CN1321962C - Hexafluoroacetone hydrate dehydrolyzing method - Google Patents
Hexafluoroacetone hydrate dehydrolyzing method Download PDFInfo
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- CN1321962C CN1321962C CNB2005101100756A CN200510110075A CN1321962C CN 1321962 C CN1321962 C CN 1321962C CN B2005101100756 A CNB2005101100756 A CN B2005101100756A CN 200510110075 A CN200510110075 A CN 200510110075A CN 1321962 C CN1321962 C CN 1321962C
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Abstract
The present invention relates to a hexafluoroacetone hydrate dehydrolyzing method which comprises following steps: (a) hexafluoroacetone hydrate is in contact with sulfur trioxide or fuming sulfuric acid, a sulfur trioxide-hexafluoroacetone gas mixture, or a hexafluoroacetone-sulfuric-monohydrate-hexafluoroacetone gas mixture, or a hexafluoroacetone-sulfuric monohydrate-sulfur trioxide-hexafluoroacetone gas mixture and the concentrated sulfuric acid are formed; (b) the gas mixture is in contact with the concentrated sulfuric acid, and the mixed sulfur trioxide and the hexafluoroacetone-sulfuric monohydrate are eliminated.
Description
Technical field
The present invention relates to a kind of method that the hexafluoroacetone hydrate dehydration is formed anhydrous Perfluoroacetone.
Background technology
Perfluoroacetone is the simplest, most important perfluor ketone compounds, also is the most basic meticulous organic fluorine chemistry product.With the Perfluoroacetone is that raw material can be made many valuable civilian or military Chemicals, for example:
(a) preparation is as the fine solvent-hexafluoroisopropanol of regenerated fiber polyester, polyethers spinning, comprehensive utilization chitin, gel chromatography etc.;
(b) the monomer H of the high-low temperature resistant of manufacturing aerospace industry use, radiation hardness, material transparent (polyimide material)
2NC
6H
4C (CF
3)
2C
6H
4NH
2, O
3C
2C
6H
3C (CF
3)
2C
6H
3C
2O
3Deng;
(c) make opticglass, microelectronic circuits plate sealer, the monomer of the soluble transparent fluoro-resin Tefluon AF of specific solvent;
(d) make coating and tackiness agent high temperature resistant, corrosion-resistant and that have higher self-extinguishing;
(e) make novel, efficient, low side effect induction type anesthesia new drug Sevoflurane (also claiming Ultane);
(f) make new, specific fluoropolymer monomer hexafluoro-isobutene;
(g) make high-low temperature resistant, the used linking agent bisphenol AF of corrosion resistant viton;
(h) make the monomer allyl group hexafluoroisopropanol (Allyl HFIP) of the novel polymeric material be used to comprise fields such as electron device.
The application of Perfluoroacetone relates to high-tech areas such as aerospace, medicine, microelectronics, is the basic material that is difficult to the industry of alternate organic fluorine.
Because Perfluoroacetone intramolecularly carbonyl carbon is subjected to two strong electron-withdrawing group CF simultaneously again
3Inductive effect, impel carbonyl carbon to demonstrate superpower positive polarity, thus Perfluoroacetone almost can with all nucleophilic compound generation cationoid reactions; The hexafluoroisopropyli,ene structure is survivable simultaneously, is the main method of introducing the hexafluoroisopropyli,ene structure in compound.The strong Electron Affinities of Perfluoroacetone molecule can be represented with following molecular formula:
The strong Electron Affinities character decision of Perfluoroacetone molecule it can with the reaction of thumping majority parent isoelectric substance, using more is that Perfluoroacetone belongs to compound and derivatives reaction thereof with fragrance, synthesizes many valuable compounds therefroms, as:
Perfluoroacetone also can with glycol reaction, the monomer of synthetic fusible, printing opacity, high temperature resistant, corrosion-resistant TefiuonAF resin:
Perfluoroacetone is colourless hypertoxic gas at normal temperatures, and the requirement of shelter that stores and transport is very high.Perfluoroacetone and water, especially can form more stable, the higher liquid of boiling point (b.p.106 ℃) with three parts of water, so the Perfluoroacetone trihydrate of the commercial form of Perfluoroacetone.
But the Perfluoroacetone trihydrate is different from acetone, is difficult to be directly used in carry out cationoid reaction.
Making dihydroxyphenyl propane with acetone and phenol reactant is example, and at 20 ℃ of phenol: acetone: the sulfuric acid mol ratio is 2: 1: 3.8 o'clock, uses 70% sulfuric acid reaction 48 hours (water content is 20.7% when beginning to react), and the dihydroxyphenyl propane yield is 40.3%; The raw material of same mol ratio uses 75.8% sulfuric acid reaction 8 hours (water content is 16.3% when beginning to react), and the dihydroxyphenyl propane yield can reach 68.5%.
Phenol and acetone reaction under acid catalysis, sulfuric acid concentration exists sulfuric acid concentration high more below 76%, the situation that reaction yield is high more; If more than 76%, along with the rising of sulfuric acid concentration, can there be the situation of more and more serious generation sulfonation by product bisphenol S in sulfuric acid concentration, therefore industrial manufacturing dihydroxyphenyl propane is controlled at sulfuric acid concentration below 76%.Available following reactional equation is represented:
But adopt the sulfuric acid catalysis system to carry out hexafluoroacetone hydrate and phenol reactant when preparing bisphenol AF, situation is just made a world of difference.Available following example explanation: adopt same starting material and proportioning, phenol for example: Perfluoroacetone: the sulfuric acid mol ratio is 2: 1: 3.8, the sulfuric acid reaction (water content is 18.1% when beginning to react) of use 70% is at 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, each reacted 10 hours, did not all find required bisphenol AF in the product; Sulfuric acid concentration is increased to 76% (water content is 14.0% when beginning to react),, does not find that still the bisphenol AF product produces in above each thermotonus; Sulfuric acid concentration is increased to 85% (water content is 8.3% when beginning to react), after temperature is greater than 50 ℃, produce the Perfluoroacetone monohydrate of loose cotton shape in the reflux exchanger, react the existence that in reaction product, can detect the by product bisphenol S after 8 hours, but the bisphenol AF product is difficult to detect.If improve sulfuric acid concentration again, reduce the water content in the reaction system, be nonsensical to synthetic bisphenol AF test, because the by product bisphenol S is too many.Continue to do acid catalysis phenol and the Perfluoroacetone reaction of adopting low water content if desired, should select the catalyzer that is difficult to produce side reaction for use.
Experiment shows phenol and Perfluoroacetone reaction under sulfuric acid catalysis, reacts hardly when water-content is higher than 14% (weight); When being lower than 8.3% (weight), water-content has the too many situation of by product bisphenol S that produces.Therefore if will bring into play the strong close electrical effect of Perfluoroacetone inherent, the Perfluoroacetone trihydrate of high-moisture partly or entirely need be dewatered.
Analyze theoretically: the Perfluoroacetone molecule should have strong Electron Affinities, but when having more moisture content in the reaction system, shows in the Perfluoroacetone molecule that strong electropositive carbonyl carbon is vulnerable to the effect of water molecules, forms the Perfluoroacetone monohydrate earlier; This moment, the positive polarity of this carbon atom did not descend, and the protic compound water around the polarization, polarized then water molecules shields the Perfluoroacetone monohydrate, make Perfluoroacetone or Perfluoroacetone monohydrate be difficult to demonstrate strong electrophilic feature again, hindered the reaction of Perfluoroacetone or Perfluoroacetone monohydrate and close isoelectric substance.This phenomenon be similar to that nucleophilic reagent is selected solvent and water-content require consistent.Available following chemical equation is represented:
From above analysis inference like this: the Perfluoroacetone water content is low more, and reactive behavior is big more.Moisture content when belonging to compound and derivatives reaction thereof in order to remove Perfluoroacetone with fragrance, relatively Chang Yong method is to use a large amount of, and the strong anhydrous hydrogen fluoride of water association, as dewatering agent.For example 4.0 kilograms of phenol, 5.0 kilogram of 95% (weight) Perfluoroacetone trihydrate, 25.0 kilograms of anhydrous hydrogen fluorides can be obtained the bisphenol AF of 60-70% yield 80-100 ℃ of hybrid reaction.
Though when Perfluoroacetone trihydrate and nucleophilic compound react, add a large amount of anhydrous hydrogen fluorides and can impel reaction to carry out.But or not reaction conversion ratio is not low, equipment corrosion is serious for its result, and a large amount of hydrogen fluoride that must add when the dereaction after the reaction.Removing in the product a large amount of hydrofluoric common methods mainly is washing, produces a large amount of, the organic acid waste water of the reluctant F-of containing thus.For example Perfluoroacetone trihydrate and phenol interact and prepare the reaction of bisphenol AF, need to add the anhydrous hydrogen fluoride of Perfluoroacetone trihydrate quality more than 5 times, and reaction yield can only reach 60-70%, and the amount that produces waste water simultaneously is about 200 times of a product bisphenol AF quality.
The situation of Perfluoroacetone reactive behavior conductively-closed by to the reaction of above Perfluoroacetone trihydrate and nucleophilic compound the time, and the situation of taking to add the remedial measures of a large amount of anhydrous hydrogen fluorides in order to improve the Perfluoroacetone reactive behavior is carried out deep analysis, this area is thought in advance the Perfluoroacetone trihydrate is carried out diminishing or processed fully, the strong parent that can partly or entirely recover Perfluoroacetone is electroactive, reduces or significantly reduce hydrofluoric usage quantity.Thereby improve reaction yield, reduce the wastewater flow rate that produces, help reducing environmental pollution, reduce production costs.
Therefore, prior art has proposed a kind of hexafluoroacetone hydrate dehydration method that makes, it is with the Perfluoroacetone hydrate and the vitriol oil (the general merchandise vitriol oil, concentration is 98%) effect, by the Vanadium Pentoxide in FLAKES drying, use cold-trap to collect anhydrous Perfluoroacetone then the gas (the Perfluoroacetone monohydrate that mainly contains Perfluoroacetone gas and carry secretly) that produces again.This hexafluoroacetone hydrate dewatering can be divided into for two steps, the first step Perfluoroacetone hydrate and vitriol oil effect, obtain carrying the Perfluoroacetone gas of part Perfluoroacetone monohydrate, at this moment can not directly use cold-trap to collect Perfluoroacetone gas (below with the reason of describing), need be with Perfluoroacetone gas by the dry further dehydration of Vanadium Pentoxide in FLAKES.But the powdered Vanadium Pentoxide in FLAKES not only causes the body gas-flow resistance big; And as long as a certain aspect powder surface absorbs water on a small quantity in the loading phosphorus pentoxide desiccator, will cause the sticking mutually connection of powder, gas-flow resistance obviously to rise, cause Perfluoroacetone trihydrate and vitriol oil mixing kettle pressure to rise, cause preparation work can't continue to carry out.Therefore the described method of producing anhydrous Perfluoroacetone only is suitable for producing a spot of Perfluoroacetone.
Anhydrous Perfluoroacetone (or claiming pure Perfluoroacetone) boiling point is-27.6 ℃, is gas under the normality, often adopts the cold-trap that will be dipped in the freezing system of dry ice～ethanol to collect anhydrous Perfluoroacetone.Perfluoroacetone monohydrate (b.p.48 ℃) is though fusing point is higher, and a spot of Perfluoroacetone monohydrate that carries in the Perfluoroacetone at normal temperatures is difficult to separate out.(15 ℃) yet at low temperatures, especially the Perfluoroacetone monohydrate will be separated out at the coil pipe of cold-trap when collecting temperature-72 ℃, forms crystallization.Stop and use cold-trap to collect further carrying out of gas phase Perfluoroacetone work.Therefore general laboratory method can only obtain a small amount of yield liquid phase Perfluoroacetone not high, that contain part Perfluoroacetone monohydrate.
Therefore, this area still needs to seek a kind of hexafluoroacetone hydrate dehydration method that makes efficiently.
The content of invention
The purpose of this invention is to provide a kind of hexafluoroacetone hydrate dehydration method that makes efficiently.
The invention provides a kind of dewatering of hexafluoroacetone hydrate, it comprises the steps:
(a) hexafluoroacetone hydrate is contacted with sulphur trioxide or oleum, to make Perfluoroacetone-sulfur trioxide gas mixture or Perfluoroacetone monohydrate-Perfluoroacetone gaseous mixture or Perfluoroacetone monohydrate-sulphur trioxide-Perfluoroacetone gaseous mixture
(b) described gaseous mixture is contacted with the vitriol oil, to remove sulphur trioxide, the Perfluoroacetone monohydrate of wherein carrying secretly.
Embodiment
In the present invention, term " oleum " is meant that sulfur trioxide content is the sulphuric acid soln of 1-65 weight %, is preferably 10-50 weight %, more preferably the oleum of 20-50 weight %.
In the present invention, term " vitriol oil " is meant that concentration is more than the 90 weight %, is preferably the above sulfuric acid of 95 weight %.
In the present invention, term " hexafluoroacetone hydrate " is meant Perfluoroacetone trihydrate or Perfluoroacetone dihydrate, better is the Perfluoroacetone trihydrate.
The inventor proposes to use sulphur trioxide strong, that dewatering efficiency is higher or oleum to make the hexafluoroacetone hydrate dehydration method on experiment basis, the inventive method can remove water a large amount of in the hexafluoroacetone hydrate once, contains Perfluoroacetone-sulfur trioxide gas mixture or Perfluoroacetone monohydrate-Perfluoroacetone gaseous mixture or Perfluoroacetone monohydrate-sulphur trioxide-Perfluoroacetone gaseous mixture in the gaseous product of formation; Then described gaseous product is fed the vitriol oil to remove sulphur trioxide or the Perfluoroacetone monohydrate is further changed into anhydrous Perfluoroacetone gas.The inventive method is not used Vanadium Pentoxide in FLAKES or other siccative fully, thereby can reduce usage quantity, minimizing raw material variety, reduction manufacturing cost, the easy defective of stopping up of elimination siccative of raw material, prepares anhydrous Perfluoroacetone easily.
The inventive method comprises the step that hexafluoroacetone hydrate is contacted with sulphur trioxide or oleum as dewatering agent, to make Perfluoroacetone gas and to form the vitriol oil.
The ratio of the amount of water has no particular limits in the amount that is applicable to sulphur trioxide in the inventive method or the sulphur trioxide in the oleum and the Perfluoroacetone hydrate.Be preferably, the sulfuric acid concentration that their reaction backs form should be used for subsequent reactions thereby the sulfuric acid that this reaction forms can be used as " vitriol oil " between 90-100%.
In the present invention, term " sulphur trioxide of significant quantity or oleum " is meant that the vitriolic concentration that the amount of sulphur trioxide in the amount of sulphur trioxide or the oleum is enough to sulphur trioxide or oleum and hexafluoroacetone hydrate reaction back are formed is 90-100%, be preferably 95-100%, more preferably 98-100%.
In the present invention, term " hexafluoroacetone hydrate " is meant Perfluoroacetone trihydrate, Perfluoroacetone dihydrate, Perfluoroacetone monohydrate or their mixture, better is the Perfluoroacetone trihydrate.
In an example of the present invention, the aqueous solution that uses 95% Perfluoroacetone trihydrate is as the Perfluoroacetone trihydrate that will dewater, wherein water-content is divided into two partly, first part contains 5% aqueous solvent, second section is the combination water that contains in the Perfluoroacetone trihydrate, is the total amount of the water that will remove after the water of its two part is added.
The contact temperature that is used to dewatering agent is contacted with hexafluoroacetone hydrate can be at 0-200 ℃.But for the reason of operation control, temperature is 20-150 ℃ preferably.
They make the duration of contact between Perfluoroacetone hydrate and sulphur trioxide or the oleum without particular limitation, as long as can fully contact.In a better example of the present invention, control Perfluoroacetone hydrate and sulphur trioxide or oleum duration of contact better were more than 0.5 second more than 0.1 second;
In order to promote the Perfluoroacetone hydrate with sulphur trioxide or oleum is capable fully contacts, better adopt and be fit to the reactor that mass transfer requires, can be to be designed to the reactor that length-to-diameter ratio is big, the volume cycle rate is bigger, also can be the bigger pipeline reactor of Reynolds number, or the molectron of the two.Those of ordinary skill in the art can easily determine suitable reactor in conjunction with its expertise after having read content disclosed by the invention.
Sulphur trioxide and the reaction of Perfluoroacetone hydrate are progressively processes of dehydration, available following The Representation Equation:
Because Perfluoroacetone is a kind of gaseous product under normal conditions, so it may carry the sulphur trioxide of a part as reagent secretly, formation Perfluoroacetone-sulfur trioxide gas mixture; Also may carry a part of Perfluoroacetone monohydrate secretly, form Perfluoroacetone monohydrate-Perfluoroacetone gaseous mixture; Also may be to carry a part of Perfluoroacetone monohydrate, sulphur trioxide formation Perfluoroacetone monohydrate-sulphur trioxide-Perfluoroacetone gaseous mixture secretly.In order to obtain more purified Perfluoroacetone product, the mixed gas that obtains can be fed in the vitriol oil.Sulphur trioxide can be absorbed by the vitriol oil (concentration is less than 100%), the Perfluoroacetone monohydrate is dewatered by the vitriol oil again because Perfluoroacetone gas difficulty is dissolved in the sulfuric acid of high density, therefore can obtain highly purified Perfluoroacetone gas products after vitriol oil effect.
In a better example of the present invention, the vitriol oil that Perfluoroacetone trihydrate and sulphur trioxide or oleum carry out forming after the dehydration reaction in use the inventive method is used for removing the sulphur trioxide of Perfluoroacetone-sulphur trioxide mixed gas, the Perfluoroacetone monohydrate of perhaps Perfluoroacetone being carried secretly further is dehydrated into pure Perfluoroacetone, perhaps not only absorbed sulphur trioxide but also sloughed water in the Perfluoroacetone monohydrate, it had further been changed into anhydrous Perfluoroacetone gas.Moisture in the anhydrous Perfluoroacetone and the vitriol oil interacts, and the concentration of the vitriol oil should be higher than 90wt%, better is higher than 95wt%, more preferably 98wt%.
The action time and the temperature of the gaseous mixture and the vitriol oil are without particular limitation, as long as can remove sulphur trioxide or Perfluoroacetone monohydrate up hill and dale.In a better example of the present invention, the vitriol oil that uses 96-98wt% is as absorption agent, at 0-200 ℃, is preferably under 20-150 ℃ the temperature and makes it to contact 0.1-1 second.
In preferred embodiment of the present invention, the inventive method comprises the steps:
(1) 0-200 ℃, more fortunately 20-150 ℃ makes the sulphur trioxide of significant quantity or oleum contact 0.01-30 second with hexafluoroacetone hydrate, better 0.5-10 second, better 0.8-1.5 second, form the gaseous mixture and the vitriol oil that contain anhydrous Perfluoroacetone, sulphur trioxide and/or Perfluoroacetone monohydrate;
(2) at 0-200 ℃, 20-150 ℃ is used the above-mentioned vitriol oil as absorption agent more fortunately, makes the gaseous mixture of formation contact 0.1-10 second with this absorption agent;
(3) collect the anhydrous Perfluoroacetone that forms with cold-trap.
Can use the cryotrap collection technique to collect the final Perfluoroacetone gas that forms of the inventive method easily and can not produce the equipment pipe blocking problem.But cryotrap is not to be unique Perfluoroacetone collection method, and those of ordinary skill in the art can easily determine the collection method of the anhydrous Perfluoroacetone that other is suitable in conjunction with its expertise after having read content disclosed by the invention.For example, can adopt pressurized liquefied technology to collect Perfluoroacetone, so that further cut down the consumption of energy, reduce cost, be convenient to the further use of Perfluoroacetone.
Embodiment further specifies the present invention below by indefiniteness.
Embodiment
1.
Perfluoroacetone monohydrate Determination on content method in the Perfluoroacetone gas
Use Hewlett-Packard's 6890 chromatographic instruments, DB5 capillary column (specification: ￠ 0.25mm * 30m); Column temperature: 30 ℃; Carrier gas: H2; Press before the post: 10psi; Electric current: 200mA.
2.
The measuring method of sulfur trioxide content in the anhydrous Perfluoroacetone gas
Use Hewlett-Packard's 6890 chromatographic instruments, DB1 capillary column (specification: ￠ 0.25mm * 30m); Column temperature: 30 ℃; Carrier gas: H2; Press before the post: 10psi; Electric current: 200mA.
Comparative example 1
Use 98% sulfuric acid as dewatering agent
In the 10000ml three-necked flask that has stirring ,-15 ℃ of condensers, dropping funnel, 98% sulfuric acid that adds 10 kilograms, under agitation drip 95% Perfluoroacetone trihydrate, control reaction temperature 40-50 ℃, take out a part and measure the content of its Perfluoroacetone monohydrate by the gas sample of condenser, the content that found that the Perfluoroacetone monohydrate is 7.5%.To import in dry ice-ethanol refrigerative cold-trap by the gas of condenser.Control drips the amount of 95% Perfluoroacetone trihydrate, makes the pressure that produces gas can not be too high, avoids making the vial blast.Find after 30 minutes that 95% Perfluoroacetone trihydrate is difficult to drip (pressure height), finds that on inspection the coil pipe of cold-trap is clogged by white solid.At this moment totally splash into 95% Perfluoroacetone trihydrate 435 gram, cold-trap about 270 grams that increase weight.Analysis learns that the white solid in the coil pipe of cold-trap is the Perfluoroacetone monohydrate, the about 15-20 gram of white solid weight., calculate Perfluoroacetone yield about 80.2% by weightening finish (270-20) gram.
By this comparative example as seen, though use the conventional vitriol oil can make anhydrous Perfluoroacetone,, then need to eliminate continually the tamper in the cold-trap coil pipe, thereby improved the dehydration cost if use the vitriol oil to make the dehydration of Perfluoroacetone trihydrate as dewatering agent.
Comparative example 2
Use 98% sulfuric acid, add the dry gas phase of Vanadium Pentoxide in FLAKES again, stop up to eliminate the cold-trap coil pipe
In the 10000ml three-necked flask that has stirring ,-15 ℃ of condensers, dropping funnel, 98% sulfuric acid that adds 10 kilograms, under agitation drip 95% Perfluoroacetone trihydrate, control reaction temperature 40-50 ℃, to (in the moisture eliminator blend of 1000 gram Vanadium Pentoxide in FLAKESs and 1000 gram glass wools by the first moisture eliminator that imports φ 100 * 500 of the gas of condenser, use glass wool can increase air penetrability), get a part of sample and measure the content of its Perfluoroacetone monohydrate, the result is 7.6%.To import again in dry ice-ethanol refrigerative cold-trap through Vanadium Pentoxide in FLAKES exsiccant sample, find after 20 minutes that the Perfluoroacetone trihydrate is difficult to drip (the reaction flask internal pressure is too high), find that on inspection moisture eliminator blocks.Cold-trap increase weight about 150 the gram.At this moment totally splash into 95% Perfluoroacetone trihydrate, 275 grams, Perfluoroacetone yield about 76.1%.
By this comparative example as seen, though use the vitriol oil can make anhydrous Perfluoroacetone as dewatering agent, and adopt the Vanadium Pentoxide in FLAKES after drying can eliminate the latch up phenomenon of cold-trap coil pipe, need to solve the latch up phenomenon of moisture eliminator.
Embodiment 1
Use 20% oleum as dewatering agent and use the aftertreatment of 98wt% sulfuric acid
1000 grams, 95% Perfluoroacetone trihydrate is dropped in 4400 grams, 20% oleum, mixing temperature is controlled at 0-100 ℃, make it thorough mixing, use aforesaid method, measure the content of Perfluoroacetone monohydrate, the result is 4.1%; Measure the content of sulphur trioxide, the result is 2.0%.
When the gas that produces is mixed with 5000 grams, 98% sulfuric acid thorough mixing temperature is controlled at 0-50 ℃, measuring wherein, the content of sulphur trioxide is 0.0%; The content of Perfluoroacetone monohydrate is 0.0%.Again gas is imported in dry ice-ethanol refrigerative cold-trap, obtain 713.6 gram Perfluoroacetones, Perfluoroacetone yield about 99.6%.
In whole dropping Perfluoroacetone trihydrate process, do not observe reaction pressure rising phenomenon, do not observe white obturator at the cold-trap coil pipe yet.
Embodiment 2
Use 50% oleum and 95% sulfuric acid successively as dewatering agent (absorption agent)
1100 grams, 90% Perfluoroacetone trihydrate is dropped in 2600 grams, 50% oleum, temperature is controlled at 30-120 ℃, make it thorough mixing.The gas that produces is restrained 95% sulfuric acid thorough mixing with 5000 again, and mixing temperature is controlled at 20-60 ℃.Measure the content of Perfluoroacetone monohydrate and sulphur trioxide in the anhydrous Perfluoroacetone gas, wherein the content of sulphur trioxide is 0.0%; The content of Perfluoroacetone monohydrate is 0.0%.Again gas is imported in dry ice-ethanol refrigerative cold-trap, obtain 740 gram Perfluoroacetones, Perfluoroacetone yield about 99.0%.
In whole dropping Perfluoroacetone trihydrate process, do not observe reaction pressure rising phenomenon, do not observe white obturator at the cold-trap coil pipe yet.
Embodiment 3
Use 65% oleum and 93% sulfuric acid successively as dewatering agent (absorption agent)
1200 grams, 85% Perfluoroacetone trihydrate is dropped in 2900 grams, 65% oleum, mixing temperature is controlled at 50-150 ℃, make it thorough mixing.The gas that produces is mixed mutually with 5000 grams, 93% sulfuric acid again, and mixing temperature is controlled at 30-80 ℃, measure the content of Perfluoroacetone monohydrate and sulphur trioxide in the anhydrous Perfluoroacetone gas, wherein the content of sulphur trioxide is 0.0%; The content of Perfluoroacetone monohydrate is 0.3%.To import in dry ice-ethanol refrigerative cold-trap by the gas of condenser, obtain 755 gram Perfluoroacetones, Perfluoroacetone yield about 97.8%.
In whole dropping Perfluoroacetone trihydrate process, do not observe reaction pressure rising phenomenon, do not observe white obturator at the cold-trap coil pipe yet.
Embodiment 4
Use sulphur trioxide and 90% sulfuric acid successively as dewatering agent (absorption agent)
With 1300 grams, 80% Perfluoroacetone trihydrate, 2300 gram sulphur trioxide phase mixtures, mixing temperature is controlled at 80-200 ℃, the gas of generation restrains 90% sulfuric acid 45-100 ℃ thorough mixing with 5000 again, and gas is imported oil free compressor (inspiratory capacity 0.1m
3/ min) be pressurized to more than the 0.5Mpa, the material that compressor is discharged [has a condenser (5 ℃ of cold water coolings) by entering the storage tank that has chuck cooling (5 ℃ of cold water coolings) on the storage tank top, the safety valve that a 0.7Mpa pressure release is arranged on condenser, can obtain containing Perfluoroacetone 750 grams of Perfluoroacetone monohydrate 1.0%, Perfluoroacetone yield about 94.6%.
Embodiment 5
Use 10% oleum and 93% sulfuric acid successively as dewatering agent (absorption agent)
1000 grams, 85% Perfluoroacetone trihydrate is dropped in 2900 grams, 10% oleum, mixing temperature is controlled at 50-150 ℃, make it thorough mixing.The gas that produces is mixed mutually with 5000 grams, 93% sulfuric acid again, and mixing temperature is controlled at 30-80 ℃, measure the content of Perfluoroacetone monohydrate and sulphur trioxide in the anhydrous Perfluoroacetone gas, wherein the content of sulphur trioxide is 0.0%; The content of Perfluoroacetone monohydrate is 0.3%.To import in dry ice-ethanol refrigerative cold-trap by the gas of condenser, obtain 755 gram Perfluoroacetones, Perfluoroacetone yield about 97.8%.
In whole dropping Perfluoroacetone trihydrate process, do not observe reaction pressure rising phenomenon, do not observe white obturator at the cold-trap coil pipe yet.
By top test-results as seen, the inventive method has been eliminated the defective that five phosphorus oxide moisture eliminators stop up in the existing method, uses the sulphur trioxide of high dewatering efficiency or oleum to substitute sulfuric acid simultaneously, has reduced the vitriolic usage quantity, improve production efficiency, reduced product cost.
Claims (12)
1. the dewatering of a hexafluoroacetone hydrate, it comprises:
(a) hexafluoroacetone hydrate is contacted with sulphur trioxide or oleum, form trioxygen-containing sulphur-Perfluoroacetone gaseous mixture or Perfluoroacetone monohydrate-Perfluoroacetone gaseous mixture or the Perfluoroacetone monohydrate-sulphur trioxide-Perfluoroacetone gaseous mixture and vitriol oil;
(b) described gaseous mixture is contacted with the vitriol oil, to remove sulphur trioxide, the Perfluoroacetone monohydrate of wherein carrying secretly.
2. the method for claim 1 is characterized in that described hexafluoroacetone hydrate is Perfluoroacetone trihydrate, Perfluoroacetone two hydrates or Perfluoroacetone monohydrate.
3. method as claimed in claim 1 or 2 is characterized in that the sulfuric acid concentration that the reaction of sulphur trioxide in sulphur trioxide or the oleum and the water in the Perfluoroacetone hydrate forms is 90-100%.
4. method as claimed in claim 3 is characterized in that the sulfuric acid concentration that reacts formation is higher than 95 weight %.
5. method as claimed in claim 4, the sulfuric acid concentration that it is characterized in that reacting formation is 98 weight %.
6. method as claimed in claim 1 or 2 is characterized in that sulphur trioxide or oleum and hexafluoroacetone hydrate operative temperature are 0～200 ℃.
7. method as claimed in claim 6 is characterized in that sulphur trioxide or oleum and hexafluoroacetone hydrate operative temperature are 20-150 ℃.
8. method as claimed in claim 1 or 2, the vitriol oil that it is characterized in that step (a) is formed is as the vitriol oil of removing sulphur trioxide, Perfluoroacetone monohydrate in the step (b).
9. method as claimed in claim 1 or 2 is characterized in that step (b) is to carry out in 0～100 ℃ temperature range.
10. method as claimed in claim 1 or 2 is characterized in that it comprises the steps:
(1) makes the sulphur trioxide of significant quantity or oleum contact 0.01-30 second with hexafluoroacetone hydrate at 0-200 ℃, form the gaseous mixture and the vitriol oil that contain anhydrous Perfluoroacetone, sulphur trioxide and/or Perfluoroacetone monohydrate;
(2) use the vitriol oil that described contact forms as absorption agent at 0-200 ℃, make the gaseous mixture of formation contact 0.1-10 second with this absorption agent;
(3) collect the anhydrous Perfluoroacetone that forms with cold-trap.
11. method as claimed in claim 10 is characterized in that making the sulphur trioxide of significant quantity or oleum contact 0.5-10 second with hexafluoroacetone hydrate at 20-150 ℃; And use the vitriol oil that described contact forms as absorption agent at 20-150 ℃.
12. method as claimed in claim 11 is characterized in that making the sulphur trioxide of significant quantity or oleum to contact 0.8-1.5 second with hexafluoroacetone hydrate.
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| CNB2005101100756A CN1321962C (en) | 2005-11-07 | 2005-11-07 | Hexafluoroacetone hydrate dehydrolyzing method |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005101100756A CN1321962C (en) | 2005-11-07 | 2005-11-07 | Hexafluoroacetone hydrate dehydrolyzing method |
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| CN1762952A CN1762952A (en) | 2006-04-26 |
| CN1321962C true CN1321962C (en) | 2007-06-20 |
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| CNB2005101100756A Active CN1321962C (en) | 2005-11-07 | 2005-11-07 | Hexafluoroacetone hydrate dehydrolyzing method |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5034784B2 (en) * | 2007-08-29 | 2012-09-26 | セントラル硝子株式会社 | Method for dehydrating hexafluroacetone hydrate |
| JP5482013B2 (en) * | 2009-08-18 | 2014-04-23 | セントラル硝子株式会社 | Method for producing hexafluoroacetone monohydrate |
| CN105130752A (en) * | 2015-08-18 | 2015-12-09 | 常熟市新华化工有限公司 | Preparation method of 1,1,1,3,3,3-hexafluoro-2-(4-styrene)propanol |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4386223A (en) * | 1980-11-11 | 1983-05-31 | Central Glass Company Limited | Method of purifying hexafluoroacetone containing chlorofluoroacetones |
| US4544772A (en) * | 1983-04-30 | 1985-10-01 | Central Glass Company, Limited | Method of purifying hexafluoroacetone hydrate |
| US6392101B2 (en) * | 2000-01-05 | 2002-05-21 | Central Glass Company, Limited | Process for purifying 1,1,1,5,5,5-hexafluoroacetylacetone |
| US6548712B2 (en) * | 2000-03-17 | 2003-04-15 | Central Glass Company, Limited | Process for producing 1,1,1,5,5,5-hexafluoroacetylacetone |
-
2005
- 2005-11-07 CN CNB2005101100756A patent/CN1321962C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4386223A (en) * | 1980-11-11 | 1983-05-31 | Central Glass Company Limited | Method of purifying hexafluoroacetone containing chlorofluoroacetones |
| US4544772A (en) * | 1983-04-30 | 1985-10-01 | Central Glass Company, Limited | Method of purifying hexafluoroacetone hydrate |
| US6392101B2 (en) * | 2000-01-05 | 2002-05-21 | Central Glass Company, Limited | Process for purifying 1,1,1,5,5,5-hexafluoroacetylacetone |
| US6548712B2 (en) * | 2000-03-17 | 2003-04-15 | Central Glass Company, Limited | Process for producing 1,1,1,5,5,5-hexafluoroacetylacetone |
Non-Patent Citations (3)
| Title |
|---|
| 六氟丙酮及其应用 张在利等，化工新型材料，第32卷第7期 2004 * |
| 六氟丙酮的应用和制备 尤来方等，有机氟工业，第1卷 1997 * |
| 六氟丙酮的应用和制备 尤来方等，有机氟工业，第1卷 1997;六氟丙酮及其应用 张在利等，化工新型材料，第32卷第7期 2004 * |
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| CN1762952A (en) | 2006-04-26 |
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