CN107382692A - The synthetic method of perfluor hexanone and application - Google Patents
The synthetic method of perfluor hexanone and application Download PDFInfo
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- CN107382692A CN107382692A CN201710795644.8A CN201710795644A CN107382692A CN 107382692 A CN107382692 A CN 107382692A CN 201710795644 A CN201710795644 A CN 201710795644A CN 107382692 A CN107382692 A CN 107382692A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/58—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in three-membered rings
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0028—Liquid extinguishing substances
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- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
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- C07D303/02—Compounds containing oxirane rings
- C07D303/48—Compounds containing oxirane rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals
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Abstract
The present invention relates to a kind of synthetic method of perfluor hexanone and application, belong to technical field of organic synthesis.Hexafluoropropylene dimmer is mixed with solvent, is cooled to 13~17 DEG C, adds oxidant, the maximum reaction product of proportion is collected, obtains perfluoroepoxide.By perfluoroepoxide under the conditions of existing for solvent and amines catalyst, isomerization, the maximum reaction product of proportion is collected, rectifying, the rectifying thing that boiling point is 48~50 DEG C is collected, obtains perfluor hexanone.Solvent includes acetonitrile and/or dimethylformamide.The synthetic method craft is simple, and product purity and synthetic yield are higher.The perfluor hexanone being synthesized into can be used for fire-fighting fire extinguishing as extinguishing chemical, good extinguishing effect and green.
Description
Technical field
The present invention relates to technical field of organic synthesis, and the synthetic method of more particularly to a kind of perfluor hexanone and application.
Background technology
Perfluor hexanone is a kind of new Hamacher operator, and its ODP value is 0, GWP value 1, belongs to green chemical combination
Thing, the harm to environment, human body are almost zero；It is colourless liquid under normal temperature, easily vaporization, normal temperature and pressure, is easy to store, heat of evaporation
Only the 1/25 of water, heat absorption capacity is strong.Put out a fire available for physics, extinguishing property is excellent, is adapted to the close expensive equipment of protection.When with
When making clean fire extinguishing agent, dangerous material are not belonging to, do not leave residue, convenient transportation upon discharge.
In perfluor hexanone production technology, fluorine-containing or perfluoroolefine impurity is also contained in addition to principal product perfluor hexanone, these
Fluorine-containing or perfluoroolefine is close with the physicochemical properties of perfluor hexanone and relative volatility is smaller, can form azeotropic material or near
Like azeotropic material.Meanwhile the organic solvent used in production technology is also smaller with the relative volatility of perfluor hexanone, it is not easy point
From having a strong impact on the purity of perfluor hexanone finished product.
Because perfluor hexanone is Halon's succedaneum of new generation, on its production technology and the Research Significance of product separating-purifying
It is higher, but in the prior art, the production technology of perfluor hexanone is complex, and loss late is higher, and yield and purity are relatively low.
Therefore, it is necessary to be improved to the production technology of perfluor hexanone.
The content of the invention
An object of the present invention is to provide a kind of synthetic method of perfluor hexanone, and the synthetic method craft is simple, production
Thing purity and synthetic yield are higher.
, will another object of the present invention is to provide a kind of application for the perfluor hexanone being synthesized into by above-mentioned synthetic method
It is used for fire-fighting fire extinguishing as extinguishing chemical, good extinguishing effect and green.
The present invention is solved its technical problem and realized using following technical scheme：
The present invention proposes a kind of synthetic method of perfluor hexanone, comprises the following steps：
Hexafluoropropylene dimmer is mixed with solvent, is cooled to 13~17 DEG C, adds oxidant, collects the anti-of proportion maximum
Product is answered, obtains perfluoroepoxide.
By perfluoroepoxide under the conditions of existing for solvent and amines catalyst, isomerization, the anti-of proportion maximum is collected
Product is answered, rectifying, the rectifying thing that boiling point is 48~50 DEG C is collected, obtains perfluor hexanone.
Preferably, the solvent mixed with hexafluoropropylene dimmer includes acetonitrile and/or dimethylformamide, with perfluor epoxy
The solvent of compound mixing includes acetonitrile and/or dimethylformamide.
The invention also provides the perfluor hexanone that a kind of synthetic method by above-mentioned perfluor hexanone is synthesized into goes out in fire-fighting
Application in fire.
The synthetic method of the perfluor hexanone of the embodiment of the present invention and the beneficial effect of application are：
Hexafluoropropylene dimmer mix with including acetonitrile and/or dimethylformamide, then again with it is oxidizing instead
Answer, the perfluoroepoxide of higher degree can be obtained.By the perfluoroepoxide of gained and amines catalyst isomerization reaction,
The thorough isomerization of perfluoroepoxide can be made, rectifying pointedly then is carried out to lower floor's thing again, it is complete so as to effectively increase
The yield and purity of fluorine hexanone.The synthetic method craft is simple, and product purity and synthetic yield are higher.The perfluor being synthesized into
Hexanone can be used for fire-fighting fire extinguishing as extinguishing chemical, good extinguishing effect and green.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer
Technical scheme be clearly and completely described.Unreceipted actual conditions person, builds according to normal condition or manufacturer in embodiment
The condition of view is carried out.Agents useful for same or the unreceipted production firm person of instrument, it is the conventional production that can be obtained by commercially available purchase
Product.
The synthetic method of the perfluor hexanone of the embodiment of the present invention is specifically described with application below.
The synthetic method of the perfluor hexanone of the present embodiment may comprise steps of：Hexafluoropropylene dimmer and solvent are mixed
Close, be cooled to 13~17 DEG C, add oxidant, oxidation reaction, collect the maximum reaction product of proportion.It is preferred that can be by oxygen
The material for changing reaction first carries out stratification, collects lower floor's thing, obtains perfluoroepoxide.
Optionally, above-mentioned solvent can be selected from least one of aprotic polar solvent, such as acetonitrile and diformazan
Base formamide.Oxidant includes hypochlorite solutions, it is preferred that hypochlorite solutions can include liquor natrii hypochloritis and time chlorine
Sour calcium solution.The mass concentration of Active Chlorine is 8~12% in hypochlorite solutions, so that hexafluoropropylene dimmer is able to abundant oxygen
Change.
Preferably, the oxidant in the embodiment of the present invention uses liquor natrii hypochloritis, and liquor natrii hypochloritis passes through dropwise addition
Mode is added into the mixture of hexafluoropropylene dimmer and acetonitrile.Specifically, such as can be by the six of 250~350 parts by weight
Fluoropropene dimer and the acetonitrile of 40~60 parts by weight are added in reactor, are stirred and are cooled to 13~17 DEG C, are then added dropwise again
The liquor natrii hypochloritis of 500~700 parts by weight.Preferably, the weight ratio of hexafluoropropylene dimmer, acetonitrile and sodium hypochlorite is
300：50：600.
By controlling the rate of addition of liquor natrii hypochloritis and carrying out jacket refrigerating, after liquor natrii hypochloritis is added
The temperature control of reaction system is in the range of -35~20 DEG C.Preferably, the liquor natrii hypochloritis of above-mentioned 500~700 parts by weight
Time for adding amounts to 7.5~8.5h.
After dripping, 25~35min is incubated, using the reacted material of chromatographic to hexafluoropropylene dimmer
Reaction is complete.It is subsequently cooled to 0~3 DEG C, stratification collects lower floor's thing, and the purity of the perfluoroepoxide is up to 95%.Its
In, time of repose can be controlled in 28~32min.
Further, above-mentioned hexafluoropropylene dimmer can obtain through following steps：By hexachloropropylene and catalyst solution
Mixing, then reacts under conditions of 30~40 DEG C and 0.1~0.15MPa, collects the maximum reaction product (lower floor's thing) of proportion.
Optionally, above-mentioned catalyst solution includes acetonitrile, the amines catalysis of 3~5 parts by weight of 90~110 parts by weight
Agent and the fluorine-containing salts of 1~3 parts by weight.Wherein, amines catalyst is preferably tetramethylethylenediamine.Fluorine-containing salts include sodium fluoride, fluorine
Change at least one of potassium, cesium fluoride, potassium bifluoride, phosphorus pentafluoride and sulfur tetrafluoride, preferably potassium fluoride.
Specifically, can be by the acetonitrile of 90~100 parts by weight, the tetramethylethylenediamine of 3~5 parts by weight and 1~3 parts by weight
Fluorine-containing salts (preferred fluorinated potassium) react 0.8~1.2h under nitrogen atmosphere, obtain yellow catalyst solution.It is preferred that reaction temperature
Degree can be controlled in 35~45 DEG C, is stirred in course of reaction.What deserves to be explained is above-mentioned nitrogen can also be replaced by indifferent gas
Body, such as argon gas.
The hexachloropropylene that 90~110 parts by weight altogether are added portionwise in catalyst solution is stated then up, in 30~40 DEG C
And reacted under conditions of 0.1~0.15MPa, 4~6min is stood every 0.8~1.2h, collects lower floor's thing.It is preferred that per hour
The amount control of the hexachloropropylene added in interior catalyst solution is in 18~22 parts by weight, preferred 18~22 kilograms of chlordenes on an hourly basis
The amount of propylene is added portionwise into 94~108 kilograms of catalyst solution.After the completion of reaction, in the hexafluoropropylene dimmer of gained
The purity of perfluoro-2-methyl-2-amylene is up to 88%.
Because the hexafluoropropylene dimmer as obtained by above-mentioned reaction includes two kinds of isomers simultaneously, reduce complete
The yield and purity of fluoro- 2- methyl -2- amylenes.Therefore the embodiment of the present invention also includes entering the hexafluoropropylene dimmer of above-mentioned gained
The further purification process of row：Above-mentioned hexafluoropropylene dimmer is mixed with acetonitrile, crown ether-like phase transfer catalysts and fluorine-containing salts,
10~15h is reacted under conditions of 40~50 DEG C, is stood, collects lower floor's thing.Wherein, crown ether-like phase transfer catalysts are selected from 18-
The amine of crown ether -6 or the amine of 15- crown ethers -5, the preferably amine of 18- crown ethers -6.
Specifically, the hexafluoropropylene dimmer of 130~170 parts by weight can be added in reactor, adds 90~120
The powdered fluorinated potassium of the acetonitrile of parts by weight, the amine of 18- crown ethers -6 of 3~5 parts by weight and 0.8~1.2 parts by weight, in 40~50 DEG C
Under conditions of 10~15h of stirring reaction.After this reaction, more than 99.9% perfluor -4- methyl in hexafluoropropylene dimmer -
2- amylenes are completely converted into perfluoro-2-methyl-2-amylene.The maximum reaction product of proportion is collected, such as can first stand 15
Minute or so, lower floor's thing is collected, obtains purity up to 88% perfluoro-2-methyl-2-amylene.
Further, rectifying can be carried out to the perfluoro-2-methyl-2-amylene of above-mentioned gained, it is 45~47 DEG C to collect boiling point,
Preferably 46 DEG C of rectifying thing, purity is obtained up to 99% perfluoro-2-methyl-2-amylene.
Further, by perfluoroepoxide under the conditions of existing for solvent and amines catalyst, isomerization reaction, cooling
To 0~5 DEG C, stratification, collect the maximum reaction product (lower floor's thing) of proportion and carry out rectifying, it is 48~50 then to collect boiling point
DEG C rectifying thing, obtain perfluor hexanone.
Optionally, the above-mentioned solvent mixed with perfluoroepoxide can also be in aprotic polar solvent extremely
Few one kind, such as acetonitrile and dimethylformamide.Because anionic donor with positive moiety and negative electricity part typically by forming,
To weaken the electrical affinity between positive moiety and negative electricity part, the two separation is set to discharge anion, preferably polarity
Larger acetonitrile.
Optionally, above-mentioned amines catalyst includes N, N- dimethyl cyclohexyl amines, double (2- dimethylaminoethyls) ethers, N,
N, N ', N '-tetramethyl Alkylenediamine, triethylamine, N, N- dimethyl benzylamines, triethanolamine and N, in N '-dimethyl pyridine
It is at least one.The selected more other catalyst of amines catalyst (such as metal fluoride) are to perfluor hexanone in the embodiment of the present invention
Synthesis there is more preferably catalytic effect, and can shorten the reaction time.It is preferred that N, N- diformazans are preferably used in the present embodiment
Basic ring hexylamine, cost is relatively low and catalytic effect is preferable, economical and practical.
Preferably, in building-up process, the weight ratio of above-mentioned perfluoroepoxide, solvent and amines catalyst is 90
~110：45~55：3~7.Specifically, can be by the perfluoroepoxide of 90~110 parts by weight, the solvent of 45~55 parts by weight
Added with the amines catalyst of 3~7 parts by weight in reactor, then isomerization reaction.Using chromatographic isomerization
Reacted material is complete to reactant reaction.Its result shows that isomerization reaction can be returned under conditions of 48~52 DEG C
10~14h of stream reaction.It is preferred that isomerization reaction is that return stirring reacts 12h, under the conditions of this, isomery under conditions of 50 DEG C
Change that the time is shorter and high conversion rate.
After isomerization reaction terminates, 0~5 DEG C is cooled to, stratification, lower floor's thing after layering is collected and carries out rectifying.So
It is 48~50 DEG C to collect boiling point afterwards, preferably 49 DEG C of rectifying thing, obtains perfluor hexanone.The purity of the perfluor hexanone is up to 99%.
What deserves to be explained is gas chromatographic detection condition involved in the embodiment of the present invention is as follows：The pressure of nitrogen
Power is 0.06MPa, and the pressure of hydrogen is 0.12MPa, and the pressure of pure air is 0.06MPa.Wherein, pure air pressure in igniting
It is 0.06MPa after igniting for 0.03MPa.Chromatographic column is CP-PoraPLOT Q used by gas chromatographic detection：53m×
0.32mm×0.45μm。
In addition, the embodiment of the present invention additionally provides the perfluor hexanone being synthesized into by above-mentioned synthetic method in fire-fighting fire extinguishing
Application.Specifically, perfluor hexanone can be used for fire-fighting fire extinguishing as extinguishing chemical, good extinguishing effect and green.
The feature and performance of the present invention are described in further detail with reference to embodiments.
Embodiment 1
Acetonitrile, 3 kilograms of tetramethylethylenediamine and the mixture of 1 kilogram of sodium fluoride and cesium fluoride of 90 kilograms of mixing,
Nitrogen, and the stirring reaction 1.2h under conditions of 35 DEG C are passed through, obtains yellow catalyst solution.Then it is every in catalyst solution
Hour adds 18 kilograms of hexachloropropylene, adds 90 kilograms of hexachloropropylene altogether.Reacted under conditions of 30 DEG C and 0.1MPa,
6min is stood every 0.8h, collects lower floor's thing, obtains the hexafluoropropene containing the perfluoro-2-methyl-2-amylene that purity is 88%
Dimer.
250 kilograms of above-mentioned hexafluoropropylene dimmer and 40 kilograms of dimethylformamide are added in reactor, stirring
And 13 DEG C are cooled to, then it is added dropwise 500 kilograms of calcium hypochlorite solution, a length of 7.5h during dropwise addition.Wherein, calcium hypochlorite solution institute
The mass concentration of the Active Chlorine contained is 8%.The temperature of reaction system after regulation addition calcium hypochlorite solution is -35 DEG C.It is added dropwise
After the completion of, 25min is incubated, is cooled to 0 DEG C, stands 28min, collects lower floor's thing, obtains the perfluoroepoxide that purity is 95%.
By 90 kilograms of above-mentioned perfluoroepoxide, 45 kilograms of dimethylformamide and 3 kilograms of double (2- dimethylaminos
Ethyl) ether and N, N, N ', the mixture of N '-tetramethyl Alkylenediamine is added in reactor, is then returned under conditions of 48 DEG C
Stream reaction 14h.0 DEG C is cooled to, stratification, lower floor's thing is collected and carries out rectifying, the rectifying thing that boiling point is 48 DEG C is collected, obtains pure
Spend the perfluor hexanone for 99.1%.
Embodiment 2
Mix 100 kilograms of acetonitrile, 5 kilograms of tetramethylethylenediamine and 3 kilograms of potassium hydro-fluoride, phosphorus pentafluoride and tetrafluoro
Change the mixture of sulphur, be passed through nitrogen, and the stirring reaction 0.8h under conditions of 45 DEG C, obtain yellow catalyst solution.Then in
22 kilograms of hexachloropropylene is added in catalyst solution per hour, adds 110 kilograms of hexachloropropylene altogether.In 40 DEG C and
Reacted under conditions of 0.15MPa, stand 4min every 1.2h, collect lower floor's thing, obtained containing the perfluor -2- first that purity is 90%
The hexafluoropropylene dimmer of base -2- amylenes.
130 kilograms of above-mentioned hexafluoropropylene dimmer is added in reactor, adds 90 kilograms of acetonitrile and dimethyl
The mixture of formamide, 3 kilograms of the amine of 15- crown ethers -5 and 0.8 kilogram of powdered fluorinated potassium, stirred under conditions of 40 DEG C anti-
Answer 15h.15min is stood, collects lower floor's thing, obtains the perfluoro-2-methyl-2-amylene that purity is 92%.Then, to above-mentioned complete
Fluoro- 2- methyl -2- amylenes carry out rectifying, collect the rectifying thing that boiling point is 45 DEG C, obtain perfluor -2- methyl that purity is 99% -
2- amylenes.
350 kilograms of above-mentioned perfluoro-2-methyl-2-amylene and 60 kilograms of acetonitrile are added in reactor, stirred and cold
But to 17 DEG C, then it is added dropwise 700 kilograms of liquor natrii hypochloritis, a length of 8.5h during dropwise addition.Wherein, contained by liquor natrii hypochloritis
The mass concentration of Active Chlorine is 12%.The temperature of reaction system after regulation addition liquor natrii hypochloritis is 20 DEG C.It is added dropwise to complete
Afterwards, 35min is incubated, is cooled to 3 DEG C, stands 32min, collects lower floor's thing, obtains the perfluoroepoxide that purity is 96%.
By 110 kilograms of above-mentioned perfluoroepoxide, the mixture of 55 kilograms of acetonitrile and dimethylformamide and 7 kilograms
Triethylamine, N, the mixture of N- dimethyl benzylamines and triethanolamine adds in reactor, then flowed back under conditions of 52 DEG C
React 10h.5 DEG C are cooled to, stratification, lower floor's thing is collected and carries out rectifying, the rectifying thing that boiling point is 50 DEG C is collected, obtains purity
For 99.2% perfluor hexanone.
Embodiment 3
Acetonitrile, 4 kilograms of tetramethylethylenediamine and 2 kilograms of the potassium fluoride of 95 kilograms of mixing, are passed through nitrogen, and in 40 DEG C
Under conditions of stirring reaction 1h, obtain yellow catalyst solution.Then the six of 20 kilograms are added per hour in catalyst solution
Chloropropene, 100 kilograms of hexachloropropylene is added altogether.Reacted under conditions of 35 DEG C and 0.13MPa, 5min stood every 1h,
Lower floor's thing is collected, obtains the hexafluoropropylene dimmer containing the perfluoro-2-methyl-2-amylene that purity is 93%.
170 kilograms of above-mentioned hexafluoropropylene dimmer added in reactor, add 120 kg acetonitrile, 5 kilograms
The amine of 18- crown ethers -6 and 1.2 kilograms of powdered fluorinated potassium, the stirring reaction 10h under conditions of 50 DEG C.15min is stood, under collection
Layer thing, obtain the perfluoro-2-methyl-2-amylene that purity is 94%.Then, essence is carried out to above-mentioned perfluoro-2-methyl-2-amylene
Evaporate, collect the rectifying thing that boiling point is 47 DEG C, obtain the perfluoro-2-methyl-2-amylene that purity is 99.3%.
300 kilograms of above-mentioned perfluoro-2-methyl-2-amylene and 50 kilograms of acetonitrile are added in reactor, stirred and cold
But to 15 DEG C, then it is added dropwise 600 kilograms of liquor natrii hypochloritis, a length of 8h during dropwise addition.Wherein, the work contained by liquor natrii hypochloritis
Property chlorine mass concentration be 10%.The temperature of reaction system after regulation addition liquor natrii hypochloritis is -7.5 DEG C.It is added dropwise to complete
Afterwards, 30min is incubated, is cooled to 1.5 DEG C, stands 30min, collects lower floor's thing, obtains the perfluoroepoxide that purity is 96.4%.
By 100 kilograms of above-mentioned perfluoroepoxide, 50 kilograms of acetonitrile and 5 kilograms of N, N- dimethyl cyclohexyl amine, N,
The mixture of N '-dimethyl pyridine, triethylamine and triethanolamine is added in reactor, then the back flow reaction under conditions of 50 DEG C
12h.2.5 DEG C are cooled to, stratification, lower floor's thing is collected and carries out rectifying, collects the rectifying thing that boiling point is 49 DEG C, obtaining purity is
99.5% perfluor hexanone.
Embodiment 4
Acetonitrile, 4 kilograms of tetramethylethylenediamine and 2 kilograms of the potassium fluoride of 95 kilograms of mixing, are passed through nitrogen, and in 40 DEG C
Under conditions of stirring reaction 1h, obtain yellow catalyst solution.Then the six of 20 kilograms are added per hour in catalyst solution
Chloropropene, 100 kilograms of hexachloropropylene is added altogether.Reacted under conditions of 35 DEG C and 0.13MPa, 5min stood every 1h,
Lower floor's thing is collected, obtains the hexafluoropropylene dimmer containing the perfluoro-2-methyl-2-amylene that purity is 93%.
150 kilograms of above-mentioned hexafluoropropylene dimmer added in reactor, add 105 kg acetonitrile, 4 kilograms
The amine of 18- crown ethers -6 and 1 kilogram of powdered fluorinated potassium, the stirring reaction 12.5h under conditions of 45 DEG C.15min is stood, under collection
Layer thing, obtain the perfluoro-2-methyl-2-amylene that purity is 95.1%.Then, essence is carried out to above-mentioned perfluoro-2-methyl-2-amylene
Evaporate, collect the rectifying thing that boiling point is 46 DEG C, obtain the perfluoro-2-methyl-2-amylene that purity is 99.4%.
300 kilograms of above-mentioned perfluoro-2-methyl-2-amylene and 50 kilograms of acetonitrile are added in reactor, stirred and cold
But to 15 DEG C, then it is added dropwise 600 kilograms of liquor natrii hypochloritis, a length of 8h during dropwise addition.Wherein, the work contained by liquor natrii hypochloritis
Property chlorine mass concentration be 10%.The temperature of reaction system after regulation addition liquor natrii hypochloritis is 5 DEG C.After being added dropwise to complete,
30min is incubated, is cooled to 0 DEG C, stands 30min, collects lower floor's thing, obtains the perfluoroepoxide that purity is 96.4%.
100 kilograms of above-mentioned perfluoroepoxide, 50 kilograms of acetonitrile and 5 kilograms of N, N- dimethyl cyclohexyl amine are added
In reactor, the then back flow reaction 12h under conditions of 50 DEG C.2.5 DEG C are cooled to, stratification, lower floor's thing is collected and carries out essence
Evaporate, collect the rectifying thing that boiling point is 49 DEG C, obtain the perfluor hexanone that purity is 99.56%.
Test example
Using embodiment 1~4 as test group 1~4, control group is separately set, control group 1 uses the perfluor hexanone of prior art
Preparation method it is as follows：It is anti-in 20~25 DEG C by hexafluoropropene and HFPO under conditions of cesium fluoride makees catalyst
Perfluor hexanone should be obtained.The yield and purity of the perfluor hexanone of comparative test group 1~4 and the gained of control group 1, its result is such as
Shown in table 1.
The yield and purity of the perfluor hexanone of table 1
As can be seen from Table 1, the synthetic method of perfluor hexanone provided in an embodiment of the present invention is compared with control group prior art
Synthetic method, the perfluor hexanone of gained have higher yield and purity.Illustrate perfluor hexanone provided in an embodiment of the present invention
Synthetic method work well, it is practical.
In summary, the synthetic method craft of the perfluor hexanone of the embodiment of the present invention is simple, product purity and synthetic yield
It is higher.It is used for fire-fighting fire extinguishing as extinguishing chemical, good extinguishing effect and green.
Embodiments described above is part of the embodiment of the present invention, rather than whole embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made
Every other embodiment, belongs to the scope of protection of the invention.
Claims (10)
1. a kind of synthetic method of perfluor hexanone, it is characterised in that comprise the following steps：Hexafluoropropylene dimmer and solvent are mixed
Close, be cooled to 13~17 DEG C, add oxidant, collect the maximum reaction product of proportion, obtain perfluoroepoxide；
By the perfluoroepoxide under the conditions of existing for solvent and amines catalyst, isomerization, the anti-of proportion maximum is collected
Product is answered, rectifying, the rectifying thing that boiling point is 48~50 DEG C is collected, obtains perfluor hexanone；
Preferably, the solvent mixed with the hexafluoropropylene dimmer includes acetonitrile and/or dimethylformamide, and described
The solvent of perfluoroepoxide mixing includes acetonitrile and/or dimethylformamide.
2. the synthetic method of perfluor hexanone according to claim 1, it is characterised in that by the hexafluoropropylene dimmer
During synthesizing the perfluoroepoxide, the hexafluoropropylene dimmer, the weight ratio of the solvent and the oxidant
For 250~350：40~60：500~700.
3. the synthetic method of perfluor hexanone according to claim 1, it is characterised in that the oxidant includes hypochlorite
The temperature of solution or oxidation reaction is -35~20 DEG C.
4. the synthetic method of perfluor hexanone according to claim 3, it is characterised in that active in the hypochlorite solutions
The mass concentration of chlorine is 8~12%.
5. the synthetic method of perfluor hexanone according to claim 1, it is characterised in that closed by the perfluoroepoxide
During the perfluor hexanone, the weight ratio of the perfluoroepoxide, the solvent and the amines catalyst is 90
~110：45~55：3~7.
6. the synthetic method of perfluor hexanone according to claim 1, it is characterised in that isomerization reaction is in 48~52 DEG C
Under conditions of 10~14h of back flow reaction.
7. the synthetic method of perfluor hexanone according to claim 1, it is characterised in that the hexafluoropropylene dimmer pass through with
Lower step obtains：By the acetonitrile, the tetramethylethylenediamine of 3~5 parts by weight and containing for 1~3 parts by weight of 90~100 parts by weight
Villiaumite reacts 0.8~1.2h under nitrogen atmosphere, obtains catalyst solution；By the hexachloropropylene of 90~100 parts by weight and 94~
The catalyst solution mixing of 118 parts by weight, then reacts under conditions of 30~40 DEG C and 0.1~0.15MPa, collects ratio
The maximum reaction product of weight；
Preferably, the fluorine-containing salts are included in sodium fluoride, potassium fluoride, cesium fluoride, potassium bifluoride, phosphorus pentafluoride and sulfur tetrafluoride
It is at least one.
8. the synthetic method of perfluor hexanone according to claim 7, it is characterised in that also include to the hexafluoropropene two
Aggressiveness carries out following operate：The hexafluoropropylene dimmer is mixed with acetonitrile, crown ether-like phase transfer catalysts and fluorine-containing salts,
10~15h is reacted under conditions of 40~50 DEG C, collects the maximum reaction product of proportion；
Preferably, the crown ether-like phase transfer catalysts are selected from the amine of 18- crown ethers -6 or the amine of 15- crown ethers -5；
It is highly preferred that the crown ether-like phase transfer catalysts are selected from the amine of 18- crown ethers -6.
9. the perfluor hexanone that the synthetic method of the perfluor hexanone as described in any one of claim 1~8 is synthesized into goes out in fire-fighting
Application in fire.
10. the perfluor hexanone that the synthetic method of perfluor hexanone according to claim 9 is synthesized into is in fire-fighting fire extinguishing
Using, it is characterised in that the perfluor hexanone is added into extinguishment product as constituent；Preferably, the extinguishment product
For extinguishing chemical.
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| CN110092713A (en) * | 2018-01-31 | 2019-08-06 | 上海汇友精密化学品有限公司 | A kind of preparation method of perfluor hexanone |
| CN110170141A (en) * | 2019-06-26 | 2019-08-27 | 厦门一泰消防科技开发有限公司 | A kind of multifunctional fire extinguishing agent and preparation method thereof |
| CN111484398A (en) * | 2019-04-22 | 2020-08-04 | 北京航天神禾防务技术有限公司 | Method for preparing perfluorohexanone |
| CN112250552A (en) * | 2020-09-15 | 2021-01-22 | 浙江巨化技术中心有限公司 | Preparation method of perfluorohexanone |
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| CN116854574A (en) * | 2023-09-04 | 2023-10-10 | 哲弗智能系统（上海）有限公司 | Preparation method of perfluoro hexanone |
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| CN110092713A (en) * | 2018-01-31 | 2019-08-06 | 上海汇友精密化学品有限公司 | A kind of preparation method of perfluor hexanone |
| CN110092713B (en) * | 2018-01-31 | 2022-03-11 | 上海汇友精密化学品有限公司 | Preparation method of perfluorohexanone |
| CN111484398A (en) * | 2019-04-22 | 2020-08-04 | 北京航天神禾防务技术有限公司 | Method for preparing perfluorohexanone |
| CN110170141A (en) * | 2019-06-26 | 2019-08-27 | 厦门一泰消防科技开发有限公司 | A kind of multifunctional fire extinguishing agent and preparation method thereof |
| CN112250552A (en) * | 2020-09-15 | 2021-01-22 | 浙江巨化技术中心有限公司 | Preparation method of perfluorohexanone |
| CN112250552B (en) * | 2020-09-15 | 2023-02-03 | 浙江巨化技术中心有限公司 | Preparation method of perfluorohexanone |
| CN112521257A (en) * | 2020-11-09 | 2021-03-19 | 浙江三美化工股份有限公司 | Process method for producing perfluorohexanone by using hexafluoropropylene as raw material and pipeline reaction device thereof |
| CN112374977A (en) * | 2020-12-18 | 2021-02-19 | 甘肃华隆芯材料科技有限公司 | Preparation method of perfluorohexanone |
| CN116854574A (en) * | 2023-09-04 | 2023-10-10 | 哲弗智能系统（上海）有限公司 | Preparation method of perfluoro hexanone |
| CN116854574B (en) * | 2023-09-04 | 2023-12-12 | 哲弗智能系统（上海）有限公司 | Preparation method of perfluoro hexanone |
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