obtain 2,2-bis-(4-aminomethyl phenyl)-HFC-236fa.
Perfluoroacetone trihydrate used in above prior synthesizing method, generally obtain by absorbing through water and refine after Propylene oxide hexafluoride isomerization, relate to multiple devices such as reactor, water absorption unit, rectifying tower in this process, and pilot process has highly toxic anhydrous Perfluoroacetone, easily causes environmental protection and safety problem.
In addition, Perfluoroacetone trihydrate is used in conventional synthesis, the water of three times of molar weights of real reaction raw material Perfluoroacetone is brought into for reaction system, and reaction itself needs to use anhydrous hydrogen fluoride as catalysts and dewatering agent, the water-content of such increase makes real reaction compare condensation reaction itself in theory needs to use more hydrogen fluoride, and in hydrogen fluoride, increasing of water-content can cause its metal to reactor to produce larger corrodibility, thus brings production safety problem into.
Summary of the invention
The object of the present invention is to provide a kind of synthetic method of diaryl hexafluoropropane compound, present method makes Propylene oxide hexafluoride isomerization and is merged in a technique with the condensation reaction of specific aromatic hydrocarbon to realize (namely so-called " changing for one pot " or one-pot react), decrease the processing step of synthesis, decrease production cost and by product generation.
Overall reaction formula is:
Two reactions related in the present invention, first reaction belongs to the Propylene oxide hexafluoride isomerization reaction of Louis acid catalysis, and second reaction belongs to the condensation reaction of Fu-Ke reaction property.Because the mechanism of second reaction is that Fu-Ke reacts, so require that the specific aromatic hydrocarbon as reaction raw materials is the aromatic hydrocarbon with one or more electron donating group, such aromatic hydrocarbon just has enough reactive behavioies of carrying out Fu-Ke and reacting.Specific aromatic hydrocarbon is like this as phenol, and the benzene that alkyl replaces is as toluene, o-Xylol, and the benzene that alkoxyl group replaces is as anisole, phenetole, and dialkyl amido benzene is as diethylaniline etc.
The present invention is achieved in that
Aromatic hydrocarbon first added with anhydrous hydrogen fluoride and mixes, then adding catalyzer, then adding Propylene oxide hexafluoride, carrying out afterwards stirring and heating; After reaction terminates, by hydrogen fluoride through gasification or washing removing, the remaining product of institute, through treating processes such as recrystallizations, obtains diaryl hexafluoropropane compound product;
Wherein, described catalyzer is one or more in antimony halides and halogenated titanium series catalysts;
Reaction formula is:
Described aromatic hydrocarbon: Propylene oxide hexafluoride: anhydrous hydrogen fluoride is preferably 1:(0.5 ~ 4 in mass ratio): (0.5 ~ 4).
The synthetic method of described diaryl hexafluoropropane compound, it is characterized in that, described aromatic hydrocarbon is the aromatic hydrocarbon with one or more electron donating group, be preferably phenol, the benzene that alkyl replaces is as toluene, o-Xylol, the benzene that alkoxyl group replaces is as anisole, phenetole, and dialkyl amido benzene is as diethylaniline etc.
The mass ratio of the summation of described aromatic hydrocarbon and described antimony halides and halogenated titanium series catalysts is 1:0.1 ~ 1:0.5, i.e. aromatic hydrocarbon quality: (antimony halides+halogenated titanium series catalysts) quality=1:0.1 ~ 1:0.5.
Described antimony halides series catalysts can be SbCl
xf
y, wherein x+y=5, x, y be more than or equal to zero integer;
Described halogenated titanium series catalysts can be TiCl
af
b, wherein a+b=4, a, b be more than or equal to zero integer.
Preferably, described catalyzer is SbClF
4, TiClF
3or the mixture of the two; Preferred further, described catalyzer is SbClF
4with TiClF
3mixture, the mass ratio of the two is preferably 2:1 ~ 1:2.
The temperature of reaction is preferably 50 to 200 DEG C, and the reaction times is preferably 1 to 12 hours.
The present invention has following beneficial effect: the synthetic method of diaryl hexafluoropropane compound of the present invention, make Propylene oxide hexafluoride isomerization and be merged in a technique with the condensation reaction of aromatic hydrocarbon to realize, thus, decrease the processing step of synthesis, decrease production cost and by product generation, decrease the safety in production process and environmental issue simultaneously; Especially use antimony halides and halogenated titanium series catalysts composite after, greatly saved the reaction times, added the yield of product.
Embodiment
Following examples are as the explanation to embodiment of the present invention, but do not limit content of the present invention.(note: the calculation of yield in following examples, with the aromatic hydrocarbon dropped into for benchmark.)
Embodiment 1
3 kilograms of toluene are dropped in the stainless steel autoclave of 50 liters, adds 20.5 kilograms of anhydrous hydrogen fluorides by pipeline, add 1 kilogram of SbClF
4, then connect the pipeline with Propylene oxide hexafluoride steel cylinder, add 6 kilograms of Propylene oxide hexafluorides.Close each charging/discharging valve behind the door, start stirring, be heated to internal temperature 150 DEG C, protect mild stirring 12 hours.After completion of the reaction, reaction product, to normal temperature, slowly imports in 10 liters of cold water by cooling reactor, and visible product solid is separated out; Filter out solid product, washing is to neutral, dry, then uses recrystallisation from isopropanol, obtain White crystalline solid, fusing point is 85 DEG C, determines that product is 2 by analysis, 2-bis-(4-aminomethyl phenyl)-HFC-236fa, weight is 4.90 kilograms, and calculating productive rate is 90.6%.
Embodiment 2
3.4 kilograms of o-Xylols are dropped in the stainless steel high-voltage device of 10 liters, adds 3.1 kilograms of anhydrous hydrogen fluorides, add 1 kilogram of TiClF
3, then connect the pipeline with Propylene oxide hexafluoride steel cylinder, add 2.8 kilograms of Propylene oxide hexafluorides.Close each charging/discharging valve behind the door, start stirring, be heated to internal temperature 175 DEG C, protect mild stirring 11 hours.After completion of the reaction, reaction product, to normal temperature, slowly imports in 10 liters of cold water by cooling reactor, and visible product solid is separated out; Filter out solid product, washing is to neutral, dry, then uses ethylene dichloride recrystallization, obtain White crystalline solid, fusing point is 76 DEG C, determines that product is 2,2-bis-(3 by analysis, 4-aminomethyl phenyl)-HFC-236fa, weight is 5.32 kilograms, and calculating productive rate is 92.4%.
Embodiment 3
3.6 kilograms of anisoles are dropped in the stainless steel high-voltage device of 10 liters, adds 1.8 kilograms of anhydrous hydrogen fluorides, add 1 kilogram of TiClF
3, then connect the pipeline with Propylene oxide hexafluoride steel cylinder, add 7 kilograms of Propylene oxide hexafluorides.Close each charging/discharging valve behind the door, start stirring, be heated to internal temperature 200 DEG C, protect mild stirring 1 hour.After completion of the reaction, reaction product, to normal temperature, slowly imports in 10 liters of cold water by cooling reactor, and visible product solid is separated out; Filter out solid product, washing is to neutral, dry, then uses isopropyl ether recrystallization, obtain White crystalline solid, fusing point is 71 DEG C, determines that product is 2 by analysis, 2-bis-(4-p-methoxy-phenyl)-HFC-236fa, weight is 5.47 kilograms, and calculating productive rate is 90.3%.
Embodiment 4
400 grams of phenol are dropped in the nickelalloy steel autoclave of 5 liters, adds 1600 grams of anhydrous hydrogen fluorides by pipeline, add 200gSbClF
4, then connect the pipeline with Propylene oxide hexafluoride steel cylinder, add 800 grams of Propylene oxide hexafluorides.Close each charging/discharging valve behind the door, start stirring, be heated to internal temperature 55 DEG C, protect mild stirring 12 hours.After completion of the reaction, reaction product, to normal temperature, slowly imports in 10 liters of cold water by cooling reactor, and visible product solid is separated out; Filter out solid product, washing is to neutral, and dry, then use ethyl alcohol recrystallization, obtain White crystalline solid, fusing point is 160 DEG C, and product is bisphenol AF, and weight is 671 grams, and calculating productive rate is 93.8%.
Embodiment 5
400 grams of phenol are dropped in the nickelalloy steel autoclave of 5 liters, adds 1600 grams of anhydrous hydrogen fluorides by pipeline, add 200gTiClF
3, then connect the pipeline with Propylene oxide hexafluoride steel cylinder, add 800 grams of Propylene oxide hexafluorides.Close each charging/discharging valve behind the door, start stirring, be heated to internal temperature 55 DEG C, protect mild stirring 12 hours.After completion of the reaction, reaction product, to normal temperature, slowly imports in 10 liters of cold water by cooling reactor, and visible product solid is separated out; Filter out solid product, washing is to neutral, and dry, then use ethyl alcohol recrystallization, obtain White crystalline solid, fusing point is 160 DEG C, and product is bisphenol AF, and weight is 662 grams, and calculating productive rate is 92.6%.
Embodiment 6
400 grams of phenol are dropped in the nickelalloy steel autoclave of 5 liters, adds 1600 grams of anhydrous hydrogen fluorides by pipeline, add 100gSbClF
4and 100gTiClF
3, then connect the pipeline with Propylene oxide hexafluoride steel cylinder, add 800 grams of Propylene oxide hexafluorides.Close each charging/discharging valve behind the door, start stirring, be heated to internal temperature 55 DEG C, protect mild stirring 12 hours.After completion of the reaction, reaction product, to normal temperature, slowly imports in 10 liters of cold water by cooling reactor, and visible product solid is separated out; Filter out solid product, washing is to neutral, and dry, then use ethyl alcohol recrystallization, obtain White crystalline solid, fusing point is 160 DEG C, and product is bisphenol AF, and weight is 696 grams, and calculating productive rate is 97.3%.
Embodiment 7
400 grams of phenol are dropped in the nickelalloy steel autoclave of 5 liters, adds 1600 grams of anhydrous hydrogen fluorides by pipeline, add 120gSbClF
4and 80gTiClF
3, then connect the pipeline with Propylene oxide hexafluoride steel cylinder, add 800 grams of Propylene oxide hexafluorides.Close each charging/discharging valve behind the door, start stirring, be heated to internal temperature 55 DEG C, protect mild stirring 12 hours.After completion of the reaction, reaction product, to normal temperature, slowly imports in 10 liters of cold water by cooling reactor, and visible product solid is separated out; Filter out solid product, washing is to neutral, and dry, then use ethyl alcohol recrystallization, obtain White crystalline solid, fusing point is 160 DEG C, and product is bisphenol AF, and weight is 692 grams, and calculating productive rate is 96.8%.
Claims (4)
1. a synthetic method for diaryl hexafluoropropane compound, is characterized in that, is first mixed in the reactor by aromatic hydrocarbon, then adds catalyzer, then add Propylene oxide hexafluoride, carry out afterwards stirring and heating with anhydrous hydrogen fluoride; After reaction terminates, removed by hydrogen fluoride, the remaining product of institute is refined, and obtains diaryl hexafluoropropane compound product;
Wherein, described catalyzer is SbClF
4with TiClF
3the mixture of mass ratio 2:1 ~ 1:2;
Described aromatic hydrocarbon is the aromatic hydrocarbon with one or more electron donating group;
2. the synthetic method of diaryl hexafluoropropane compound as claimed in claim 1, is characterized in that, aromatic hydrocarbon: Propylene oxide hexafluoride: anhydrous hydrogen fluoride is 1:(0.5 ~ 4 in mass ratio): (0.5 ~ 4).
3. the synthetic method of diaryl hexafluoropropane compound as claimed in claim 1, it is characterized in that, described aromatic hydrocarbon is selected from phenol, the benzene that alkyl replaces or the benzene that alkoxyl group replaces.
4. the synthetic method of the diaryl hexafluoropropane compound according to any one of claim 1-3, is characterized in that, the temperature of reaction is 50 to 200 DEG C, and the reaction times is 1 to 12 hours.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3321515A (en) * | 1963-04-24 | 1967-05-23 | Du Pont | Method of making fluorinated carbonyl compounds |
| CN101851147A (en) * | 2010-06-01 | 2010-10-06 | 三明市海斯福化工有限责任公司 | Synthesis method of diaryl hexafluoropropane compound |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3321515A (en) * | 1963-04-24 | 1967-05-23 | Du Pont | Method of making fluorinated carbonyl compounds |
| CN101851147A (en) * | 2010-06-01 | 2010-10-06 | 三明市海斯福化工有限责任公司 | Synthesis method of diaryl hexafluoropropane compound |
Non-Patent Citations (1)
| Title |
|---|
| 六氟丙酮制备的研究进展;李辉等;《济南大学学报(自然科学版)》;20070425;第21卷(第01期);第45页第1.5节 * |
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