Method and device for synthesizing perfluoropentanone based on halogenated hydrocarbon carbonylation method
Through the halogenated hydrocarbon carbonylation method, perfluoroiodopropane or perfluorobromide butane and palladium or nickel catalysts are used to control the temperature and pressure in the autoclave, which solves the problem of low synthesis activity of perfluoro compound and achieves efficient synthesis of perfluoropentanone.
Patent Information
- Application Number
- CN202510531183.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-25
- Publication Date
- 2025-08-01
AI Technical Summary
The existing perfluoro compound synthesis methods have low reactivity and need to be carried out under extreme conditions. The synthesis method is single and cumbersome.
The halogenated hydrocarbon carbonylation method is used, perfluoroiodopropane or perfluorobromide butane is used as starting materials, palladium complex or nickel catalyst promotes the activation of C-F bonds, potassium fluoride or tetrabutyl ammonium fluoride is added as additives, and carbonyl compounds are generated through carbon monoxide. The reaction is carried out in an autoclave, with the temperature and pressure controlled at 100-150°C and 5-10MPa, and the two-stage reaction is 12-48 hours.
The efficient synthesis of perfluoropentanone under relatively mild conditions has been achieved, which improves the reactive activity and selectivity and simplifies the synthesis process.
Smart Images
Figure CN120398656A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of perfluoropentanone preparation, and specifically to a synthesis method and device of perfluoropentanone based on the carbonylation method of halogenated hydrocarbons. Background Art
[0002] Perfluoro-3-methyl-2-butanone (C5F 10 O), also known as perfluoro-3-methyl-2-butanone or perfluorohexanone (it should be noted that the naming of "perfluoropentanone" and "perfluorohexanone" may be distinguished due to different carbon chain lengths, but here "perfluoropentanone" specifically refers to the C5F 10 O structure), is a perfluoroketone compound. Perfluoropentanone is a perfluorinated compound in which all hydrogen atoms in the molecule are replaced by fluorine atoms, having extremely high chemical stability and thermal stability. It is a colorless, odorless, non-flammable low-pressure liquefiable gas at room temperature, which is convenient for storage and transportation. Its ozone depletion potential (ODP) is 0 and its global warming potential (GWP) is extremely low, being environmentally friendly;
[0003] In the existing synthesis methods of perfluorinated compounds, due to the high bond energy of the C-F bond (about 485 kJ / mol) in perfluorinated compounds, the reaction activity is low, and functional group conversion needs to be achieved under extreme conditions. The existing technologies mostly rely on fluorination reagents (such as potassium fluoride, hydrogen fluoride) or free radical initiation systems, and the synthesis methods are relatively single and cumbersome.
[0004] Therefore, it is necessary to provide a new synthesis method and device of perfluoropentanone based on the carbonylation method of halogenated hydrocarbons to solve the above technical problems. Summary of the Invention
[0005] To solve the above technical problems, the present invention provides a synthesis method of perfluoropentanone based on the carbonylation method of halogenated hydrocarbons.
[0006] The synthesis method of perfluoropentanone based on the carbonylation method of halogenated hydrocarbons provided by the present invention includes:
[0007] (1): Using perfluoroiodopropane (C3F7I) or perfluorobromobutane (C4F9Br) as the starting material as the halogenated hydrocarbon substrate, usually (1.0 equiv);
[0008] (2): By adding a palladium complex (such as Pd(OAc)2 / PPh3) or a nickel catalyst (such as Ni(cod)2) as the main catalyst (0.01 - 0.1 equiv), the selectivity for perfluorinated substrates is improved through ligand regulation. Potassium fluoride (KF) or tetrabutylammonium fluoride (TBAF) is added as an additive and catalyst promoter to facilitate C-F bond activation and promote the reaction of halogenated hydrocarbons with carbon monoxide to form carbonyl compounds. Their iodine / bromine atoms are more likely to leave, which is beneficial to the carbonylation reaction. The bottom output end of the operating rotary motor rotates to drive the stirring blades to stir the compound;
[0009] (3): Then, carbon monoxide (CO) gas is added to the inside of the reaction kettle as the carbonyl source, usually (5 - 10 equiv). It is necessary to ensure the CO solubility and reaction efficiency in the autoclave;
[0010] (4): During the reaction, the internal reaction temperature of the reaction kettle needs to be raised to 100 - 150 °C, and the CO pressure needs to be raised to 5 - 10 MPa. The two-stage reaction is maintained. The first stage is 12 - 24 hours, and the second stage is 24 - 48 hours.
[0011] A reaction device includes a support frame. The inside of the support frame is fixedly connected with a reaction kettle. The top of the reaction kettle is fixedly connected with a top cover. An opening is provided at the top of the top cover. Grooves are provided on both sides of the opening. Threaded holes are provided at the bottom of the two groups of grooves. A rotary motor is movably connected inside the opening. Locking plates are fixedly connected to both sides of the rotary motor. Through holes are provided at the top of the two groups of locking plates. Bolts are movably connected inside the two groups of through holes. The bottoms of the two groups of bolts are engaged with the threaded holes. A pull rod is fixedly connected to the top of the rotary motor. The stirring blades can be conveniently disassembled and cleaned through the provided locking plates.
[0012] Preferably, the bottom output end of the rotary motor is fixedly connected with a rotating shaft, and the bottom end of the rotating shaft is fixedly connected with stirring blades. The compound can be more fully mixed through the provided stirring blades.
[0013] Preferably, a first input pipe and a second input pipe are fixedly connected to the top of the top cover. Gas valves are sleeved on both the first input pipe and the second input pipe. The catalyst can be input through the provided first input pipe, and carbon monoxide can be input through the provided second input pipe.
[0014] Preferably, a third input pipe is fixedly connected to one side of the reaction kettle. A first valve is sleeved on the third input pipe. An output pipe is fixedly connected to the bottom of the reaction kettle. A second valve is sleeved on the output pipe. The halogenated hydrocarbon substrate can be input into the reaction kettle through the provided third input pipe, and the perfluoropentanone synthesized by the reaction can be output through the provided output pipe.
[0015] Preferably, a heating device is installed on one side of the reactor. The inner output end of the heating device penetrates to the inside of the reactor, and the output end is fixedly connected with a heating coil. The heating coil is wound around the inner wall of the reactor, and the inside of the reactor can be heated by the provided heating coil.
[0016] Preferably, an explosion-proof valve is installed at the rear of the reactor. The provided explosion-proof valve can prevent the internal pressure of the reactor from dropping.
[0017] Preferably, a temperature sensor is installed on the front side of the reactor, and a pressure sensor is installed on the front side of the reactor. A display is fixedly connected to the front side of the support frame. The air valve, the first valve, the temperature sensor, the pressure sensor, the second valve, the heating device and the rotating motor are electrically connected to the display through wires, and the other ends of the wires are connected to the controller outside. The various parameters inside the reactor can be intuitively displayed through the provided display.
[0018] Compared with the related art, the synthesis method and device of perfluoropentanone based on the carbonylation method of halogenated hydrocarbons provided by the present invention have the following beneficial effects:
[0019] The present invention provides a synthesis method and device of perfluoropentanone based on the carbonylation method of halogenated hydrocarbons;
[0020] 1. The present invention can synthesize perfluoropentanone through the provided reactor. When it is necessary to synthesize perfluoropentanone through the reactor, the controller outside can be operated to control the first valve to adjust the third input pipe 7 to input perfluoropropyl iodide or perfluorobutyl bromide, operate the controller to control the air valve to adjust the first input pipe to input a palladium complex or a nickel catalyst, operate the controller to control the air valve to adjust the second input pipe to input carbon monoxide, operate the controller to control the bottom output end of the rotating motor to rotate, drive the rotating shaft and the stirring blades fixedly connected to the bottom end to stir and mix the compounds, and operate the controller to control the heating device to heat and pressurize the inside of the reactor 2 through the heating coil 15. The temperature is raised to 100 - 150 °C, and the pressure is raised to 5 - 10 MPa. Keep the two-stage reaction, the first stage is 12 - 24 hours, and the second stage is 24 - 48 hours, so as to realize the synthesis of perfluoropentanone through the carbonylation reaction of halogenated hydrocarbons;
[0021] 2. The present invention can facilitate the disassembly of the rotary motor and the stirring blades through the set locking plate. After the long-term use of the reaction kettle, the bolts at the top of the locking plate can be rotated by using tools to release the meshing connection between the bolts and the threaded holes. By connecting the lifting chain to the pull rod and pulling the lifting chain with a crane to drive the rotary motor and the stirring blades to move upward and take them out through the top opening of the reaction kettle, it is convenient to clean. When reinstallation is required, the crane pulls the lifting chain to drive the cleaned rotary motor and the stirring blades to enter the interior of the reaction kettle through the top opening of the reaction kettle. Align the through holes of the locking plate with the threaded holes, and install the rotary motor on the top of the reaction kettle by the meshing connection of the bolts and the threaded holes, so as to facilitate the installation of the rotary motor and subsequent use of the reaction kettle. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Figure 1 is the overall structural schematic diagram of a reaction device in the present invention;
[0023] Figure 2 is the top view sectional structural schematic diagram of a reaction device in the present invention;
[0024] Figure 3 is the front view sectional structural schematic diagram of a reaction device in the present invention;
[0025] Figure 4 is the side view sectional structural schematic diagram of a reaction device in the present invention.
[0026] Reference numerals in the figures: 1, support frame; 2, reaction kettle; 3, top cover; 4, first input pipe; 5, second input pipe; 6, air valve; 7, third input pipe; 8, first valve; 9, temperature sensor; 10, pressure sensor; 11, output pipe; 12, second valve; 13, display; 14, heating device; 15, heating coil; 16, rotary motor; 17, pull rod; 18, rotating shaft; 19, stirring blade; 20, locking plate; 21, bolt; 22, electric wire; 23, explosion-proof valve; 24, threaded hole. DETAILED DESCRIPTION OF THE EMBODIMENTS
[0027] In order to make the objectives, technical solutions and advantages of the present invention clearer and more understandable, the present invention will be further described in detail below with reference to the drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.
[0028] The following describes the specific implementation of the present invention in detail with reference to specific embodiments.
[0029] Please refer to Figures 1 to 4, A synthesis method of perfluoropentanone based on the carbonylation of halogenated hydrocarbons provided by an embodiment of the present invention, the synthesis method of perfluoropentanone based on the carbonylation of halogenated hydrocarbons includes:
[0030] (1): Using perfluoroiodopropane (C3F7I) or perfluorobromobutane (C4F9Br) as the starting material as the halogenated hydrocarbon substrate, usually (1.0 equiv);
[0031] (2): By adding a palladium complex (such as Pd(OAc)2 / PPh3) or a nickel catalyst (such as Ni(cod)2) as the main catalyst (0.01 - 0.1 equiv), the selectivity for perfluoro substrates is improved through ligand regulation. Potassium fluoride (KF) or tetrabutylammonium fluoride (TBAF) is added as an additive and catalyst promoter to promote C-F bond activation and promote the reaction of the halogenated hydrocarbon with carbon monoxide to form a carbonyl compound. Its iodine / bromine atom is more likely to leave, which is beneficial to the carbonylation reaction. The bottom output end of the operating rotary motor rotates to drive the stirring blades to stir the compound;
[0032] (3): Then, carbon monoxide (CO) gas is added to the inside of the reaction kettle as the carbonyl source, usually (5 - 10 equiv). It is necessary to ensure the CO solubility and reaction efficiency in the autoclave;
[0033] (4): When the reaction is carried out, the internal reaction temperature of the reaction kettle needs to be raised to 100 - 150 °C, and the CO pressure is raised to 5 - 10 MPa. The two-stage reaction is maintained, the first stage is 12 - 24 hours, and the second stage is 24 - 48 hours;
[0034] In the embodiment of the present invention, please refer to Figure 1 and Figure 4 , A reaction device, including a support frame 1. The inner side of the support frame 1 is fixedly connected with a reaction kettle 2. The top of the reaction kettle 2 is fixedly connected with a top cover 3. An opening is provided at the top of the top cover 3. Grooves are provided on both sides of the opening. Threaded holes 24 are provided at the bottoms of the two groups of grooves. A rotary motor 16 is movably connected inside the opening. Locking plates 20 are fixedly connected to both sides of the rotary motor 16. Through holes are provided at the tops of the two groups of locking plates 20. Bolts 21 are movably connected inside the two groups of through holes. The bottoms of the two groups of bolts 21 are engaged with the threaded holes 24. A pull rod 17 is fixedly connected to the top of the rotary motor 16. The stirring blades 19 can be conveniently disassembled and cleaned through the provided locking plates 20.
[0035] It should be noted that: By operating the outer controller, the first valve 8 can be controlled to adjust the perfluoroisoiodopropane or perfluorobromobutane input through the third input pipe 7. By operating the controller to control the gas valve 6, the palladium complex or nickel catalyst can be adjusted to be input through the first input pipe 4. By operating the controller to control the gas valve 6, carbon monoxide can be adjusted to be input through the second input pipe 5. By operating the controller to control the bottom output end of the rotating motor 16 to rotate, the rotating shaft 18 and the stirring blades 19 fixedly connected to the bottom end are driven to stir and mix the compound. By operating the controller to control the heating device 14 to heat and pressurize the interior of the reaction kettle 2 through the heating coil 15, the temperature is raised to 100 - 150 °C and the pressure is raised to 5 - 10 MPa, and a two-stage reaction is maintained. The first stage is 12 - 24 hours and the second stage is 24 - 48 hours, thereby realizing the synthesis of perfluoropentanone through the carbonylation reaction of halogenated hydrocarbons. After the long-term use of the reaction kettle 2 is completed, the bolt 21 at the top of the locking plate 20 can be rotated by using a tool to release the meshing connection between the bolt 21 and the threaded hole 24. By connecting the lifting chain to the pull rod 17, the lifting chain is pulled by a crane to drive the rotating motor 16 and the stirring blades 19 to be taken out upward through the top opening of the reaction kettle 2, so as to facilitate cleaning. When reinstallation is required, the lifting chain is pulled by a crane to drive the cleaned rotating motor 16 and the stirring blades 19 to enter the interior of the reaction kettle 2 through the top opening of the reaction kettle 2. The through hole of the locking plate 20 is aligned with the threaded hole, and the rotating motor 16 is installed on the top of the reaction kettle 2 through the meshing connection of the bolt 21 and the threaded hole 24, thereby realizing the convenient installation of the rotating motor for subsequent use of the reaction kettle.
[0036] In an embodiment of the present invention, please refer to Figure 1 and [[ID=⑥]] Figure 4 The bottom output end of the rotating motor 16 is fixedly connected with a rotating shaft 18, and the bottom end of the rotating shaft 18 is fixedly connected with stirring blades 19. By providing the stirring blades 19, the mixing of the compound can be made more sufficient.
[0037] In an embodiment of the present invention, please refer to Figure 1 and Figure 4 The top of the top cover 3 is fixedly connected with a first input pipe 4 and a second input pipe 5. Gas valves 6 are sleeved on both the first input pipe 4 and the second input pipe 5. The catalyst can be input through the provided first input pipe 4, and carbon monoxide can be input through the provided second input pipe 5.
[0038] In an embodiment of the present invention, please refer to Figure 1 and Figure 4, one side of the reaction kettle 2 is fixedly connected with a third input pipe 7, a first valve 8 is sleeved on the third input pipe 7, the bottom of the reaction kettle 2 is fixedly connected with an output pipe 11, and a second valve 12 is sleeved on the output pipe 11. The halogenated hydrocarbon substrate can be input into the reaction kettle 2 through the provided third input pipe 7, and the synthesized perfluoropentanone can be output through the provided output pipe 11.
[0039] In an embodiment of the present invention, please refer to Figure 1 and Figure 4 , a heating device 14 is installed on one side of the reaction kettle 2, the inner output end of the heating device 14 penetrates to the inside of the reaction kettle 2, and the output end is fixedly connected with a heating coil 15. The heating coil 15 is wound around the inner wall of the reaction kettle 2. The inside of the reaction kettle 2 can be heated through the provided heating coil 15.
[0040] In an embodiment of the present invention, please refer to Figure 1 and Figure 4 , an explosion-proof valve 23 is installed at the rear side of the reaction kettle 2. The inside of the reaction kettle 2 can be prevented from losing pressure through the provided explosion-proof valve 23.
[0041] In an embodiment of the present invention, please refer to Figure 1 and Figure 4 , a temperature sensor 9 is installed on the front side of the reaction kettle 2, a pressure sensor 10 is installed on the front side of the reaction kettle 2, a display 13 is fixedly connected to the front side of the support frame 1, and the air valve 6, the first valve 8, the temperature sensor 9, the pressure sensor 10, the second valve 12, the heating device 14 and the rotary motor 16 are electrically connected to the display 13 through a wire 22. The other end of the wire 22 is connected to an external controller. Various parameters inside the reaction kettle 2 can be visually displayed through the provided display 13.
[0042] The working principle of a reaction device provided by the present invention is as follows:
[0043] When in use, first, the first valve 8 can be controlled by operating the outer controller to adjust the perfluoroisopropyl iodide or perfluorobromobutane input through the third input pipe 7. The gas valve 6 can be controlled by operating the controller to adjust the palladium complex or nickel catalyst input through the first input pipe 4. The gas valve 6 can be controlled by operating the controller to adjust the carbon monoxide input through the second input pipe 5. The bottom output end of the rotating motor 16 can be controlled by operating the controller to rotate, driving the rotating shaft 18 and the stirring blades 19 fixedly connected to the bottom end to stir and mix the compounds. The heating device 14 can be controlled by operating the controller to heat and pressurize the inside of the reaction kettle 2 through the heating coil 15. The temperature is raised to 100 - 150 °C, and the pressure is raised to 5 - 10 MPa. The two-stage reaction is maintained, with the first stage lasting for 12 - 24 hours and the second stage lasting for 24 - 48 hours, thereby realizing the synthesis of perfluoropentanone through the carbonylation reaction of halogenated hydrocarbons. After the long-term use of the reaction kettle 2, the bolt 21 at the top of the locking plate 20 can be rotated by using tools to release the meshing connection between the bolt 21 and the threaded hole 24. By connecting the lifting chain to the pull rod 17, the lifting chain is pulled by the crane to drive the rotating motor 16 and the stirring blades 19 to be taken out upward through the top opening of the reaction kettle 2, thus facilitating cleaning. When reinstallation is required, the crane pulls the lifting chain to drive the cleaned rotating motor 16 and the stirring blades 19 to enter the inside of the reaction kettle 2 through the top opening of the reaction kettle 2. Align the through hole of the locking plate 20 with the threaded hole, and install the rotating motor 16 on the top of the reaction kettle 2 by meshing the bolt 21 with the threaded hole 24, thereby realizing the convenient installation of the rotating motor for subsequent use of the reaction kettle.
[0044] The above are only embodiments of the present invention, and thus do not limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made by using the content of the specification and drawings of the present invention, or directly or indirectly applied in other related technical fields, shall be similarly included within the patent protection scope of the present invention.
Claims
1. A method for synthesizing perfluoropentanone based on the carbonylation method of halogenated hydrocarbons, characterized in that, It includes the following steps: (1): Using perfluoroiodopropane (C3F7I) or perfluorobromobutane (C4F9Br) as the starting material as the haloalkane substrate, usually (1.0 equiv); (2): By adding a palladium complex (such as Pd(OAc)2 / PPh3) or a nickel catalyst (such as Ni(cod)x) as the main catalyst (0.01 - 0.1 equiv), improving the selectivity for the perfluoro substrate through ligand regulation, adding potassium fluoride (KF) or tetrabutylammonium fluoride (TBAF) as additives and catalyst aids to promote C-F bond activation and promote the reaction of the haloalkane with carbon monoxide to form a carbonyl compound, whose iodine / bromine atom is more likely to leave, facilitating the carbonylation reaction, and rotating the bottom output end of the operating rotary motor to drive the stirring blades to stir the compound; (3): Then add carbon monoxide (CO) gas as the carbonyl source to the inside of the reaction kettle, usually (5 - 10 equiv), and it is necessary to ensure the CO solubility and reaction efficiency in the autoclave; (4): When carrying out the reaction, it is necessary to raise the internal reaction temperature of the reaction kettle to 100 - 150 °C and the CO pressure to 5 - 10 MPa, maintaining a two-stage reaction, the first stage for 12 - 24 hours and the second stage for 24 - 48 hours.
2. A reaction device, characterized in that: Applied to the synthesis method described in claim 1, it includes a support frame (1), the inside of the support frame (1) is fixedly connected with a reaction kettle (2), the top of the reaction kettle (2) is fixedly connected with a top cover (3), an opening is provided at the top of the top cover (3), grooves are provided on both sides of the opening, threaded holes (24) are provided at the bottom of the two groups of grooves, a rotary motor (16) is movably connected inside the opening, locking plates (20) are fixedly connected to both sides of the rotary motor (16), through holes are provided at the top of the two groups of locking plates (20), bolts (21) are movably connected inside the two groups of through holes, the bottoms of the two groups of bolts (21) are meshed and connected with the threaded holes (24), and a pull rod (17) is fixedly connected to the top of the rotary motor (16).
3. The synthesis method and device of perfluoropentanone based on the carbonylation method of halogenated hydrocarbons according to claim 2, characterized in that: The bottom output end of the rotary motor (16) is fixedly connected with a rotating shaft (18), and the bottom end of the rotating shaft (18) is fixedly connected with a stirring blade (19).
4. The synthesis method and device of perfluoropentanone based on the carbonylation method of halogenated hydrocarbons according to claim 2, characterized in that: A first input pipe (4) and a second input pipe (5) are fixedly connected to the top of the top cover (3), and air valves (6) are sleeved on both the first input pipe (4) and the second input pipe (5).
5. The synthesis method and device of perfluoropentanone based on the carbonylation method of halogenated hydrocarbons according to claim 2, characterized in that: A third input pipe (7) is fixedly connected to one side of the reaction kettle (2), a first valve (8) is sleeved on the third input pipe (7), an output pipe (11) is fixedly connected to the bottom of the reaction kettle (2), and a second valve (12) is sleeved on the output pipe (11).
6. A method and device for synthesizing perfluoropentanone based on the carbonylation method of halogenated hydrocarbons according to claim 2, characterized in that: A heating device (14) is installed on one side of the reaction kettle (2), the inner output end of the heating device (14) penetrates to the inside of the reaction kettle (2), and the output end is fixedly connected with a heating coil (15), and the heating coil (15) is wound around the inner wall of the reaction kettle (2).
7. A method and apparatus for synthesizing perfluoropentanone based on the carbonylation method of halogenated hydrocarbons according to claim 2, characterized in that: An explosion-proof valve (23) is installed at the rear of the reaction kettle (2).
8. A method and device for synthesizing perfluoropentanone based on the carbonylation method of halogenated hydrocarbons according to claim 2, characterized in that: A temperature sensor (9) is installed on the front side of the reactor (2), a pressure sensor (10) is installed on the front side of the reactor (2), a display (13) is fixedly connected to the front side of the support frame (1), and the air valve (6), the first valve (8), the temperature sensor (9), the pressure sensor (10), the second valve (12), the heating device (14) and the rotary motor (16) are electrically connected to the display (13) through a wire (22), and the other end of the wire (22) is connected to an external controller.