Ultrasonic wave-promoted continuous polymerization apparatus for preparing fluoropolymers

Abstract

The utility model discloses a kind of continuous polymerization devices for preparing fluorine-containing polymer of ultrasonic wave promotion, it includes mixing component, ultrasonic wave component and reaction pipeline, the outer surface of the mixing component has multiple medium input port and one mixing output port, the reaction pipeline is connected in the mixing output port and with the mixing component inner intercommunication, to make the mixture material in the mixing component flow into in the reaction pipeline by the mixing output port, the reaction pipeline is located in the ultrasonic wave component, to make the ultrasonic wave component act on the outer surface of the reaction pipeline and the mixture material in the reaction pipeline.In the process of polymerization reaction, after adding ultrasonic wave technology, make polymerization reaction steady, uniform, and do not block reaction pipeline.Simultaneously, make mixture material adopt the way of flat plug flow to carry out reaction, monomer concentration is constant distribution in reaction pipeline, and the obtained polymer product performance is stable, and batch repeatability is good.

Description

Technical Field

[0001] This invention belongs to the technical field of polymer material preparation devices, and specifically relates to an ultrasonic-promoted continuous polymerization device for preparing fluoropolymers. Background Technology

[0002] Perfluoroether rubber is a type of fluorinated elastomer in which all hydrogen atoms on the carbon atoms of the main chain and side chains are replaced by fluorine atoms, and the side chains contain ether bonds. It is a fluororubber that completely lacks carbon-hydrogen bonds. It is produced by introducing perfluoroalkyl ether chains into the main chain of fluororubber macromolecules through emulsion copolymerization. The introduction of perfluoroether groups effectively improves the low-temperature flexibility of the fluororubber molecular chain, fundamentally overcoming the shortcomings of poor low-temperature performance of fluororubber, while retaining its advantages such as high-temperature resistance and resistance to various media. It is the rubber with the best heat resistance and chemical resistance among all synthetic rubbers. Furthermore, it possesses excellent mechanical properties, flame retardancy, and electrical insulation, and is widely used in aerospace, chemical, petroleum, nuclear energy, and semiconductor fields, and is widely regarded as a revolutionary new material. However, with the rapid development of industries such as aerospace, oil refining, chemical, electronics, machinery, high-temperature steam systems, nuclear power plants, and special instruments, there is an urgent need for perfluoroether rubbers that can withstand more extreme environmental conditions: ① Low-temperature resistant perfluoroether rubber: resistant to low temperatures (-30℃) and strong oxidizing media; ② High-temperature resistant perfluoroether rubber: resistant to high temperatures (325℃) and chemical media.

[0003] Perfluoroelastomer (PFE) rubber is produced by compounding raw rubber, vulcanizing agents, fillers, etc. Raw rubber is the base material of PFE rubber and determines the properties of rubber products. With the development of the national economy and modern high technology, the demand for PFE rubber is increasing year by year. Therefore, it is urgent to conduct research on the synthesis of PFE raw rubber.

[0004] Emulsion polymerization typically uses water as the reaction medium, with monomers, emulsifiers, initiators, and other auxiliaries added. As the polymerization reaction proceeds, monomers continuously enter the micelles and continue polymerization, achieving high polymerization rates and molecular weights. The emulsion viscosity does not change significantly during the reaction, which is beneficial for stirring and heat transfer. Therefore, perfluoroether raw rubber is generally synthesized using emulsion polymerization.

[0005] Perfluoroether raw rubber is produced by emulsion copolymerization of tetrafluoroethylene, perfluoroalkyl vinyl ethers, and a third monomer with a sulfurization point. Under emulsion polymerization conditions, fluorinated monomers like tetrafluoroethylene exist in the gas phase, thus their emulsion copolymerization mechanism differs from classical emulsion copolymerization. The dissolution process of gas-phase fluorinated monomers is very slow, and the stirring method and rate have a significant impact on the emulsion polymerization reaction. Furthermore, tetrafluoroethylene and perfluoroalkyl vinyl ethers have different solubilities in the emulsion, and there is also competition between different fluorinated monomers. Therefore, the emulsion copolymerization of fluorinated monomers is a very complex process. The synthesis of perfluoroether raw rubber is an exothermic reaction. In the early stages, heat needs to be provided to the reactants to initiate the reaction; after the reaction begins, excess heat must be removed to maintain a stable operating temperature. Therefore, controlling the polymerization temperature is the most difficult aspect and is another key factor affecting the quality of the raw rubber. The emulsion polymerization system of fluorinated monomers follows the general rules of free radical polymerization, but it also has the characteristic of simultaneously increasing the polymerization rate and polymer molecular weight, exhibiting a unique reaction process and polymerization mechanism. The proportions of fluorinated monomers and the quantity and distribution of vulcanizing monomers in raw rubber play a decisive role in achieving the properties of perfluoroether rubber. Therefore, in-depth research on the emulsion copolymerization reaction of fluorinated monomers and its apparatus is of great significance for synthesizing raw rubber with specific compositions and structures, and for preparing perfluoroether rubber resistant to high and low temperatures.

[0006] Fluoropolymers and perfluoroether raw rubbers are commonly produced using emulsion polymerization.

[0007] To achieve emulsion polymerization, the following fundamental problems must be solved:

[0008] 1) Removal of polymerization heat; 2) Good material mixing; 3) Maintaining a certain residence time; 4) Controlling the degree of backmixing in the continuous polymerization process; 5) Adhesion to the wall and coating.

[0009] Emulsion polymerization can be broadly classified into two categories based on its operation: batch or semi-continuous and continuous. Batch and semi-continuous polymerization equipment uses stirred tank reactors, while continuous polymerization equipment often uses multi-stage continuous stirred tank reactors or other reactor equipment. For emulsion polymerization processes, the stirred tank reactors for batch and semi-continuous polymerization are the same. However, continuous polymerization has many different reaction engineering characteristics.

[0010] Existing continuous polymerization equipment technologies can be mainly divided into three categories, which are described below:

[0011] 1) Continuous polymerization reactor (tank type):

[0012] Chinese patent CN210146004U reports "a continuous production equipment for resin emulsions". Japanese patent JP4-363303 (December 16, 1992) reports "a continuous polymerization method and apparatus". Both belong to the category of batch-type continuous polymerization reactors.

[0013] 2) Continuous polymerization reactor combining pipelines and batch reactor:

[0014] European Patent EP01603394A2 (1985) reported "continuous free radical polymerization in a surface-wiping reactor". It is a continuous polymerization reactor combining a pipeline and a batch reactor.

[0015] 3) Pipeline and microchannel continuous polymerization reactor:

[0016] Patents US0315301A1 (2015) and WO171584A1 (2013) report a "continuous emulsion polymerization reactor and pigging system". Japanese Patent Application Publication No. 2006-350340 (December 28, 2006) reports a continuous emulsion polymerization method. Chinese Patent CN111704694A (September 25, 2020) reports a "continuous production process and continuous production apparatus for emulsion polymers and their applications". All these patents report continuous polymerization reactors using pipelines and microchannels.

[0017] The continuous polymerization apparatuses reported in the above patents are all developed for conventional olefins and related polymerization reactions. The polymerization reaction of fluorinated olefins has certain special characteristics, and it is necessary to develop a continuous polymerization apparatus containing tetrafluoroethylene monomer specifically.

[0018] For example, in the early 1950s, a serious explosion occurred during the early production of tetrafluoroethylene at Imperial Chemical Industries (ICI) in the UK. On March 31, 2006, during the production of perfluoroalkyl iodides at Zhejiang Jusheng Fluorochemical Co., Ltd., a significant amount of explosive substances, including tetrafluoroethylene, was found in the reactor (R101) during the pilot-scale polymerization reaction. Even after nitrogen purging, the oxygen content in reactor (R101) remained excessive, and the pressure was abnormal, creating factors that could trigger a tetrafluoroethylene explosion. This resulted in the explosion of tetrafluoroethylene and other explosive substances. Five people died and two were injured. One contributing factor was the use of an intermittent reactor for the experiment; such a safety accident could have been avoided if a continuous polymerization reactor had been used.

[0019] The production of perfluoroether rubber is inseparable from the polymerization reaction of tetrafluoroethylene, which is full of explosion hazards. Moreover, fluoropolymers have poor solubility and are prone to agglomeration and clogging of reactors. Based on the existing technology, better continuous polymerization equipment needs to be developed. Utility Model Content

[0020] The technical problem to be solved by this utility model is to overcome the defects of existing devices for producing fluoropolymers, such as easy agglomeration and blockage, and to provide an ultrasonically promoted continuous polymerization device for producing fluoropolymers.

[0021] The present invention solves the above-mentioned technical problems through the following technical solution:

[0022] An ultrasonically promoted continuous polymerization apparatus for preparing fluoropolymers is characterized in that it includes a mixing component, an ultrasonic component, and a reaction pipeline. The outer surface of the mixing component has multiple media inlets and a mixing outlet. The reaction pipeline is connected to the mixing outlet and communicates with the interior of the mixing component, so that the mixture in the mixing component flows into the reaction pipeline through the mixing outlet. The reaction pipeline is located inside the ultrasonic component, so that the ultrasonic component acts on the outer surface of the reaction pipeline and the mixture inside the reaction pipeline.

[0023] Preferably, the mixing component includes an inner gas tube and an outer mixing tube. The outer mixing tube is sleeved on the inner gas tube. The bottom wall of the inner wall of the inner gas tube has a through hole so that the gas in the inner gas tube can enter the gap between the inner wall of the outer mixing tube and the outer surface of the inner gas tube for mixing. One end of the outer mixing tube and the inner gas tube both have the medium inlet port, and the other end of the outer mixing tube has the mixing outlet port for connecting to the reaction pipeline.

[0024] Preferably, the mixing component further includes a circulation pipeline and a circulation pump. The circulation pipeline is connected to both ends of the gas inner tube so that a gas circulation passage is formed between the gas inner tube and the circulation pipeline. The circulation pump is connected to the circulation passage.

[0025] And / or, the mixing component further includes a first jacketed tube, which covers the outer surface of the mixing outer tube, so that a first temperature control cavity is formed between the first jacketed tube and the mixing outer tube;

[0026] And / or, the gas inner tube and the mixing outer tube are arranged horizontally and concentrically.

[0027] Preferably, the diameter of the mixing outer tube is 1.5-3.0 times the diameter of the gas inner tube;

[0028] And / or, a plurality of the through holes are spaced apart along the length of the gas inner tube, and the distance between any two adjacent through holes is 2-10 times the diameter of the gas inner tube;

[0029] And / or, one or three through holes are provided along the circumference of the gas inner tube;

[0030] And / or, the through hole is a cylindrical through hole; or, the cross-sectional shape of the through hole is trapezoidal, and the larger end of the through hole faces the mixing outer tube.

[0031] Preferably, the number of the mixing components is one; or, the number of the mixing components is multiple, and the multiple mixing components are connected in series.

[0032] And / or, the ultrasound-promoted continuous polymerization apparatus for preparing fluoropolymers further includes a heat exchanger, with the mixing component located within the heat exchanger.

[0033] Preferably, the ultrasonic component includes an ultrasonic container and an ultrasonic generator, the reaction pipeline is disposed inside the ultrasonic container, and the ultrasonic generator is connected to the ultrasonic container.

[0034] Preferably, the ultrasound-promoted continuous polymerization apparatus for preparing fluoropolymers further includes a controller electrically connected to the ultrasonic component and used to control the switching of the ultrasonic component and its output power.

[0035] And / or, the ultrasonic component further includes a second jacketed tube, which covers the outer surface of the ultrasonic container to form a second temperature-controlled cavity between the second jacketed tube and the ultrasonic container.

[0036] Preferably, the inner wall of the reaction pipeline is provided with a blocking part, one end of the blocking part is connected to the inner wall of the reaction pipeline, and the other end of the blocking part extends inward and protrudes.

[0037] Preferably, the shape of the blocking part is a long strip or a cylinder;

[0038] And / or, a plurality of the blocking portions are spaced apart along the length of the reaction pipeline, and the distance between any two adjacent blocking portions is 2-10 times the diameter of the reaction pipeline;

[0039] And / or, two or three of the blocking parts are provided along the circumference of the reaction pipeline;

[0040] And / or, adjacent blocking portions are staggered from each other along the length of the reaction conduit.

[0041] Preferably, the reaction pipeline is in the shape of a double helical coil;

[0042] And / or, the material of the reaction pipeline is stainless steel, PTFE tubing, graphite, or silicon carbide.

[0043] And / or, the ultrasound-promoted continuous polymerization apparatus for preparing fluoropolymers further includes a collection component, wherein the inlet and outlet of the reaction pipeline are respectively connected to the mixing component and the collection component.

[0044] Based on common knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of this utility model.

[0045] The positive and progressive effects of this utility model are as follows:

[0046] This invention discloses an ultrasonic-promoted continuous polymerization apparatus for preparing fluoropolymers. The mixture from the mixing component enters the reaction pipeline for polymerization. The reaction pipeline is located within the ultrasonic component, which, by incorporating ultrasonic technology during the polymerization process, prevents scale formation in the reaction pipeline. Furthermore, the ultrasound enhances the mixing effect of the mixture, resulting in a stable and uniform polymerization reaction without clogging the reaction pipeline. The reaction pipeline is easy to clean after the reaction, making it suitable for large-scale industrial production. Simultaneously, the continuous polymerization apparatus provided by this patent allows the mixture to react in a plug flow manner, maintaining a constant monomer concentration distribution within the reaction pipeline. This results in polymer products with stable performance and good batch repeatability. Attached Figure Description

[0047] Figure 1 This is a schematic diagram of the structure of an ultrasonic-promoted continuous polymerization apparatus for preparing fluoropolymers according to an embodiment of the present invention.

[0048] Figure 2 This is a schematic diagram of the internal structure of the hybrid component according to an embodiment of the present invention.

[0049] Figure 3 This is a schematic diagram of the structure of various gas inner tubes and through holes according to embodiments of this utility model.

[0050] Figure 4 This is a schematic diagram of the structure in which multiple hybrid components are connected in series in an embodiment of the present invention.

[0051] Figure 5 This is a schematic diagram of the internal structure of the reaction pipeline in an embodiment of the present invention.

[0052] Figure 6 This is a schematic diagram of the structure of various reaction pipelines and blocking parts according to embodiments of this utility model.

[0053] Explanation of reference numerals in the attached figures:

[0054] Reaction line 1

[0055] Blocking part 11

[0056] Hybrid Component 2

[0057] Gas inner tube 21

[0058] Through hole 211

[0059] Hybrid outer tube 22

[0060] Circulation pipe 23

[0061] Circulation pump 24

[0062] Ultrasonic component 3

[0063] Ultrasonic container 31

[0064] Ultrasonic generator 32

[0065] Collect Part 4

[0066] 100 single-unit supply equipment

[0067] Emulsifier supply equipment 200

[0068] Initiator supply equipment 300 Detailed Implementation

[0069] The present invention will be described more clearly and completely below by way of embodiments and in conjunction with the accompanying drawings, but the present invention is not limited to the scope of the embodiments.

[0070] like Figures 1 to 6 As shown in the figure, this utility model discloses an ultrasonic-promoted continuous polymerization apparatus for preparing fluoropolymers. The ultrasonic-promoted continuous polymerization apparatus for preparing fluoropolymers includes a mixing component 2, an ultrasonic component 3, and a reaction pipeline 1. The outer surface of the mixing component 2 has multiple media inlets and a mixing outlet. The reaction pipeline 1 is connected to the mixing outlet and communicates with the inside of the mixing component 2, so that the mixture in the mixing component 2 flows into the reaction pipeline 1 through the mixing outlet. The reaction pipeline 1 is located inside the ultrasonic component 3, so that the ultrasonic component 3 acts on the outer surface of the reaction pipeline 1 and the mixture inside the reaction pipeline 1.

[0071] Multiple media inlets of the mixing component 2 are respectively connected to the monomer supply device 100 and the emulsifier supply device 200, and are used to supply monomers and emulsifiers (aqueous solutions) respectively. The monomers and emulsifiers (aqueous solutions) are injected into the mixing component 2 and thoroughly mixed. After mixing, they flow from the mixing outlet to the reaction pipeline 1. The mixture in the mixing component 2 enters the reaction pipeline 1 for polymerization. The reaction pipeline 1 is located inside the ultrasonic component 3, so that after adding ultrasonic technology during the polymerization reaction, the generated polymer is less likely to form scale in the reaction pipeline 1, and the ultrasonic waves can enhance the mixing effect of the mixture, making the polymerization reaction stable and uniform, and without clogging the reaction pipeline 1. The reaction pipeline 1 is easy to clean after the reaction, making it suitable for large-scale industrial production. At the same time, the continuous polymerization device provided by this patent allows the mixture to react in a plug flow manner, and the monomer concentration in the reaction pipeline 1 is a constant distribution, resulting in polymer products with stable performance and good batch repeatability.

[0072] Monomers can include tetrafluoroethylene, hexafluoropropylene, and perfluoroolefins containing ether bonds, such as trifluoromethoxytrifluorovinyl ether (PMVE) and trifluoromethoxydifluoromethoxytrifluorovinyl ether (MOVE). Emulsifiers are generally surfactants, used to control the polymerization rate, polymer composition, and molecular weight. Adding surfactants during polymerization increases the solid content of the resulting emulsion without causing in-reactor coagulation. Commonly used emulsifiers include ammonium perfluorooctanoate, ammonium perfluorononanoate, and ammonium hexafluorononanoate.

[0073] Because different types of perfluorinated monomers have significantly different polymerization reactivity, traditional intermittent batch polymerization can lead to unstable polymer product performance. However, the continuous polymerization reactor provided in this patent uses a plug flow method for the reaction, resulting in a constant monomer concentration distribution within the pipeline. This results in polymer products with stable performance and good batch repeatability. Furthermore, the use of ultrasonic accelerator technology ensures a smooth and uniform polymerization reaction without clogging the reactor pipelines. The reactor is also easy to clean after the reaction, making it suitable for large-scale industrial production.

[0074] The ultrasonic-promoted continuous polymerization apparatus for preparing fluoropolymers also includes an initiator supply device 300. The initiator supply device 300 can be connected to the media inlet and communicate with the mixing component 2, or it can be connected to the mixing outlet and communicate with the inlet of the reaction pipeline 1. The initiator supply device 300 is used to replenish the initiator. There are two ways to add the initiator: First, if the initiator will not initiate a polymerization reaction in the mixing component 2, it can be added from the media inlet of the mixing component 2. Second, if the initiator can initiate a polymerization reaction in the mixing component 2, the initiator is added from the mixing outlet of the mixing component 2 and directly introduced into the reaction pipeline 1 via a pipeline.

[0075] Water-soluble compounds can be used as initiators, including peroxides, persulfates, and azo compounds, whose half-life should be less than 2 minutes at temperatures of 95–138 °C.

[0076] like Figure 1 , Figure 2 and Figure 3 As shown, the mixing component 2 includes an inner gas tube 21 and an outer mixing tube 22. The outer mixing tube 22 is sleeved on the inner gas tube 21. A through hole 211 is provided on the bottom wall of the inner wall of the inner gas tube 21 so that the gas in the inner gas tube 21 can enter the gap between the inner wall of the outer mixing tube 22 and the outer surface of the inner gas tube 21 through the through hole 211 for mixing. One end of the outer mixing tube 22 and the inner gas tube 21 both have a medium inlet. The other end of the outer mixing tube 22 has a mixing outlet for connecting to the reaction pipeline 1.

[0077] Gaseous monomers enter the mixing component 2 through the inner gas tube 21, while liquid monomers, emulsifiers, and other liquid materials enter the mixing component 2 through the outer mixing tube 22 and are located in the space between the inner wall of the outer mixing tube 22 and the outer surface of the inner gas tube 21. The inner gas tube 21 has a through hole 211, through which the gaseous monomers inside the inner gas tube 21 enter the space between the inner wall of the outer mixing tube 22 and the outer surface of the inner gas tube 21 and mix with the liquid materials. After mixing, the materials are directly introduced into the reaction pipeline 1 through the mixing outlet for polymerization reaction.

[0078] The mixing component 2 also includes a circulation pipe 23 and a circulation pump 24. The circulation pipe 23 is connected to both ends of the gas inner pipe 21 to form a gas circulation path between the gas inner pipe 21 and the circulation pipe 23. The circulation pump 24 is connected to the circulation path. The circulation pump 24 is used to provide power. Unmixed residual gas monomers in the gas inner pipe 21 will be circulated back into the gas inner pipe 21 through the circulation pipe 23 and the circulation pump 24 for use. They will then be combined with fresh gas monomers and enter the mixing component 2 again through the medium inlet for reuse.

[0079] In this embodiment, the gas inner tube 21 and the mixing outer tube 22 are arranged horizontally and concentrically. The diameter of the mixing outer tube 22 is 1.5-3.0 times the diameter of the gas inner tube 21. The mixing component 2 adopts a double-tube structure, and when the diameter of the gas inner tube 21 is 1.0, the diameter of the mixing outer tube 22 is between 1.5 and 3.0 times.

[0080] The through holes 211 are located at the lower part of the gas inner tube 21. There are multiple through holes 211, which are spaced apart along the length of the gas inner tube 21, and the distance between any two adjacent through holes 211 is 2-10 times the diameter of the gas inner tube 21. The number of through holes 211 is arranged according to the diameter distribution of the gas inner tube 21, so that the gas monomers in the gas inner tube 21 can enter the mixing outer tube 22 and achieve uniform mixing.

[0081] like Figure 3 As shown, a through hole 211 can be provided along the circumference of the gas inner tube 21, that is, there is one through hole 211 around the gas inner tube 21, and the through hole 211 is located at the bottom of the gas inner tube 21. Three through holes 211 can also be provided along the circumference of the gas inner tube 21, that is, there are three through holes 211 around the gas inner tube 21.

[0082] The through hole 211 can be cylindrical; the cross-sectional shape of the through hole 211 can also be trapezoidal, with the larger end of the through hole 211 facing the mixing outer tube 22. The average diameter of the through hole 211 is between 0.05 and 0.5 mm.

[0083] In one embodiment, the mixing component 2 further includes a first jacketed tube, which covers the outer surface of the mixing outer tube 22, thereby forming a first temperature-controlled cavity between the first jacketed tube and the mixing outer tube 22. By adding a first jacketed tube to the outer surface of the mixing outer tube 22 and forming a first temperature-controlled cavity, an external cooling or heating medium can flow into the first temperature-controlled cavity to cool or heat the mixture inside the mixing component 2, thereby achieving cooling or heating of the material during the mixing process.

[0084] In another embodiment, the ultrasound-promoted continuous polymerization apparatus for preparing fluoropolymers further includes a heat exchanger, within which the mixing component 2 is located. The entire mixing component 2 is immersed in the heat exchanger, which contains a heat transfer medium, thereby achieving heating or cooling.

[0085] The number of hybrid components 2 can be one. For example... Figure 4 As shown, there are multiple mixing components 2 connected in series. When the material needs to be fully mixed and a single mixing component 2 is not enough, multiple mixing components 2 need to be connected in series to make the material mix more thoroughly.

[0086] Cleaning method and steps for mixing component 2:

[0087] 1) Use water or other solvents that are soluble in raw materials, such as ethanol, to inject into the gas inner tube 21 to clean the gas inner tube 21 and the mixing outer tube 22;

[0088] 2) Use nitrogen gas to enter through the mixing outer tube 22 and backwash 2-3 times;

[0089] 3) Rinse the gas inner tube 21 2-3 times with water or other solvent;

[0090] 4) Clean the mixing component 2 by rinsing it with nitrogen gas through the inlet of the gas inner tube 21 2-3 times.

[0091] The advantages of the mixing component 2 are: the through hole 211 of the gas inner tube 21 is opened at the lower part of the gas inner tube 21, and the gas pressure and gravity cause it to rush out of the gas inner tube 21, which is conducive to the full mixing of gas and liquid materials.

[0092] like Figure 1 As shown, the ultrasonic component 3 includes an ultrasonic container 31 and an ultrasonic generator 32. The reaction pipeline 1 is disposed inside the ultrasonic container 31, and the ultrasonic generator 32 is connected to the ultrasonic container 31. The ultrasonic container 31 is used to contain a medium, so that the reaction pipeline 1 is located in the medium. The ultrasonic generator 32 acts on the ultrasonic container 31 and the internal reaction pipeline 1, so that after adding ultrasonic technology during the polymerization reaction, the generated polymer is less likely to form scale in the reaction pipeline 1, and the ultrasonic waves can enhance the mixing effect of the mixture, making the polymerization reaction stable and uniform, and without clogging the reaction pipeline 1. After the reaction, the reaction pipeline 1 is easy to clean, making it suitable for large-scale industrial production. The medium can be water or other heat transfer media.

[0093] The ultrasonic-promoted continuous polymerization apparatus for preparing fluoropolymers also includes a controller electrically connected to the ultrasonic component 3 and used to control the switching and output power of the ultrasonic component 3. By controlling the switching and output power of the ultrasonic generator 32, the temperature of the medium can be controlled, effectively enhancing the mixing effect of the mixture. The ultrasonic component 3 can be heated or cooled using water or other heat transfer media, with a temperature control range from room temperature to 300°C.

[0094] The ultrasonic component 3 also includes a second jacketed tube, which covers the outer surface of the ultrasonic container 31, forming a second temperature-controlled cavity between the second jacketed tube and the ultrasonic container 31. By adding a second jacketed tube to the outer surface of the ultrasonic container 31 and forming a second temperature-controlled cavity, external cooling or heating media can flow into the second temperature-controlled cavity to cool or heat the media inside the ultrasonic container 31, thereby controlling the temperature of the media and effectively enhancing the mixing effect of the mixture.

[0095] like Figure 1 , Figure 5 and Figure 6As shown, a baffle 11 is provided on the inner wall of the reaction pipeline 1. One end of the baffle 11 is connected to the inner wall of the reaction pipeline 1, and the other end of the baffle 11 extends inward and protrudes. By providing the baffle 11 in the reaction pipeline 1, it is beneficial to fully mix the materials during the polymerization reaction and to facilitate heat transfer. At the same time, the ultrasonic component 3 makes it difficult for scale to form inside the reaction pipeline 1, effectively preventing polymer deposits from forming on the inner surface of the reaction pipeline 1 and affecting the mass and heat transfer of the reaction, or even blocking the pipeline and causing safety accidents, thus ensuring high safety and stability.

[0096] like Figure 5 and Figure 6 As shown, the shape of the blocking part 11 can be a long strip or a cylinder. There are multiple blocking parts 11, which are spaced apart along the length of the reaction pipeline 1, and the distance between any two adjacent blocking parts 11 is 2 to 10 times the diameter of the reaction pipeline 1.

[0097] Two blocking parts 11 can be provided along the circumference of the reaction pipeline 1, that is, there are two blocking parts 11 on one cross section of the reaction pipeline 1 when viewed from the side, and there are two blocking parts 11 on one circumference of the reaction pipeline 1; three blocking parts 11 can be provided along the circumference of the reaction pipeline 1, that is, there are three blocking parts 11 on one cross section of the reaction pipeline 1 when viewed from the side, and there are three blocking parts 11 on one circumference of the reaction pipeline 1.

[0098] Multiple baffles 11 are evenly spaced along one circumference of the reaction pipeline 1. Adjacent baffles 11 along the length of the reaction pipeline 1 are staggered, which is more conducive to the full mixing of materials during the polymerization reaction and to heat transfer.

[0099] In this embodiment, the reaction pipeline 1 is shaped like a double helical coil, meaning that the reaction pipeline 1 adopts a double helical coil reactor. The reaction pipeline 1 is in the shape of two helical coils and is distributed inside the ultrasonic container 31, which is beneficial for the full reaction of materials and heat dissipation. The material of the reaction pipeline 1 can be stainless steel, PTFE tubing, graphite, or silicon carbide.

[0100] The ultrasonic-promoted continuous polymerization apparatus for preparing fluoropolymers also includes a collection component 4. The inlet and outlet of the reaction pipeline 1 are connected to the mixing component 2 and the collection component 4, respectively. The collection component 4 is used to collect the fluoropolymer. The material flowing out of the reaction pipeline 1 enters the product collection component 4, and the crude fluoropolymer can be obtained. After conventional processing, the crude perfluoroether raw rubber can be obtained.

[0101] This invention relates to an ultrasonic-promoted continuous polymerization apparatus for preparing fluoropolymers. Through repeated experiments, it has been found that ultrasonic technology effectively overcomes the aforementioned shortcomings and deficiencies. After incorporating ultrasonic technology into the polymerization reaction, the generated polymer is less prone to scaling on the inner wall of the reaction pipe 1 and the surface of the baffle 11, and the ultrasound enhances the mixing effect of the materials. The materials react in a plug flow manner, resulting in a constant monomer concentration distribution in the pipe, leading to stable polymer product performance and good batch repeatability. The polymerization process is safe, as excess heat is promptly dissipated, preventing explosions caused by excessive polymerization; production efficiency is high. Furthermore, the ultrasonic-promoted technology ensures a stable and uniform polymerization reaction, without clogging the reactor pipes. The reactor is easy to clean after the reaction, making it suitable for large-scale industrial production. All components are connected via pipes and flanges.

[0102] While specific embodiments of this utility model have been described above, those skilled in the art should understand that these are merely illustrative examples, and the scope of protection of this utility model is defined by the appended claims. Those skilled in the art can make various changes or modifications to these embodiments without departing from the principles and essence of this utility model, but all such changes and modifications fall within the scope of protection of this utility model.

Claims

1. An ultrasound-promoted continuous polymerization apparatus for preparing fluoropolymers, characterized in that, It includes a mixing component, an ultrasonic component, and a reaction pipeline. The outer surface of the mixing component has multiple media inlets and a mixing outlet. The reaction pipeline is connected to the mixing outlet and communicates with the interior of the mixing component, so that the mixture in the mixing component flows into the reaction pipeline through the mixing outlet. The reaction pipeline is located inside the ultrasonic component, so that the ultrasonic component acts on the outer surface of the reaction pipeline and the mixture inside the reaction pipeline.

2. The ultrasonically promoted continuous polymerization apparatus for preparing fluoropolymers as described in claim 1, characterized in that, The mixing component includes an inner gas tube and an outer mixing tube. The outer mixing tube is sleeved on the inner gas tube. The bottom wall of the inner wall of the inner gas tube has a through hole so that the gas in the inner gas tube can enter the gap between the inner wall of the outer mixing tube and the outer surface of the inner gas tube for mixing. One end of the outer mixing tube and the inner gas tube both have the medium inlet. The other end of the outer mixing tube has the mixing outlet for connecting to the reaction pipeline.

3. The ultrasonically promoted continuous polymerization apparatus for preparing fluoropolymers as described in claim 2, characterized in that, The mixing component also includes a circulation pipeline and a circulation pump. The circulation pipeline is connected to both ends of the gas inner tube so that a gas circulation passage is formed between the gas inner tube and the circulation pipeline. The circulation pump is connected to the circulation passage. And / or, the mixing component further includes a first jacketed tube, which covers the outer surface of the mixing outer tube, so that a first temperature control cavity is formed between the first jacketed tube and the mixing outer tube; And / or, the gas inner tube and the mixing outer tube are arranged horizontally and concentrically.

4. The ultrasonically promoted continuous polymerization apparatus for preparing fluoropolymers as described in claim 2, characterized in that, The diameter of the mixing outer tube is 1.5-3.0 times the diameter of the gas inner tube; And / or, a plurality of the through holes are spaced apart along the length of the gas inner tube, and the distance between any two adjacent through holes is 2-10 times the diameter of the gas inner tube; And / or, one or three through holes are provided along the circumference of the gas inner tube; And / or, the through hole is a cylindrical through hole; or, the cross-sectional shape of the through hole is trapezoidal, and the larger end of the through hole faces the mixing outer tube.

5. The ultrasonically promoted continuous polymerization apparatus for preparing fluoropolymers as described in claim 1, characterized in that, The number of the hybrid component is one; or, the number of the hybrid components is multiple, and the multiple hybrid components are connected in series. And / or, the ultrasound-promoted continuous polymerization apparatus for preparing fluoropolymers further includes a heat exchanger, with the mixing component located within the heat exchanger.

6. The ultrasonically promoted continuous polymerization apparatus for preparing fluoropolymers as described in claim 1, characterized in that, The ultrasonic component includes an ultrasonic container and an ultrasonic generator, the reaction pipeline is disposed inside the ultrasonic container, and the ultrasonic generator is connected to the ultrasonic container.

7. The ultrasonically promoted continuous polymerization apparatus for preparing fluoropolymers as described in claim 6, characterized in that, The ultrasonic-promoted continuous polymerization apparatus for preparing fluoropolymers also includes a controller electrically connected to the ultrasonic component and used to control the switching and output power of the ultrasonic component. And / or, the ultrasonic component further includes a second jacketed tube, which covers the outer surface of the ultrasonic container to form a second temperature-controlled cavity between the second jacketed tube and the ultrasonic container.

8. The ultrasonically promoted continuous polymerization apparatus for preparing fluoropolymers as described in claim 1, characterized in that, The inner wall of the reaction pipeline is provided with a blocking part, one end of which is connected to the inner wall of the reaction pipeline, and the other end of which extends inward and protrudes.

9. The ultrasonically promoted continuous polymerization apparatus for preparing fluoropolymers as described in claim 8, characterized in that, The shape of the blocking part is a long strip or a cylinder; And / or, a plurality of the blocking portions are spaced apart along the length of the reaction pipeline, and the distance between any two adjacent blocking portions is 2-10 times the diameter of the reaction pipeline; And / or, two or three of the blocking parts are provided along the circumference of the reaction pipeline; And / or, adjacent blocking portions are staggered from each other along the length of the reaction conduit.

10. The ultrasonically promoted continuous polymerization apparatus for preparing fluoropolymers as described in claim 1, characterized in that, The reaction pipeline is shaped like a double spiral coil; And / or, the material of the reaction pipeline is stainless steel, PTFE tubing, graphite, or silicon carbide. And / or, the ultrasound-promoted continuous polymerization apparatus for preparing fluoropolymers further includes a collection component, wherein the inlet and outlet of the reaction pipeline are respectively connected to the mixing component and the collection component.

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