CN106542981A - The preparation method of nine carbon ketone of perfluor - Google Patents
The preparation method of nine carbon ketone of perfluor Download PDFInfo
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- CN106542981A CN106542981A CN201610841960.XA CN201610841960A CN106542981A CN 106542981 A CN106542981 A CN 106542981A CN 201610841960 A CN201610841960 A CN 201610841960A CN 106542981 A CN106542981 A CN 106542981A
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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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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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Abstract
The invention belongs to fluorine chemical field, and in particular to a kind of preparation method of nine carbon ketone of perfluor, with hexafluoropropylene oxide and hexafluoropropene gas as raw material, it is catalyzed with loaded catalyst, reaction temperature is 50 300 DEG C；Wherein, the active component of described loaded catalyst is alkali metal fluoride, and catalyst carrier is activated carbon；Quality accounting of the described active component in described loaded catalyst is 1% 60%；The draft speed ratio of described hexafluoropropylene oxide and hexafluoropropene gas is more than 2, and draft speed is 4.5g/h 100g/h.The reagent that the preparation method of the present invention is used is simple and easy to get, and preparation process is simple, safety, and the response time is short, and product yield is high, and purity is high, is adapted to large-scale production.
Description
Technical field
The invention belongs to fluorine chemical field, and in particular to a kind of preparation method of nine carbon ketone of perfluor.
Background technology
In recent years, for the discharge for reducing the destruction to atmospheric ozone, limiting greenhouse gases, and then the mankind are protected to rely life
The environment deposited, the property of the fluorine-containing material to using as cold-producing medium, shielding gas, abluent, extinguishing chemical and solvent are proposed more
High request.Fluorinated ketones contained compound because of its good inertia, heat stability and hydrolytic stability, in use with short big
Gas persistent period and low global warming potential, and get the attention.
The property of fluorinated ketones contained compound is the key for determining its application, wherein, with low boiling, high volatile, low
Poison, do not fire, the property such as insulating properties is strong, easily vaporization, heat absorption capacity be strong and be easy to the fluorine ketone of accumulating and be suitable for use as extinguishing chemical, in USP
In 6478979, Rivers etc. discloses application of the perfluorinated ketone in fire extinguishing.The commodity Novec that Minnesota Mining and Manufacturing Company releases
1230, molecular formula is CF3CF2C (O) CF (CF3) 2, is a kind of environmental protection extinguishing chemical for being capable of life-time service.Perfluor ketone can
With oxygen mix, produce radio frequency plasma property can be used for cleaning CVD chamber, physical vapour deposition (PVD)
Room or etching chamber.The standard cleaning gas such as NF3 that the purge gas and semicon industry are used, CF4, C2F6, c-C4F8O and
C3F8 is compared, and can be shortened scavenging period and be reduced PFC discharges.Patent CN 1505694A is reported used in Gas-phase reactor
Perfluor ketone containing 4 to 7 carbon atoms is taken when removing unwanted deposit, etching dielectric and metal material as active gasess
Obtained good effect.Meanwhile, the active gasess of the perfluor ketone are alternatively arranged as Fluorine source, prepare fluorine-containing or fluorine doped material.Patent
CN1809324A and patent CN101346335A report respectively halo perfluor ketone and containing heteroatomic perfluor ketone in cold-producing medium, go out
The application in fiery agent, abluent, additive, foaming agent, solvent, aerosol propellants and agrochemical field.At present, still persistently need
The fluorine-containing ketone compounds of various different application performance requirements can be met.For example, persistently need with various different boilings
The fluorinated ketones contained of scope, heat stability, hydrolytic stability, viscosity characteristicses and molecular weight.
Document (I.M.Fenichev, V.V.Berenblit, T.A.Bispen, N.V.Lebedev, and
D.D.Moldavskii,Catalytic synthesis of certain perfluorinated ketones and
study of their structure by 19F NMR spectroscopy Russian Journal of Applied
Chemistry, 2013, vol.86, No.8, pp.1243-1251) report, with hexafluoropropylene oxide and hexafluoropropene as raw material
There is nine carbon of novel perfluoro that a kind of molecular formula is CF3CF2CF2OCF (CF3) C (O) CF (CF3) CF3 during production perfluor hexanone
Ketogenesiss, and its structure being confirmed by 19F NMR, but using the nine carbon ketone of perfluor during method in above-mentioned document
Yield is extremely low, therefore, a kind of new synthetic method with feature in high yield need to be developed to prepare nine carbon ketone of sterling perfluor.Mesh
Before, the property of the nine carbon ketone of perfluor and its application in fields such as cold-producing medium, abluent, extinguishing chemical, shielding gas are also showed no report
Road.
The content of the invention
It is an object of the invention to overcome the low yield of nine carbon ketone of prior art perfluor, and industrialized shortcoming is not easy to,
A kind of preparation method of nine carbon ketone of perfluor is provided.
To realize that the technical scheme adopted by the purpose of the present invention is：
The preparation method of nine carbon ketone of a kind of perfluor, with hexafluoropropylene oxide and hexafluoropropene gas as raw material, with support type
Catalyst is catalyzed, and reaction temperature is 50-300 DEG C；
Reaction is as shown in formula (I)：
Wherein, the active component of described loaded catalyst is alkali metal fluoride, and catalyst carrier is activated carbon；Institute
Quality accounting of the active component stated in described loaded catalyst is 1%-60%；
The draft speed ratio of described hexafluoropropylene oxide and hexafluoropropene gas is more than 2, and draft speed is 5g/h-
100g/h。
Described alkali metal fluoride is the one kind in LiF, NaF, KF, RbF or CsF.
Described reaction temperature is 100-200 DEG C, the accounting of described active component in described loaded catalyst
Quality is 10%-40%；The draft speed of hexafluoropropene is 10-20g/h.Described active component is in described supported catalyst
Quality accounting in agent is 10%-20%.
Described reaction temperature is 100-150 DEG C, the accounting of described active component in described loaded catalyst
Quality is 10%-20%；The draft speed of hexafluoropropene is 10-20g/h, and described active component is in described supported catalyst
Quality accounting in agent is 10%-20%.
Specifically, comprise the steps:
A. the preparation of loaded catalyst：1) it is 0.1-10mol/ to weigh described alkali metal fluoride configuration quality concentration
The aqueous solution of L, in above-mentioned solution adds activated carbon, is sufficiently stirred for, and mixing time is 5～60h；2) stop stirring, will mixing
Liquid is put in Muffle furnace, evaporates wherein moisture, and evaporating temperature is 50～200 DEG C, under conditions of vacuum and room temperature, is fully dried extremely
Constant weight, that is, be obtained black powder catalyst；3) weigh, calculate the load of alkali metal fluoride in the loaded catalyst
Amount, repeat step 1) -2 such as not up to if requirement)；
B. reacted:1) loaded catalyst obtained in step a is added in the reaction column, by hexafluoropropylene oxide with
Hexafluoropropene gas reaction bulb is connected with the reaction column for being filled with described loaded catalyst；2) check device air-tightness, control
The draft speed of desired reaction temperature and unstrpped gas, after the completion of reaction, opens outlet valve, now carries out condensation receipts to product
Collection；3) head product to collecting carries out the test of infrared and gas chromatogram.
Preferably, the mass concentration of described alkali metal fluoride is 0.1-0.5mol/L.
Compared with prior art, the invention has the beneficial effects as follows：
(1) reagent that preparation method of the invention is used is simple and easy to get, and preparation process is simple, safety, and the response time is short, produces
Product high income, is adapted to large-scale production；
(2) preparation method of the invention, gas chromatogram and infrared test show that products obtained therefrom purity is all higher than 80%, preferably
Embodiment can even be up to more than 99%, and the impurity profit for producing is separated beneficial to purification, the product after purification through rectification
99.99% standard can be obtained.
(3) the of the invention nine carbon ketone of perfluor for obtaining has good characteristic, can apply and multiple fields.
Description of the drawings
Fig. 1 to be illustrated and obtain its boiling point-saturated vapor pressure curve under the nine carbon ketone different pressures of perfluor that embodiment 4 is generated.
Fig. 2 illustrates the gas chromatogram of the nine carbon ketone of perfluor that embodiment 4 is generated.
Fig. 3 illustrates the infrared chromatogram of the nine carbon ketone of perfluor that embodiment 4 is generated.
Specific embodiment
In order that those skilled in the art more fully understand technical scheme, below in conjunction with the accompanying drawings and most
The present invention is described in further detail for good embodiment.
Embodiment 1：a：The preparation of loaded catalyst：1) cesium fluoride (CsF) for weighing 0.06 mole is configured to 1L concentration
For the aqueous solution of 0.06mol/L, 100g activated carbons are added in above-mentioned solution, is sufficiently stirred for, mixing time is 10 hours；2) stop
Only stir, mixed liquor is put in into Muffle furnace, evaporate wherein moisture, evaporating temperature is 80 degrees Celsius, under conditions of vacuum and room temperature
Fully it is dried to constant weight, that is, obtains black powder catalyst；3) weigh, calculate cesium fluoride (CsF) in the loaded catalyst
Load capacity be 5%.
b：Synthesis nine carbon ketone of perfluor：1) cesium fluoride (CsF) catalyst that 50g load capacity is 5% is added in reaction column, will
Hexafluoropropylene oxide is connected with hexafluoropropene gas reaction raw materials with the reaction column for being filled with catalyst；2) check device air-tightness,
Controlling reaction temperature is 100 DEG C, and pressure is normal pressure, and hexafluoropropylene oxide and hexafluoropropene, Hexafluoropropylene third are passed through in system
The Ventilation Rate of alkane is 10g/h, and the Ventilation Rate of hexafluoropropene is 4.5g/h, after ventilation 1h, opens outlet valve, now to producing
Product carry out condensation collection；3) head product to collecting carries out the test of infrared and gas chromatogram, and analysis result shows：Wherein perfluor
Nine carbon ketone contents more than 90%, conversion rate of products 85%, gas chromatographic analysiss result such as table 1 are illustrated：
Table 1
| Content (%) | Composition |
| 91.265 | Nine carbon ketone of perfluor |
| 2.912 | Hexafluoropropylene oxide |
| 1.827 | Hexafluoropropene |
| 3.996 | Other |
Embodiment 2：a：The preparation of loaded catalyst：1) weigh 0.8 mole of cesium fluoride (CsF) and be configured to 1L concentration and be
The aqueous solution of 0.8mol/L, adds 100g activated carbons in above-mentioned solution, is sufficiently stirred for, and mixing time is 10 hours；2) stop
Mixed liquor is put in Muffle furnace by stirring, evaporates wherein moisture, and evaporating temperature is 200 degrees Celsius, is filled under conditions of vacuum and room temperature
Divide and be dried to constant weight, that is, obtain black powder catalyst；3) weigh, calculate cesium fluoride (CsF) in the loaded catalyst
Load capacity is 50%.
b：Synthesis nine carbon ketone of perfluor：1) cesium fluoride (CsF) catalyst that 50g load capacity is 50% is added in the reaction column,
Hexafluoropropylene oxide is connected with hexafluoropropene gas reaction raw materials with the reaction column for being filled with catalyst；2) check device is airtight
Property, controlling reaction temperature is 160 DEG C, and pressure is normal pressure, and hexafluoropropylene oxide and hexafluoropropene are passed through in system, Hexafluoropropylene
The Ventilation Rate of propane is 100g/h, and the Ventilation Rate of hexafluoropropene is 42g/h, after ventilation 1h, opens outlet valve, now right
Product carries out condensation collection；3) head product to collecting carries out the test of infrared and gas chromatogram, and analysis result shows：It is wherein complete
Nine carbon ketone content more than 90% of fluorine, conversion rate of products 82%, gas chromatographic analysiss result such as table 2 are illustrated：
Table 2
| Content (%) | Composition |
| 92.846 | Nine carbon ketone of perfluor |
| 2.825 | Hexafluoropropylene oxide |
| 1.873 | Hexafluoropropene |
| 2.456 | Other |
Embodiment 3:
a：The preparation of loaded catalyst：1) potassium fluoride (KF) for weighing 0.12 mole is configured to 1L concentration for 0.12mol/
The aqueous solution of L, adds 100g activated carbons in above-mentioned solution, is sufficiently stirred for, and mixing time is 10 hours；2) stop stirring, will
Mixed liquor is put in Muffle furnace, evaporates wherein moisture, and evaporating temperature is 50 degrees Celsius, is fully dried extremely under conditions of vacuum and room temperature
Constant weight, that is, obtain black powder catalyst；3) weigh, the load capacity for calculating cesium fluoride (KF) in the loaded catalyst is
25%.
b：Synthesis nine carbon ketone of perfluor：1) potassium fluoride (KF) catalyst that 50g load capacity is 25% is added in reaction column, will
Hexafluoropropylene oxide is connected with hexafluoropropene gas reaction raw materials with the reaction column for being filled with catalyst；2) check device air-tightness,
Controlling reaction temperature is 120 DEG C, and pressure is normal pressure, and hexafluoropropylene oxide and hexafluoropropene, Hexafluoropropylene third are passed through in system
The Ventilation Rate of alkane is 50g/h, and the Ventilation Rate of hexafluoropropene is 22g/h, after ventilation 1h, opens outlet valve, now to producing
Product carry out condensation collection；3) head product to collecting carries out the test of infrared and gas chromatogram, and analysis result shows：Wherein perfluor
Nine carbon ketone contents 93.584%, conversion rate of products 87%, gas chromatographic analysiss result such as table 3 are illustrated：
Table 3
| Content (%) | Composition |
| 93.584 | Nine carbon ketone of perfluor |
| 2.871 | Hexafluoropropylene oxide |
| 1.796 | Hexafluoropropene |
| 1.749 | Other |
Embodiment 4
a：The preparation of loaded catalyst：1) potassium fluoride (KF) for weighing 0.12 mole is configured to 1L concentration for 0.12mol/
The aqueous solution of L, adds 100g activated carbons in above-mentioned solution, is sufficiently stirred for, and mixing time is 10 hours；2) stop stirring, will
Mixed liquor is put in Muffle furnace, evaporates wherein moisture, and evaporating temperature is 80 degrees Celsius, is fully dried extremely under conditions of vacuum and room temperature
Constant weight, that is, obtain black powder catalyst；3) weigh, the load capacity for calculating potassium fluoride (KF) in the loaded catalyst is
5%.
b：Synthesis nine carbon ketone of perfluor：1) potassium fluoride (KF) catalyst that 50g load capacity is 5% is added in reaction column, will
Hexafluoropropylene oxide is connected with hexafluoropropene gas reaction raw materials with the reaction column for being filled with catalyst；2) check device air-tightness,
Controlling reaction temperature is 100 DEG C, and pressure is normal pressure, and hexafluoropropylene oxide and hexafluoropropene, Hexafluoropropylene third are passed through in system
The Ventilation Rate of alkane is 50g/h, and the Ventilation Rate of hexafluoropropene is 20g/h, after ventilation 1h, opens outlet valve, now to producing
Product carry out condensation collection；3) head product to collecting carries out the test of infrared and gas chromatogram, as shown in Figure 2 and Figure 3.Analysis knot
Fruit shows：Wherein nine carbon ketone content more than 99% of perfluor, conversion rate of products 95%, gas chromatographic analysiss result such as table 4 are illustrated：
Table 4
| Content (%) | Composition |
| 99.098 | Nine carbon ketone of perfluor |
| 0.902 | Other |
Embodiment 5
a：The preparation of loaded catalyst：1) lithium fluoride (LiF) for weighing 0.5 mole is configured to 1L concentration for 0.5mol/L
Aqueous solution, in above-mentioned solution add 100g activated carbons, be sufficiently stirred for, mixing time be 10 hours；2) stop stirring, will be mixed
Close liquid and be put in Muffle furnace, evaporate wherein moisture, evaporating temperature is 50 degrees Celsius, is fully dried to perseverance under conditions of vacuum and room temperature
Weight, that is, obtain black powder catalyst；3) weigh, the load capacity for calculating lithium fluoride (LiF) in the loaded catalyst is
10%.
b：Synthesis nine carbon ketone of perfluor：1) lithium fluoride (LiF) catalyst that 50g load capacity is 10% is added in the reaction column,
Hexafluoropropylene oxide is connected with hexafluoropropene gas reaction raw materials with the reaction column for being filled with catalyst；2) check device is airtight
Property, controlling reaction temperature is 300 DEG C, and pressure is normal pressure, and hexafluoropropylene oxide and hexafluoropropene are passed through in system, Hexafluoropropylene
The Ventilation Rate of propane is 100g/h, and the Ventilation Rate of hexafluoropropene is 40g/h, after ventilation 1h, opens outlet valve, now right
Product carries out condensation collection；3) head product to collecting carries out the test of infrared and gas chromatogram, and analysis result shows：It is wherein complete
Nine carbon ketone content more than 89% of fluorine, conversion rate of products 95%, gas chromatographic analysiss result such as table 5 are illustrated：
Table 5
| Content (%) | Composition |
| 79.021 | Nine carbon ketone of perfluor |
| 20.979 | Other |
Embodiment 6
a：The preparation of loaded catalyst：1) potassium fluoride (KF) for weighing 5 moles is configured to the water that 1L concentration is 5mol/L
Solution, adds 100g activated carbons in above-mentioned solution, is sufficiently stirred for, and mixing time is 10 hours；2) stop stirring, by mixed liquor
Muffle furnace is put in, wherein moisture is evaporated, evaporating temperature is 80 degrees Celsius, is fully dried to constant weight under conditions of vacuum and room temperature,
Black powder catalyst is obtained；3) weigh, the load capacity for calculating potassium fluoride (KF) in the loaded catalyst is 60%.
b：Synthesis nine carbon ketone of perfluor：1) potassium fluoride (KF) catalyst that 50g load capacity is 50% is added in reaction column, will
Hexafluoropropylene oxide is connected with hexafluoropropene gas reaction raw materials with the reaction column for being filled with catalyst；2) check device air-tightness,
Controlling reaction temperature is 50 DEG C, and pressure is normal pressure, and hexafluoropropylene oxide and hexafluoropropene, hexafluoropropylene oxide are passed through in system
Ventilation Rate be 50g/h, the Ventilation Rate of hexafluoropropene is 20g/h, after ventilation 1h, opens outlet valve, now to product
Carry out condensation collection；3) head product to collecting carries out the test of infrared and gas chromatogram, and analysis result shows：Wherein perfluor nine
Carbon ketone content more than 89%, conversion rate of products 89%, gas chromatographic analysiss result such as table 6 are illustrated：
Table 6
| Content (%) | Composition |
| 89.121 | Nine carbon ketone of perfluor |
| 4.241 | Hexafluoropropylene oxide |
| 2.162 | Hexafluoropropene |
| 4.476 | Other |
Embodiment 7
a：The preparation of loaded catalyst：1) potassium fluoride (KF) for weighing 0.01 mole is configured to 1L concentration for 0.01mol/
The aqueous solution of L, adds 100g activated carbons in above-mentioned solution, is sufficiently stirred for, and mixing time is 10 hours；2) stop stirring, will
Mixed liquor is put in Muffle furnace, evaporates wherein moisture, and evaporating temperature is 80 degrees Celsius, is fully dried extremely under conditions of vacuum and room temperature
Constant weight, that is, obtain black powder catalyst；3) weigh, the load capacity for calculating potassium fluoride (KF) in the loaded catalyst is
1%.
b：Synthesis nine carbon ketone of perfluor：1) potassium fluoride (KF) catalyst that 50g load capacity is 5% is added in reaction column, will
Hexafluoropropylene oxide is connected with hexafluoropropene gas reaction raw materials with the reaction column for being filled with catalyst；2) check device air-tightness,
Controlling reaction temperature is 100 DEG C, and pressure is normal pressure, and hexafluoropropylene oxide and hexafluoropropene, Hexafluoropropylene third are passed through in system
The Ventilation Rate of alkane is 50g/h, and the Ventilation Rate of hexafluoropropene is 20g/h, after ventilation 1h, opens outlet valve, now to producing
Product carry out condensation collection；3) head product to collecting carries out the test of infrared and gas chromatogram, and analysis result shows：Wherein perfluor
Nine carbon ketone contents more than 82%, conversion rate of products 82%, gas chromatographic analysiss result such as table 7 are illustrated：
Table 7
| Content (%) | Composition |
| 82.723 | Nine carbon ketone of perfluor |
| 8.371 | Hexafluoropropylene oxide |
| 4.746 | Hexafluoropropene |
| 2.411 | Other |
With the performance test of nine carbon ketone of perfluor obtained in embodiment 4：
(1) by the nine carbon ketone of perfluor for obtaining according to GB/T 261-2008《Flashing test-Bin Siji-Martin remains silent cup
Method》Determine, no flash-point, it was demonstrated that the fluorine ketone of the present invention is non-combustible, can be applied as extinguishing chemical.
(2) as determine different pressures under obtained by nine carbon ketone of perfluor boiling point, obtain its boiling point-saturated vapor pressure curve
(Fig. 1 is illustrated), calculates the saturated vapor pressure of the fluorine ketone at 37 DEG C for 38 millimetress of mercury, the boiling point under 25 DEG C, 1atm
For 112 DEG C；Simultaneously determine hydrocarbon, halogenated hydrocarbons, Chlorofluorocarbons (CFCs), HFC, siloxanes, alcohol, ester, ether, monochlorotoluene, benzotrifluoride,
Dissolubility of the compounds such as PFPE in nine carbon ketone of gained perfluor, as a result shows that the fluorine ketone in the present invention is volatile, dissolving
Performance is high, is suitably used as abluent, solvent, especially can be used as the solvent of dissolving Perfluoropolyether lubricant.Relative to prior art
In C5-C7 perfluor ketone, C9 perfluors ketone is more beneficial for due to the characteristic that its surface tension is little, boiling point is high compared with C5-C7 perfluor ketone
Produce and separate, and cleaning efficiency is higher.C9 perfluor ketone is used as that chip abluent dirt-removing power is strong, has a safety feature, do not pollute
Environment；Washing process enables in particular to form protecting film in chip surface to chip without any damage, completely cuts off air, prevent in air water and its
Its molecule corrodes chip, and antioxidation facilitates the carrying out of next step processing technology.Prove that nine carbon ketone of perfluor can be used as in quasiconductor
In terms of purge gas and applied.
(3) vapour deposition (CVD) room is removed to nine carbon ketone of gained perfluor according to the method adopted in patent CN1505694A
The ability of middle silicon substrate deposit is tested.Nine carbon ketone of gained perfluor is formed into plasma with oxygen mix, by determining
Into CVD chamber and the quality from indoor expellant gas (including catabolite), the utilization rate for calculating the fluorine ketone is 62%.
Relative to the CF of comparative example3C(O)CF(CF3)2Utilization rate be 40%, CF3CF2C(O)CF(CF3)2Utilization rate be 38%, obtain
The utilization rate for going out the nine carbon ketone of perfluor of the present invention is higher.By to SiF under different activities gas flow rate4The test of removal rate,
Show that the fluorine ketone of the present invention also effectively can remove silica-base material from CVD chamber under very low active gasess flow velocity.
By two perfluor ketone CF in the nine carbon ketone of perfluor and CN1505694A of the present invention3C(O)CF(CF3)2And
CF3CF2C(O)CF(CF3)2It is compared.Comparison gas are from CVD chamber and the matter from indoor expellant gas (including catabolite)
Amount, the utilization rate for calculating the fluorine ketone is 62%, relative to the CF of comparative example3C(O)CF(CF3)2Utilization rate be 40%,
CF3CF2C(O)CF(CF3)2Utilization rate be 38%, draw the present invention nine carbon ketone of perfluor utilization rate it is higher.
Meanwhile, relative to traditional abluent gas COF2, nine carbon ketone of perfluor is nontoxic for this, can use safely.Mice is entered
4 hours suction-type acute toxic tests of row find：CF3CF2CF2OCF(CF3)C(O)CF(CF3)CF3LD50 be more than 5000PPm,
By nine carbon ketone of 50mg perfluors by oral administration to stomach, without dead mouse and mice is without any Novel presentation after two weeks.
(4) the gas shield performance of nine carbon ketone of gained perfluor is tested by container of 200mL Aluminum Drums.Aluminum Drum used
Bung of the top for diameter 1cm, the discharge of addition and gas for raw material；Aluminum Drum inner surface is Jing polishings except oxide layer
Unsalted surface.It is put into nine carbon ketone of 30mL perfluors in one bucket, bung is in opening-wide state, when the small volume of wherein nine carbon ketone of perfluor
Add nine carbon ketone when 10mL thereto；Another bucket makes bung open wide and is put in air；To Aluminum Drum inwall after placing 48 hours
Detected, it is found that the Aluminum Drum inwall equipped with nine carbon ketone of perfluor is still metallic aluminium, the Aluminum Drum inwall being positioned in air is generated
Aluminum oxide passivation film.Test result proves that gained perfluor ketone has good anti-oxidation protection performance.
(5) performance of leaking hunting of nine carbon ketone of gained perfluor is verified by object of study of the seam of two panels circuit board.
The joint seal of wherein No. 1 circuit board is bad, has gap, and the joint seal of No. 2 circuit boards is intact.Two panels circuit board is put in dry
Above net filter paper, nine carbon ketone liquid of perfluor is respectively dropped into into No. 1 and No. 2 circuit board seam crossings with syringe, as a result discovery 1 is electric
Road plate seam crossing liquid disappears, and the filter paper below circuit board gets wet, and the liquid of No. 2 circuit board seam crossings is polymerized to a drop.The detection
As a result show：As the surface tension of the perfluor ketone is little, when joint seal is bad gap, nine carbon ketone of perfluor meeting moment is from seam
Gap slides, so as to leak hunting to object of study.
(6) nine carbon ketone of 100mL perfluors is heated to reflux into 7 days at a temperature of 112 DEG C of normal pressure；Nine carbon of 100mL perfluors is taken separately
Ketone is added thereto to brazing metal, at a temperature of 112 DEG C of normal pressure is heated to reflux 7 days；By gas chromatographic measurement, the perfluor
The purity of nine carbon ketone is basically unchanged (table 8 is illustrated).Test result show the nine carbon ketone of perfluor have good heat stability and
Mechanical compatibility (will not affect typical building material) in an unfavourable manner；The nine carbon ketone itself also has excellent electric compatible
Property, do not fire, environmental friendliness, to performances such as the dissolubility differences of polar substancess.Above-mentioned performance proves that gained nine carbon ketone of perfluor is suitable to make
For heat transport fluid.
Table 8
| Sample | Relative purity (gas chromatogram) |
| 112 DEG C of nine carbon ketone of 1.100mL perfluors 7 days | 99.02% |
| 112 DEG C of nine carbon ketone of 2.100mL perfluors 7 days | 98.25% |
| Nine carbon ketone of 3.100mL perfluors+112 DEG C of solder 7 days | 98.76% |
| Nine carbon ketone of 4.100mL perfluors+112 DEG C of solder 7 days | 98.93% |
Test result indicate that, the nine carbon ketone of perfluor of the present invention, can be in quasiconductor purge gas due to its excellent performance
The application of aspect, application that can be in as cold-producing medium, as the application in extinguishing chemical, as the application in heat transport fluid,
As the application in shielding gas, as the application leaked hunting in agent.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (4)
1. the preparation method of nine carbon ketone of a kind of perfluor, it is characterised in that with hexafluoropropylene oxide and hexafluoropropene gas as raw material,
It is catalyzed with loaded catalyst, reaction temperature is 50-300 DEG C；
Reaction is as shown in formula (I)：
Wherein, the active component of described loaded catalyst is alkali metal fluoride, and catalyst carrier is activated carbon；Described
Quality accounting of the active component in described loaded catalyst is 1%-60%；
The draft speed ratio of described hexafluoropropylene oxide and hexafluoropropene gas is more than 2, and draft speed is 4.5g/h-100g/
h。
2. various applications of nine carbon ketone of perfluor according to claim 1, it is characterised in that described alkali metal fluoride
For the one kind in LiF, NaF, KF, RbF or CsF.
3. various applications of nine carbon ketone of perfluor according to claim 1, described reaction temperature are 100-160 DEG C, institute
Accounting quality of the active component stated in described loaded catalyst is 5%-10%；The draft speed of hexafluoropropene is
20-50g/h。
4. various applications of nine carbon ketone of perfluor according to claim 1, it is characterised in that described nine carbon ketone of perfluor
Preparation comprises the steps:
A. the preparation of loaded catalyst：1) described alkali metal fluoride configuration quality concentration is weighed for 0.06-5mol/L's
Aqueous solution, in above-mentioned solution adds activated carbon, is sufficiently stirred for, and mixing time is 5～60h；2) stop stirring, mixed liquor is put
In Muffle furnace, evaporation wherein moisture, evaporating temperature is 50～200 DEG C, under conditions of vacuum and room temperature, is fully dried to perseverance
Weight, that is, be obtained black powder catalyst；3) weigh, calculate the load capacity of alkali metal fluoride in the loaded catalyst,
The repeat step 1) -2 if not up to requiring)；
B. reacted:1) loaded catalyst obtained in adding step a in reaction column, by hexafluoropropylene oxide and hexafluoro
Propylene gas reaction bulb is connected with the reaction column for being filled with described loaded catalyst；2) check device air-tightness, needed for control
The draft speed of reaction temperature and unstrpped gas, after the completion of reaction, opens outlet valve, now carries out condensation collection to product；
3) head product to collecting carries out the test of infrared and gas chromatogram.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111514923A (en) * | 2020-03-27 | 2020-08-11 | 天津市长芦化工新材料有限公司 | Modified silicon dioxide mesoporous catalyst and preparation method thereof |
Citations (3)
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|---|---|---|---|---|
| CN1505694A (en) * | 2001-04-24 | 2004-06-16 | 3M | Use of perfluoroketones as vapor reactor cleaning, etching, and doping gases |
| CN1809324A (en) * | 2003-06-18 | 2006-07-26 | 纳幕尔杜邦公司 | Methods using fluoroketones for: extinguishing fire, preventing fire, and reducing or eliminating the flammability of a flammable working fluid |
| WO2011119421A1 (en) * | 2010-03-26 | 2011-09-29 | 3M Innovative Properties Company | Fluoroether diketones for high temperature heat transfer |
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2016
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Patent Citations (3)
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|---|---|---|---|---|
| CN1505694A (en) * | 2001-04-24 | 2004-06-16 | 3M | Use of perfluoroketones as vapor reactor cleaning, etching, and doping gases |
| CN1809324A (en) * | 2003-06-18 | 2006-07-26 | 纳幕尔杜邦公司 | Methods using fluoroketones for: extinguishing fire, preventing fire, and reducing or eliminating the flammability of a flammable working fluid |
| WO2011119421A1 (en) * | 2010-03-26 | 2011-09-29 | 3M Innovative Properties Company | Fluoroether diketones for high temperature heat transfer |
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| I.M.FENICHEV等: "Catalytic Synthesis of Certain Perfluorinated Ketones and Study of Their Structure by 19F NMR Spectroscopy", 《RUSSIAN JOURNAL OF APPLIED CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111514923A (en) * | 2020-03-27 | 2020-08-11 | 天津市长芦化工新材料有限公司 | Modified silicon dioxide mesoporous catalyst and preparation method thereof |
| CN111514923B (en) * | 2020-03-27 | 2023-06-27 | 天津市长芦化工新材料有限公司 | Modified silicon dioxide mesoporous catalyst and preparation method thereof |
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