CN114619640B - Preparation equipment and preparation method of perfluorosulfonic acid proton membrane - Google Patents
Preparation equipment and preparation method of perfluorosulfonic acid proton membrane Download PDFInfo
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- CN114619640B CN114619640B CN202210430883.4A CN202210430883A CN114619640B CN 114619640 B CN114619640 B CN 114619640B CN 202210430883 A CN202210430883 A CN 202210430883A CN 114619640 B CN114619640 B CN 114619640B
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- 239000012528 membrane Substances 0.000 title claims abstract description 40
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 32
- 238000003860 storage Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 230000005540 biological transmission Effects 0.000 claims description 15
- 238000007664 blowing Methods 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 238000006073 displacement reaction Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 238000003490 calendering Methods 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- -1 perfluorosulfonic acid ion Chemical class 0.000 claims description 9
- 238000005192 partition Methods 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 8
- 238000001125 extrusion Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0011—Combinations of extrusion moulding with other shaping operations combined with compression moulding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/27—Cleaning; Purging; Avoiding contamination
- B29C48/2715—Cleaning; Purging; Avoiding contamination of plasticising units
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/91—Heating, e.g. for cross linking
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the technical field of proton membrane preparation, in particular to equipment and a method for preparing a perfluorosulfonic acid proton membrane, which comprise an extruder body, wherein the extruder body comprises a first frame, an electric heater is arranged at the top of a machine barrel, and a rotating shaft is arranged at one side of the motor, which is close to a storage bin; the thermal cycle assembly comprises a first shell arranged above the electric heater and a second shell arranged above the machine body, wherein the second shell is arranged in an inclined structure, and the first shell and the second shell are fixedly connected. The invention effectively prevents the problems that the heat consumption of the outer surface of the molten raw material is accelerated in the conveying process, the outer surface of the raw material is hardened, and the surface of the film body is locally broken and damaged in the film forming process due to the hardening area, thereby influencing the quality of the perfluorosulfonic acid proton exchange film after the film forming.
Description
Technical Field
The invention relates to the technical field of proton membrane preparation, in particular to equipment and a method for preparing a perfluorosulfonic acid proton membrane.
Background
The perfluorosulfonic acid proton exchange membrane is a high molecular polymer of a hydrogen ion good conductor and an electronic insulator, and has excellent mechanical, thermal, chemical and electrochemical stability, so that the perfluorosulfonic acid proton exchange membrane has been widely used for preparing ozone by water electrolysis, preparing hydrogen and oxygen by water electrolysis, and preparing an electromechanical synthesis and gas sensor;
at present, the forming process of the perfluorosulfonic acid proton exchange membrane mainly comprises the following steps: extrusion molding, solution molding and composite molding; the extrusion molding process can be divided into melt extrusion molding and gel extrusion molding, and the melt extrusion molding is divided into melt extrusion casting molding and melt extrusion calendaring molding;
In the prior art, raw materials are stirred and then put into an extruder for melt extrusion, and the extruded molten raw materials are conveyed into a calender in a crawler-type manner for calender molding;
In the preparation process, as the temperature of the melted raw material after extrusion is too high, but the outside air temperature is low, the heat consumption of the outer surface of the melted raw material is accelerated during conveying, the outer surface of the raw material is hardened, and the hardening area can cause local rupture and damage of the surface of a film during film formation when the raw material is subjected to pressure delay, so that the quality of the perfluorosulfonic acid proton exchange film after film formation is influenced;
therefore, there is a need for a perfluorosulfonic acid proton membrane manufacturing apparatus and method that solve the above problems.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide a preparation device and a preparation method of a perfluorosulfonic acid proton membrane, which are used for solving the problems that in the prior art, the heat consumption of the outer surface of a molten raw material is accelerated in the conveying process, the outer surface of the raw material is hardened, and the surface of the membrane is locally broken and damaged in the hardening area during membrane formation, so that the quality of the perfluorosulfonic acid proton exchange membrane after membrane formation is affected.
The aim of the invention can be achieved by the following technical scheme: the utility model provides a preparation facilities of perfluorosulfonic acid proton membrane, includes the extruder is whole, the extruder is whole to be including frame one, and frame one's top is provided with motor, feed bin, barrel and mould from right to left in proper order respectively, and is fixed connection between motor, feed bin, barrel and the mould, electric heater is installed at the top of barrel, the motor is close to one side of feed bin is provided with the rotation axis, the hopper is installed at the top of feed bin, the inside bearing of feed bin is connected with axostylus axostyle one, and axostylus axostyle one end with the rotation axis of motor is connected, the outside swing joint of axostylus axostyle one has the loop bar, and the externally mounted of loop bar has the helicoid, the kicking block one is installed to the one end of axostylus axostyle, and the inside swing joint of kicking block one has the kicking block two, the baffle is still installed to the inside of feed bin, and be bearing connection between baffle and the axostylus axostyle one; the conveyor comprises a second frame and a machine body arranged at the top of the second frame; the control panel is arranged on the outer wall of the motor; the thermal cycle assembly comprises a first shell arranged above the electric heater and a second shell arranged above the machine body, wherein the second shell is arranged in an inclined structure, and the first shell and the second shell are fixedly connected.
The method is further characterized in that: the first shell and the second shell are arranged in a semicircular structure, a plurality of groups of through holes are uniformly distributed outside the first shell in an array mode, a spoiler is installed at one end of the second shell away from the first shell, one end of the spoiler away from the second shell is arranged in an arc-shaped structure, and an air blowing assembly is arranged at one side of the first shell away from the second shell.
The method is further characterized in that: the thermal cycle subassembly still including install in the connecting block of the outside both sides of casing, and the screw rod one is installed to the bottom of connecting block, screw rod one's outside threaded connection has swivel nut one, and the externally mounted of swivel nut one has the worm wheel, the bottom bearing of worm wheel is connected with the link plate, and link plate outside one side with frame one is connected, the both sides of frame one bottom all are connected with axostylus axostyle two through the bearing, and the worm is all installed to the both sides of axostylus axostyle two outside, the worm with be the meshing connection between the worm wheel, one side of frame one outside still is provided with axostylus axostyle three, and the both sides of axostylus axostyle three outside all are connected with the connecting seat through the bearing, the connecting seat install in frame one outer wall, two sets of axostylus axostyle two with the outside of axostylus axostyle three is all installed the sprocket, and the external engagement of sprocket is connected with the chain, axostylus axostyle three with be connected through drive assembly between the axostyle one.
The method is further characterized in that: the air blowing assembly comprises an air pipe arranged at the top of the frame, an air opening is arranged on one side, close to the electric heater, of the air pipe, the air opening is arranged in an arc-shaped structure, and a connecting pipe I used for connecting external air blowing equipment is arranged on one side outside the air pipe.
The method is further characterized in that: the transmission assembly comprises a connecting frame which is movably connected to the outside of the shaft rod, two sides of the outside of the connecting frame are connected with the inner wall of the storage bin, an external bearing of the connecting frame is connected with a first gear, one side of the first gear is provided with a second chuck, the external bearing of the second chuck is connected with a lantern ring, one side of the first chuck, which is close to the second chuck, is in a saw-tooth shape, a connecting rod is movably connected to the outside of the lantern ring, sliding grooves are formed in two sides of the inside of the connecting rod, sliding rods are slidably connected to the inside of the sliding grooves, the sliding rods are mounted on the second chuck, a fourth shaft rod is mounted at the top of the connecting rod, the fourth shaft rod is movably connected to the inner wall of the storage bin through bearings, one side of the fourth shaft rod is provided with a second gear, the external engagement of the second gear is connected with a rack plate, one end of the rack plate is provided with an electric push rod, one side of the first gear is engaged with a third gear, the inside of the third gear is mounted with a fifth gear, one side of the third gear is connected with the fourth shaft rod is movably connected to the inner wall of the storage bin, and the fourth shaft rod is further provided with the sixth shaft rod is movably connected to the second shaft rod through the sixth shaft assembly.
The method is further characterized in that: the displacement assembly comprises a push plate movably connected to the outside of the shaft rod, the push plate is connected with the sleeve rod, a second threaded sleeve is installed at two ends of one side of the push plate, the second threaded sleeve penetrates through the partition plate, a second screw rod is connected with the inner wall of the storage bin through a bearing seat, a gear five is installed on the outside of the second screw rod, the gear five is meshed with the gear one, a plurality of groups of clamping blocks are uniformly distributed on the outside of the shaft rod one, grooves are formed in the sleeve rod, movably connected with the clamping blocks, openings are formed in two sides of the inside of the top block, fixing plates are movably connected with the outer wall of the sleeve rod, a supporting block is arranged between the fixing plates, a notch matched with the supporting block is formed in the inner wall of the sleeve rod, a spring is arranged in the notch, and two ends of the spring are fixedly connected with the supporting block and the inner wall of the notch.
The method is further characterized in that: the inside swing joint of barrel has the inner skleeve, and the one end of inner skleeve with be connected through the mount between the kicking block two, the inside of axostylus axostyle one is provided with the desilting subassembly.
The method is further characterized in that: the dredging assembly comprises a water tank arranged in the shaft rod I, a water gap is formed in the outer portion of the shaft rod I in an annular mode, the water gap is distributed in the left section, the middle section and the right section of the shaft rod I, a connecting pipe II staggered with the water gap is formed in the outer portion of the loop bar, an annular pipe is arranged in the outer portion of the shaft rod I, a sliding plate is movably connected to the inner portion of the annular pipe, the outer wall of the sliding plate is connected with a storage bin, a connecting pipe III is arranged on one side of the outer portion of the sliding plate, the connecting pipe III is communicated with the inner portion of the annular pipe, and one end of the connecting pipe III penetrates through the storage bin to extend to the outer surface of the storage bin so as to be connected with external water supply equipment through the connecting pipe III.
The method is further characterized in that: the two sides of the bottom of the machine barrel are respectively provided with a first vent pipe and a second vent pipe, the first vent pipe and the second vent pipe are connected through a connecting pipe in four directions, one side of the bottom of the machine barrel is also provided with a drain outlet, the bottom of the inner sleeve is provided with holes matched with the first vent pipe, the second vent pipe and the drain outlet, and the holes are mutually staggered with the first vent pipe, the second vent pipe and the drain outlet.
The preparation method of the perfluorosulfonic acid proton membrane is characterized by comprising the following steps:
Step one: preparing a solution;
Putting perfluorosulfonic acid ion membrane resin into a reaction kettle, and then sequentially adding diethylene glycol, ethanol, isopropanol, xylene, cyclohexanone, dimethyl sulfoxide, propylene glycol, dimethylformamide and water, wherein the heating temperature is 90-200 ℃ (the maximum cannot exceed 250 ℃);
step two: generating gel;
Stirring the mixed solution for 10min, standing and naturally cooling to obtain perfluorosulfonic acid ionic membrane resin gel;
Step three: extruding the film;
adding perfluorosulfonic acid ionic membrane resin gel into the whole extruder, extruding the melted raw material through the whole extruder, and conveying through a machine body;
Step four: conveying and calendaring;
In the conveying process, redundant heat outside the electric heater is blown to the inside of the second shell through air supply operation of an air port, hot air flow is caused to flow back through the spoiler, the outside of the raw material is insulated, hardening of the outside of the raw material is avoided, and the raw material is added into a calender through a machine body to be calendered into a film;
Step five: forming a film and shaping;
And evaporating the solvent in the perfluorosulfonic acid ion membrane resin gel by using a hot roller and a hot channel to obtain the perfluorosulfonic acid ion membrane.
The invention has the beneficial effects that: according to the invention, the air port is used for supplying air, redundant heat outside the electric heater is blown to the inside of the second shell, hot air flow is caused to flow back through the spoiler, the outside of the raw material is insulated, hardening of the outside of the raw material is avoided, calendaring molding is facilitated by the calendaring machine, the inside is continuously flushed through water injection at the water port and continuously injected air is injected into the first vent pipe and the second vent pipe, internal residue is removed, the problem that the internal residue is difficult to clean is avoided, the operation is time-consuming and labor-consuming, the problem of influence on subsequent processing is effectively prevented, the heat consumption of the outer surface of the molten raw material is accelerated in the conveying process, the hardening area can cause local rupture and damage of the surface of the film during film forming, and the problem of influence on the quality of the perfluorosulfonic proton exchange film after film forming is solved;
1. Through the arrangement of the thermal circulation assembly and the blowing assembly, the normal heat discharge of the electric heater is not influenced, heat can be transmitted to the machine body through the second shell, so that the hardening of the outer surface of the raw material is avoided, meanwhile, through the arrangement of the spoiler, when hot air flows in contact with the spoiler, the hot air flows in a backflow manner through the arc arrangement of the spoiler, and the hot air flows in the backflow manner through the air port, so that the redundant heat on the surface of the electric heater can be moved to the second shell, meanwhile, the heat can be dissipated outside the electric heater, and the damage of the electric heater caused by excessive heat aggregation is avoided;
2. The transmission assembly is arranged, the rack plate is driven to move by the electric push rod, and under the action of meshing connection of the second gear and the rack plate, the first chuck and the second chuck are clamped to drive the first gear to rotate, so that the third shaft rod and the fifth gear synchronously rotate to drive the thermal cycle assembly and the displacement assembly to work;
3. through being provided with displacement subassembly and desilting subassembly, through the effect of swivel nut two and screw rod two threaded connection, the drive loop bar is removed for skew between axostylus axostyle one and the loop bar, thereby kicking block two carry out the shutoff to the clout of inside, simultaneously kicking block two drive inner skleeve removal, make hole and breather pipe one, breather pipe two and drain one-to-one, thereby be convenient for breather pipe one and breather pipe two are to the inside injection gas of barrel, simultaneously, under to outside bath operation through the mouth of a river, clear up the residual material of feed bin and barrel inside, and under the effect through the injection gas, inside rivers roll, wash away to inside residual material, usability and suitability have been improved.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a schematic perspective view of the present invention;
FIG. 2 is a schematic view of the partial perspective view of FIG. 1 in accordance with the present invention;
FIG. 3 is a schematic elevational cross-sectional view of the present invention;
FIG. 4 is a schematic view of the partial perspective cross-sectional structure of FIG. 1 in accordance with the present invention;
FIG. 5 is a schematic perspective view of a thermal cycle assembly of the present invention;
FIG. 6 is a schematic perspective view of the blowing assembly of the present invention;
FIG. 7 is a schematic perspective view of a drive assembly and displacement assembly of the present invention;
FIG. 8 is an enlarged schematic view of the structure of FIG. 7A in accordance with the present invention;
FIG. 9 is a schematic perspective view of the cross-section of FIG. 7 in accordance with the present invention;
FIG. 10 is a schematic side view in cross-section of a portion of the transmission assembly of the present invention;
FIG. 11 is a schematic partial perspective view of a displacement assembly of the present invention;
fig. 12 is a schematic perspective view of the top block two, the inner sleeve and the fixing frame of the present invention.
In the figure:
1. an extruder as a whole; 101. a first frame; 102. a storage bin; 103. a barrel; 104. a mold; 105. an electric heater; 106. a motor; 107. a hopper; 108. a first shaft lever; 109. a loop bar; 110. spiral leaves; 111. a first ejector block; 112. a second ejector block; 113. a partition plate;
2. A conveyor as a whole; 201. a second frame; 202. a body;
3. A control panel;
4. A thermal cycling assembly; 401. a first shell; 402. a second shell; 403. a through hole; 404. a spoiler; 405. a connecting block; 406. a first screw; 407. a first screw sleeve; 408. a worm wheel; 409. a connecting plate; 410. a second shaft lever; 411. a worm; 412. a third shaft lever; 413. a connecting seat; 414. a sprocket; 415. a chain;
5. A transmission assembly; 501. a connecting frame; 502. a first gear; 503. a first chuck; 504. a second chuck; 505. a collar; 506. a connecting rod; 507. a chute; 508. a slide bar; 509. a shaft lever IV; 510. a second gear; 511. rack plate; 512. an electric push rod; 513. a third gear; 514. a shaft lever V; 515. a fourth gear; 516. a shaft lever six; 517. a pulley transmission structure;
6. an air blowing assembly; 601. an air duct; 602. an air port; 603. a first connecting pipe;
7. A displacement assembly; 701. a push plate; 702. a second screw sleeve; 703. a second screw; 704. a fifth gear; 705. a clamping block; 706. an opening; 707. a fixing plate; 708. abutting blocks; 709. a spring;
712. an inner sleeve; 713. a fixing frame;
8. A dredging assembly; 801. a water tank; 802. a water gap; 803. a second connecting pipe; 804. an annular tube; 805. a slide plate; 806. a third connecting pipe; 807. a first vent pipe; 808. a second vent pipe; 809. a connecting pipe IV; 810. and a sewage outlet.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1-12, a preparation device of a perfluorosulfonic acid proton membrane comprises an extruder body 1, wherein the extruder body 1 comprises a first frame 101, a motor 106, a storage bin 102, a machine barrel 103 and a die 104 are sequentially arranged at the top of the first frame 101 from right to left, the motor 106, the storage bin 102, the machine barrel 103 and the die 104 are fixedly connected, an electric heater 105 is arranged at the top of the machine barrel 103, a rotating shaft is arranged at one side of the motor 106, which is close to the storage bin 102, a hopper 107 is arranged at the top of the storage bin 102, a first shaft rod 108 is connected with an inner bearing of the storage bin 102, one end of the first shaft rod 108 is connected with the rotating shaft of the motor 106, a sleeve rod 109 is movably connected with the outer part of the first shaft rod 108, a spiral blade 110 is arranged at one end of the first shaft 108, a top block 111 is movably connected with a second top block 112, a partition 113 is also arranged at the inner part of the storage bin 102, and the partition 113 is in bearing connection with the first shaft rod 108;
the conveyor body 2, the conveyor body 2 comprises a second frame 201 and a machine body 202 arranged on the top of the second frame 201;
a control panel 3 mounted on the outer wall of the motor 106;
The thermal cycle assembly 4, the thermal cycle assembly 4 includes a first housing 401 disposed above the electric heater 105 and a second housing 402 disposed above the machine body 202, and the second housing 402 is disposed in an inclined structure, and the first housing 401 and the second housing 402 are fixedly connected.
The first shell 401 and the second shell 402 are arranged in a semicircular structure, a plurality of groups of through holes 403 are uniformly distributed on the outer surface of the first shell 401 in an array, a spoiler 404 is arranged at one end, far away from the first shell 401, of the second shell 402, the spoiler 404 is arranged in an arc-shaped structure at one end, far away from the second shell 402, of the first shell 401, an air blowing component 6 is arranged at one side, far away from the second shell 402, of the first shell, the normal heat of the electric heater 105 is not influenced, heat can be transmitted to the machine body 202 through the second shell 402, hardening of the outer surface of a raw material is avoided, and meanwhile, when a hot air flow is contacted with the spoiler 404, the hot air flow is buffered through the arc-shaped arrangement of the spoiler 404, so that the hot air flow flows back, and heat accumulation inside the second shell 402 is further ensured;
the thermal cycle component 4 further comprises a connecting block 405 installed on two sides of the outer part of the first shell 401, a first screw rod 406 is installed at the bottom of the connecting block 405, a first screw sleeve 407 is connected to the outer thread of the first screw rod 406, a worm wheel 408 is installed at the outer part of the first screw sleeve 407, a connecting plate 409 is connected to the bottom bearing of the worm wheel 408, one side of the outer part of the connecting plate 409 is connected with the first frame 101, two sides of the bottom of the first frame 101 are connected with a second shaft rod 410 through bearings, two sides of the outer part of the second shaft rod 410 are respectively provided with a worm 411, the worm 411 is in meshed connection with the worm wheel 408, one side of the outer part of the first frame 101 is also provided with a third shaft rod 412, two sides of the third shaft rod 412 are respectively connected with a connecting seat 413 through bearings, the connecting seat 413 is installed on the outer wall of the first frame 101, two groups of the second shaft rods 410 and the third shaft rod 412 are respectively provided with a sprocket 414, the outer part of the sprocket 414 is in meshed connection with a chain 415, the third shaft rod 412 is connected with the second shaft rod 108 through a transmission component 5, and the first screw sleeve is driven to rotate under the action of the meshing connection of the worms 408 and 411, so that the first screw sleeve 406 is driven to lift the first shaft 406 to perform lifting operation, and the first shell 401 and the second shell 402 are lifted and move;
The air blowing assembly 6 comprises an air pipe 601 arranged at the top of the first frame 101, an air port 602 is arranged at one side of the air pipe 601 close to the electric heater 105, the air port 602 is arranged in an arc-shaped structure, a first connecting pipe 603 for connecting external air blowing equipment is arranged at one side of the outer part of the air pipe 601, and hot air flow in the first shell 401 is blown conveniently through the arc-shaped arrangement of the air port 602, so that the hot air is gathered in the second shell 402, and hardening caused by sudden reduction of the temperature of the outer surface of raw materials is avoided;
The transmission component 5 comprises a connecting frame 501 movably connected to the outside of a first shaft rod 108, two sides of the outside of the connecting frame 501 are connected with the inner wall of a storage bin 102, a first gear 502 is connected to an outer bearing of the connecting frame 501, a first chuck 503 is arranged on one side of the first gear 502, a second chuck 504 is arranged on one side of the first chuck 503 far away from the first gear 502, a lantern ring 505 is connected to an outer bearing of the second chuck 504, one side of the first chuck 503, which is close to the second chuck 504, is in a zigzag shape, a connecting rod 506 is movably connected to the outside of the lantern ring 505, sliding grooves 507 are formed in two sides of the inside of the connecting rod 506, sliding rods 508 are connected to the inside of the sliding grooves 507 in a sliding manner, the sliding rods 508 are arranged on the second chuck 504, a fourth shaft 509 is arranged at the top of the connecting rod 506, the fourth shaft 509 is movably connected to the inner wall of the storage bin 102 through a bearing, a second gear 510 is arranged on one side of the outside of the fourth shaft 509, the external meshing of the gear II 510 is connected with a rack plate 511, one end of the rack plate 511 is provided with an electric push rod 512, the electric push rod 512 is connected with the inner wall of the bin 102, one side of the external part of the gear I502 is connected with a gear III 513 in a meshing manner, the internal of the gear III 513 is provided with a shaft lever five 514, one side of the external part of the gear III 513 is also connected with a gear IV 515 in a meshing manner, the internal of the gear IV 515 is provided with a shaft lever six 516, both ends of the shaft lever five 514 and the shaft lever six 516 are movably connected with the inner wall of the bin 102 through bearings, the shaft lever six 516 and the external part of the shaft lever three 412 are in transmission connection through a belt pulley transmission structure 517, two sides of the external part of the gear I502 are also provided with a displacement assembly 7, and the two sides of the external part of the gear I502 are clamped with the chuck I503, so that the gear I502 is driven to rotate to drive the thermal cycle assembly 4 and the displacement assembly 7 to move, and usability is improved;
The displacement assembly 7 comprises a push plate 701 movably connected to the outside of the first shaft rod 108, the push plate 701 is connected with a sleeve rod 109, two ends of one side of the push plate 701 close to the transmission assembly 5 are provided with a second screw sleeve 702, the second screw sleeve 702 penetrates through the partition plate 113 to be connected with a second screw rod 703 in a threaded manner, one end of the second screw rod 703 is connected with the inner wall of the storage bin 102 through a bearing seat, a fifth gear 704 is arranged outside the second screw rod 703, the fifth gear 704 is meshed with the first gear 502, a plurality of groups of clamping blocks 705 are uniformly distributed on the outside of the first shaft rod 108 in a ring shape, grooves movably connected with the clamping blocks 705 are formed in the sleeve rod 109, openings 706 are formed in two sides of the inside of the first top block 111, a fixing plate 707 is movably connected to the inside of the opening 706, the fixing plate 707 is connected with the outer wall of the sleeve rod 109, a propping block 708 is arranged between the fixing plates 707, a notch matched with the propping block 708 is formed in the inner wall of the sleeve rod 109, a spring 709 is arranged in the notch, two ends of the spring 709 are fixedly connected with the propping block 708 and the inner wall of the notch, the sleeve rod 109 is conveniently pushed to displace through threaded connection of the threaded sleeve II 702 and the threaded rod II 703, so that the dredging assembly 8 leaks out, the fixing plates 707 drive the top block II 112 to synchronously displace, the residual materials in the die 104 are extruded, the subsequent preparation is avoided, the top block II 112 moves, and simultaneously, the inner sleeve 712 synchronously moves, so that holes on the inner sleeve 712 are aligned with the vent pipe I807, the vent pipe II 808 and the drain outlet 810, and subsequent operation is convenient;
an inner sleeve 712 is movably connected inside the machine barrel 103, one end of the inner sleeve 712 is connected with the second top block 112 through a fixing frame 713, a dredging component 8 is arranged inside the first shaft rod 108, water is conveniently filled inside the storage bin 102 and the machine barrel 103 through the arrangement of the dredging component 8, and residual raw materials inside are eliminated so as to avoid influencing subsequent processing;
The dredging assembly 8 comprises a water tank 801 arranged inside a first shaft rod 108, a water gap 802 is formed in the outer portion of the first shaft rod 108 in an annular shape, the water gap 802 is distributed in the left section, the middle section and the right section of the first shaft rod 108, a second connecting pipe 803 which is staggered with the water gap 802 is formed in the outer portion of a sleeve rod 109, an annular pipe 804 is arranged in the outer portion of the first shaft rod 108, a sliding plate 805 is movably connected in the annular pipe 804, the outer wall of the sliding plate 805 is connected with a storage bin 102, a third connecting pipe 806 is arranged on one side of the outer portion of the sliding plate 805, the third connecting pipe 806 is communicated with the inner portion of the annular pipe 804, one end of the third connecting pipe 806 penetrates through the storage bin 102 to be connected with external water supply equipment through the third connecting pipe 806, rotary water supply is facilitated through the arrangement of the annular pipe 804 and the sliding plate 805, and meanwhile water injection flushing is facilitated through the arrangement of the annular pipe 802;
The two sides of the bottom of the machine barrel 103 are respectively provided with a first vent pipe 807 and a second vent pipe 808, the first vent pipe 807 and the second vent pipe 808 are connected through a fourth connecting pipe 809, one side of the bottom of the machine barrel 103 is also provided with a drain outlet 810, the bottom of the inner sleeve 712 is provided with holes matched with the first vent pipe 807, the second vent pipe 808 and the drain outlet 810, the holes are mutually staggered with the first vent pipe 807, the second vent pipe 808 and the drain outlet 810, and the holes can be connected with an external air pump through the fourth connecting pipe 809, so that air is conveniently injected into the first vent pipe 807 and the second vent pipe 808, water in the storage bin 102 and the machine barrel 103 is rolled, residual materials in the storage bin 102 and the machine barrel 103 are further cleaned, and raw materials are separated from the inner walls of the storage bin 102 and the machine barrel 103;
a preparation method of a perfluorosulfonic acid proton membrane comprises the following steps:
Step one: preparing a solution;
Putting perfluorosulfonic acid ion membrane resin into a reaction kettle, and then sequentially adding diethylene glycol, ethanol, isopropanol, xylene, cyclohexanone, dimethyl sulfoxide, propylene glycol, dimethylformamide and water, wherein the heating temperature is 90-200 ℃ (the maximum cannot exceed 250 ℃);
step two: generating gel;
Stirring the mixed solution for 10min, standing and naturally cooling to obtain perfluorosulfonic acid ionic membrane resin gel;
Step three: extruding the film;
adding perfluorosulfonic acid ionic membrane resin gel into the whole extruder 1, extruding the melted raw material through the whole extruder 1, and then conveying through a machine body 202;
Step four: conveying and calendaring;
In the conveying process, the air is supplied through an air port 602 to blow and move redundant heat outside the electric heater 105 into the second shell 402, hot air flows back through the spoiler 404 to keep the outside of the raw materials warm, so that the outside of the raw materials are prevented from hardening, and the raw materials are added into a calender through the machine body 202 to be calendered into a film;
Step five: forming a film and shaping;
And evaporating the solvent in the perfluorosulfonic acid ion membrane resin gel by using a hot roller and a hot channel to obtain the perfluorosulfonic acid ion membrane.
Working principle: during operation, wind is discharged from the inside of the wind gap 602 through connecting external blowing equipment, so that redundant heat on the external surface of the electric heater 105 is blown into the inside of the second shell 402, and the heat is reflowed through the arc-shaped arrangement of the spoiler 404, so that a large amount of hot air is accumulated in the inside of the second shell 402, and hardening caused by larger temperature difference during raw material extrusion is avoided;
When the internal residue cleaning device is required to clean, the electric push rod 512 is driven to drive the rack plate 511 to move, under the action of meshing connection of the gear II 510 and the rack plate 511, the chuck I503 and the chuck II 504 are clamped, so that the gear I502 is driven to rotate, the gear II 704 and the gear III 513 around the gear I502 are driven to rotate at the same time, so that the sleeve 109 is driven to move outside the shaft II 108 under the action of threaded connection of the internal screw sleeve II 702 and the screw II 703, the top block II 112 is driven to seal the die 104, and at the same time, the inner sleeve 712 is synchronously moved, so that holes correspond to the vent pipe I807, the vent pipe II 808 and the drain 810, at the moment, the air pump connected with the outside of the connecting pipe IV 809 is operated to inject air into the interior, meanwhile, the connecting pipe III 806 injects water into the water source, washes the interior from the water port 802, and forms continuous flushing operation on the interior together with the air, and the residue is cleaned;
In operation, the third gear 513 drives the fourth gear 515 to rotate, and the third shaft 412 is driven to rotate under the action of the belt pulley transmission structure 517, so that the worm 411 and the worm gear 408 are in meshed connection, and the second housing 402 moves upwards, exposing the whole extruder 1, facilitating the inspection of the outside, and ending the operation.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (7)
1. A perfluorosulfonic acid proton membrane preparation apparatus, comprising:
The extruder is characterized in that the extruder is an extruder body (1), the extruder body (1) comprises a first frame (101), a motor (106), a bin (102), a machine barrel (103) and a die (104) are sequentially arranged at the top of the first frame (101) from right to left, the motor (106), the bin (102), the machine barrel (103) and the die (104) are fixedly connected, an electric heater (105) is arranged at the top of the machine barrel (103), a rotating shaft is arranged at one side, close to the bin (102), of the motor (106), a hopper (107) is arranged at the top of the bin (102), a first shaft rod (108) is connected with an inner bearing of the bin (102), one end of the first shaft rod (108) is connected with the rotating shaft of the motor (106), a sleeve rod (109) is movably connected to the outside of the sleeve rod (109), a spiral blade (110) is arranged at the outside of the sleeve rod (109), a first top block (111) is arranged at one end of the first shaft rod (108), a top block (111) is movably connected with a second top block (112), a second top block (113) is arranged inside the bin (102), and a partition plate (113) is arranged between the first shaft rod (108) and the partition plate (113);
The conveyor integrated body (2), the conveyor integrated body (2) comprises a second frame (201) and a machine body (202) arranged at the top of the second frame (201);
a control panel (3) mounted on the outer wall of the motor (106);
The thermal cycle assembly (4), the thermal cycle assembly (4) comprises a first shell (401) arranged above the electric heater (105) and a second shell (402) arranged above the machine body (202), the second shell (402) is arranged in an inclined structure, and the first shell (401) and the second shell (402) are fixedly connected;
The device comprises a first shell (401) and a second shell (402), wherein the first shell (401) and the second shell (402) are arranged in a semicircular structure, a plurality of groups of through holes (403) are uniformly distributed on the outer portion of the first shell (401) in an array mode, a spoiler (404) is arranged at one end, away from the first shell (401), of the second shell (402), the spoiler (404) is arranged at one end, away from the second shell (402), of the second shell in an arc-shaped structure, and an air blowing assembly (6) is arranged at one side, away from the second shell (402), of the first shell (401);
The thermal cycle component (4) further comprises connecting blocks (405) arranged on two sides of the outer part of the first shell (401), a first screw rod (406) is arranged at the bottom of each connecting block (405), a first screw sleeve (407) is connected to the outer threads of each screw rod (406), a worm wheel (408) is arranged on the outer part of each screw sleeve (407), a connecting plate (409) is connected to a bottom bearing of each worm wheel (408), one side of the outer part of each connecting plate (409) is connected with the first frame (101), two sides of the bottom of the first frame (101) are connected with a second shaft rod (410) through bearings, two sides of the outer part of each second shaft rod (410) are respectively provided with a worm (411), each worm (411) is connected with the worm wheel (408) in a meshed mode, one side of the outer part of the first frame (101) is also provided with a third shaft rod (412), two sides of the outer part of each third shaft rod (412) are respectively connected with a connecting seat (413) through bearings, two groups of second shafts (410) and third shaft rods (414) are respectively connected with a chain wheel (415) through a chain wheel (108), and the third shaft rod (412) is connected with the outer part of the second shaft rod (412);
The air blowing assembly (6) comprises an air pipe (601) arranged at the top of the first frame (101), an air port (602) is arranged on one side, close to the electric heater (105), of the air pipe (601), the air port (602) is arranged in an arc-shaped structure, and a first connecting pipe (603) used for connecting external air blowing equipment is arranged on one side of the outer portion of the air pipe (601).
2. The apparatus according to claim 1, wherein the transmission assembly (5) comprises a connecting frame (501) movably connected to the outside of the first shaft (108), wherein two sides of the outside of the connecting frame (501) are connected with the inner wall of the storage bin (102), a first gear (502) is connected to an external bearing of the connecting frame (501), a first chuck (503) is mounted on one side of the first gear (502), a second chuck (504) is disposed on one side of the first chuck (503) far away from the first gear (502), a collar (505) is connected to an external bearing of the second chuck (504), one side of the first chuck (503) and one side of the second chuck (504) close to each other are zigzag, a connecting rod (506) is movably connected to the outside of the collar (505), sliding grooves (507) are formed in two sides of the inside of the connecting rod (506), sliding bars (508) are connected in a sliding manner, the first gear (503) is mounted on the second chuck (504), a fourth gear (509) is mounted on the inner wall of the top of the connecting rod (506), a fourth shaft (509) is movably connected to the second shaft (510), one side of the fourth shaft (509) is meshed with the fourth shaft (510), the one end of rack board (511) is installed electric putter (512), and electric putter (512) with the inner wall of feed bin (102) is connected, the outside one side meshing of gear one (502) is connected with gear three (513), and the internally mounted of gear three (513) has five (514) of axostylus axostyle, the outside one side still meshing of gear three (513) is connected with four (515) of axostylus axostyle, and the internally mounted of gear four (515) has six (516) of axostylus axostyle, five (514) of axostylus axostyle with the both ends of six (516) of axostylus axostyle all pass through bearing swing joint in the inner wall of feed bin (102), six (516) of axostylus axostyle with the outside of axostyle three (412) is connected through belt pulley transmission structure (517) transmission, the outside both sides of gear one (502) still are provided with displacement subassembly (7).
3. The apparatus of claim 2, wherein the displacement assembly (7) comprises a push plate (701) movably connected to the outside of the first shaft rod (108), the push plate (701) is connected with the sleeve rod (109), two ends of the push plate (701) close to one side of the transmission assembly (5) are respectively provided with a second screw sleeve (702), the second screw sleeve (702) penetrates through the partition plate (113) and is in threaded connection with a second screw rod (703), one end of the second screw rod (703) is connected with the inner wall of the storage bin (102) through a bearing seat, a fifth gear (704) is mounted on the outside of the second screw rod (703), the fifth gear (704) is in meshed connection with the first gear (502), a plurality of groups of clamping blocks (705) are uniformly distributed on the outside of the first shaft rod (108), grooves movably connected with the clamping blocks (705) are formed in the interior of the sleeve rod (109), two sides of the interior of the first screw rod (111) are respectively provided with an opening (706), the interior of the opening (706) is in threaded connection with a second screw rod (703), a fixed plate (708) is arranged between the fixed plate (707) and the inner wall (707) is provided with a groove opening (708), two ends of the spring (709) are fixedly connected with the abutting block (708) and the inner wall of the notch.
4. The equipment for preparing the perfluorosulfonic acid proton membrane according to claim 1, wherein an inner sleeve (712) is movably connected in the machine barrel (103), one end of the inner sleeve (712) is connected with the second top block (112) through a fixing frame (713), and a dredging assembly (8) is arranged in the first shaft rod (108).
5. The preparation device of a perfluorosulfonic acid proton membrane according to claim 4, wherein the dredging component (8) comprises a water tank (801) arranged inside the first shaft rod (108), a water gap (802) is formed in an annular shape outside the first shaft rod (108), the water gap (802) is distributed in a left section, a middle section and a right section of the first shaft rod (108), a second connecting pipe (803) staggered with the water gap (802) is formed in the outer portion of the loop bar (109), an annular pipe (804) is arranged in the outer portion of the first shaft rod (108), a sliding plate (805) is movably connected inside the annular pipe (804), a third connecting pipe (806) is arranged on one side of the outer portion of the sliding plate (805), the third connecting pipe (806) is communicated with the inner portion of the annular pipe (804), and one end of the third connecting pipe (806) penetrates through the outer surface of the storage bin (102) to be connected with external water supply equipment through the third connecting pipe (806).
6. The perfluorosulfonic acid proton membrane preparation device according to claim 4, wherein a first vent pipe (807) and a second vent pipe (808) are respectively installed on two sides of the bottom of the machine barrel (103), the first vent pipe (807) and the second vent pipe (808) are connected through a fourth connecting pipe (809), a drain outlet (810) is further formed in one side of the bottom of the machine barrel (103), holes matched with the first vent pipe (807), the second vent pipe (808) and the drain outlet (810) are formed in the bottom of the inner sleeve (712), and the holes are mutually staggered with the first vent pipe (807), the second vent pipe (808) and the drain outlet (810).
7. A method for preparing a perfluorosulfonic acid proton membrane, which is characterized by adopting the equipment for preparing the perfluorosulfonic acid proton membrane according to claims 1-6, and comprising the following steps:
Step one: preparing a solution;
Putting perfluorosulfonic acid ion membrane resin into a reaction kettle, and then sequentially adding diethylene glycol, ethanol, isopropanol, xylene, cyclohexanone, dimethyl sulfoxide, propylene glycol, dimethylformamide and water, wherein the heating temperature is 90-200 ℃;
step two: generating gel;
Stirring the mixed solution for 10min, standing and naturally cooling to obtain perfluorosulfonic acid ionic membrane resin gel;
Step three: extruding the film;
adding perfluorosulfonic acid ionic membrane resin gel into the whole extruder (1), extruding the melted raw material through the whole extruder (1), and then conveying the raw material through a machine body (202);
Step four: conveying and calendaring;
During conveying, air supply operation is carried out through an air port (602) on the first frame (101) of the air blowing component (6), redundant heat outside the electric heater (105) is blown to the inside of the second shell (402), hot air flows back through the spoiler (404), the outside of the raw materials is kept warm, hardening of the outside of the raw materials is avoided, and the raw materials are added into a calender through the machine body (202) to be calendered into a film;
Step five: forming a film and shaping;
And evaporating the solvent in the perfluorosulfonic acid ion membrane resin gel by using a hot roller and a hot channel to obtain the perfluorosulfonic acid ion membrane.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210430883.4A CN114619640B (en) | 2022-04-22 | 2022-04-22 | Preparation equipment and preparation method of perfluorosulfonic acid proton membrane |
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| CN202210430883.4A CN114619640B (en) | 2022-04-22 | 2022-04-22 | Preparation equipment and preparation method of perfluorosulfonic acid proton membrane |
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