Polymerization device for preparing anion exchange resin by super acid catalysis method and application

Abstract

The invention provides a polymerization device for preparing anion exchange resin through a super acid catalysis method and application, the polymerization device comprises a stator outer cylinder with a mixing cavity inside, a rotor arranged in the mixing cavity, a quenching assembly arranged at the bottom of the stator outer cylinder, an outer circulating pipe and a heat exchange jacket arranged on the periphery of the stator outer cylinder in a sleeving manner, the rotor pushes the polymer material to be mixed in the mixing cavity and move from top to bottom at the same time, the outer circulating pipe is used for communicating the quenching assembly with the upper part of the mixing cavity, so that the polymer material circularly flows among the mixing cavity, the quenching assembly and the outer circulating pipe and is subjected to polymerization reaction, and heat exchange and temperature control are performed on the mixing cavity through a cooling medium in the heat exchange jacket; wherein the stator outer cylinder is made of borosilicate glass, and the rotor, the quenching assembly and the outer circulating pipe are all made of polytetrafluoroethylene materials. The technical problems that in the anion exchange resin preparation process, high corrosion is caused by a super acid catalyst, polymerization products are difficult to flow, and the rapid heat exchange effect is poor are solved.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of ion exchange resin preparation, and in particular to a polymerization device for preparing anion exchange resin by a super acid catalysis method and application thereof. BACKGROUND

[0002] Alkaline anion exchange membrane is a polyelectrolyte that can conduct hydroxide anions, which is composed of a polymer backbone and cationic functional groups. Alkaline anion exchange membrane has a very wide range of applications, and it is an important part of separation devices, purification devices and electrochemical components, playing a crucial role in chlor-alkali industry, water treatment industry, heavy metal recovery, hydrometallurgy and electrochemical industry. Among them, alkaline anion exchange membrane fuel cell and alkaline anion exchange membrane water electrolyzer are two important application fields of alkaline anion exchange membrane, which have important significance for sustainable hydrogen energy field.

[0003] For alkaline anion exchange membrane, alkali resistance stability is one of the important factors affecting its service life, which depends on the chemical stability of the polymer backbone and the cationic functional groups. Under strong alkali conditions, the polymer backbone is prone to oxidation, hydrolysis and cleavage, etc., resulting in a decrease in molecular weight and chain scission; the cationic functional groups are prone to nucleophilic substitution, Hofmann elimination and cationic oxidation-reduction, etc., resulting in a decrease in cation density and functional group degeneration, and the above-mentioned reactions will cause problems such as a decrease in the conductivity of the alkaline anion exchange membrane, a decrease in mechanical strength and dimensional changes. Alkaline anion exchange membrane needs to have good conductivity, mechanical strength, chemical stability, etc. to adapt to the continuous development of various emerging processes, but at present, most of the alkaline anion exchange membranes still have problems such as low ionic conductivity, insufficient mechanical strength, high swelling rate and poor stability in high-temperature alkaline environment.

[0004] Improving the performance of anion exchange membrane depends largely on the design and synthesis of high-performance anion exchange resin. Polybenzimidazole (PBI) is a kind of polymer material with high chemical stability, thermal stability and mechanical strength, and its main chain is composed of repeating benzimidazole rings, which can conduct hydrogen ions after acid protonation; at the same time, it can also transfer hydroxide after alkali doping. In addition, by means of block, graft, crosslinking, etc. to the polybenzimidazole molecular chain, or introducing new functional groups into the main chain, the performance of anion exchange membrane can also be improved.

[0005] In order to further improve the alkali resistance of anion exchange membrane, avoid and alleviate the problems of polymer main chain rupture and degradation of cationic functional groups caused by nucleophilic substitution and other reactions in alkaline aqueous solution, the current research direction is to design and synthesize various new polymers from the molecular structure. For example, the Chinese invention patent with application number 2023117142545 and the title "anion exchange resin containing rigid twisted structure and its preparation method and application" discloses the synthesis of anion exchange resin copolymer under the catalysis of super acid triflic acid, which shows good alkali stability and conductivity; for example, the Chinese patent with application number 2024111288514 and the title "preparation method and application of high alkali-resistant polyarylene alkylene piperidine cation polymer with branched structure" enhances the interaction between polymer molecular chains and increases the molecular weight of the polymer, so that the water swelling of the prepared anion exchange membrane is inhibited, thereby showing outstanding electrical conductivity and mechanical properties. At the same time, the piperidine cation is linked to the polymer backbone with branched structure through flexible spacer, so that the prepared anion exchange membrane has outstanding alkali resistance; for example, the Chinese patent with application number 2025104420541 and the title "block polyaryl piperidine polymer, anion exchange membrane and preparation method thereof" discloses a preparation process including preparation of block polyaryl piperidine polymer, preparation of quaternized block polyaryl piperidine polymer, and preparation of anion exchange membrane. The block polyaryl piperidine polymer and anion exchange membrane are prepared by one-pot method, the preparation process does not need to purify the oligomer for multiple times, the preparation is simple, the regular segment arrangement can form efficient microphase separation structure driven by thermodynamics, and the electrical conductivity of the anion exchange membrane is enhanced.

[0006] Through the above technical means, the alkali resistance of the polymer molecular structure can be obviously improved, and the conductivity, swelling rate and mechanical strength of the prepared anion exchange membrane can be significantly improved. However, the above polymerization process is limited to small-scale preparation in the laboratory, and strong organic acids (including triflic acid, methanesulfonic acid, etc.) are used as catalysts, which have strong corrosion and bring great difficulty to the selection of polymerization equipment for industrial scale-up. In addition, in the above super acid catalyzed polymerization process, the reaction heat needs to be removed in time to maintain the polymerization reaction system at a low temperature state to avoid polymerization process branching and crosslinking, so as to synthesize linear polymers. When the polymerization process occurs branching and crosslinking reaction, the prepared polymer is difficult to dissolve in organic solvent, and the polymer casting solution cannot be prepared and the anion exchange membrane cannot be prepared by solution casting method.

[0007] The process of preparing alkali-resistant anion exchange resin by superacid catalysis is characterized by high corrosion and the need for rapid heat exchange. Especially in industrial applications (the industrial production process of alkali-resistant anion exchange resin), there are problems such as high material corrosion, poor heat exchange effect, and high viscosity polymerization product discharge. At present, no effective solution has been provided.

[0008] Therefore, the present invention proposes a polymerization apparatus and its application for preparing anion exchange resin by superacid catalysis, in order to solve at least one of the above-mentioned technical problems. Summary of the Invention

[0009] The purpose of this invention is to provide a polymerization apparatus and its application for preparing anion exchange resins by superacid catalysis. Addressing the characteristics of high material corrosivity and strict temperature control requirements in the superacid catalysis process for preparing alkali-resistant anion exchange resins, this invention achieves the desired high purity of the product.

[0010] The objective of this invention can be achieved through the following methods: This invention provides a polymerization apparatus for preparing anion exchange resins by superacid catalysis, comprising: The stator outer cylinder is a vertically arranged cylindrical structure with a mixing chamber inside. The upper part of the stator outer cylinder is provided with a feed inlet communicating with the mixing chamber, through which polymer material is injected into the mixing chamber. A rotor is rotatably disposed within the mixing chamber, and the rotation of the rotor drives the polymer material to move downwards while being mixed within the mixing chamber; A quenching component is disposed at the bottom of the stator outer cylinder; An external circulation pipe is connected between the quenching component and the stator outer cylinder. The external circulation pipe is used to connect the quenching component and the upper part of the mixing chamber, so that the polymer material undergoes a polymerization reaction during the circulation flow between the mixing chamber, the quenching component and the external circulation pipe. A heat exchange jacket is fitted around the outer periphery of the stator outer cylinder to exchange heat and control the temperature of the mixing chamber through the cooling medium inside the heat exchange jacket. The stator outer cylinder is made of borosilicate glass, and the rotor, the quenching component, and the external circulation pipe are all made of polytetrafluoroethylene.

[0011] In a preferred embodiment of the present invention, the quenching component includes: A quenching plate is disposed at the bottom of the stator outer cylinder, and the quenching plate has a plurality of material leakage holes communicating with the mixing chamber; A quenching tube is disposed at the bottom of the quenching plate, and the interior of the quenching tube is connected to a plurality of material leakage holes. The quenching tube has a return port and a discharge port. One end of the external circulation pipe is connected to the return port, and the other end of the external circulation pipe is connected to the upper part of the mixing chamber, so that the polymer material circulates sequentially between the mixing chamber, the interior of the quenching tube, and the external circulation pipe.

[0012] In a preferred embodiment of the present invention, a plurality of the material leakage holes are evenly and spaced apart on the quenching plate, each of the material leakage holes having a diameter of 2 mm to 4 mm, and the sum of the cross-sectional areas of the plurality of material leakage holes in the horizontal direction accounting for 30% to 75% of the plate surface area of ​​the quenching plate.

[0013] In a preferred embodiment of the present invention, the rotor has a vertically extending columnar structure, and the outer wall surface of the rotor has a spirally extending groove to push the polymer material from top to bottom when the rotor is rotating.

[0014] In a preferred embodiment of the present invention, the rotor has a trapezoidal or triangular cross-section.

[0015] In a preferred embodiment of the present invention, the stator outer cylinder is coaxially arranged with the rotor, and there is a gap of 1 mm to 1.5 mm between the interior of the stator outer cylinder and the outer edge of the rotor.

[0016] In a preferred embodiment of the present invention, the polymerization apparatus for preparing anion exchange resin by superacid catalysis further includes a drive motor, the drive motor being located above the stator outer cylinder, and the output shaft of the drive motor passing through the stator outer cylinder and connected to the top of the rotor.

[0017] In a preferred embodiment of the present invention, the top of the stator outer cylinder is sealed with a top cover, the output shaft of the drive motor is connected to the top of the connecting shaft via a coupling, and the connecting shaft is connected to the top of the rotor.

[0018] In a preferred embodiment of the present invention, a heat exchange cavity is formed between the heat exchange jacket and the stator outer cylinder, and the top and bottom of the heat exchange jacket have a medium inlet and a medium outlet communicating with the heat exchange cavity, respectively, so that the cooling medium can circulate in the heat exchange cavity.

[0019] In a preferred embodiment of the present invention, the polymerization apparatus for preparing anion exchange resin by superacid catalysis further includes a support and a base, the bottom of the support is fixed to the top surface of the base, and the stator outer cylinder or the heat exchange jacket is detachably mounted on the support.

[0020] This invention provides an application of a polymerization apparatus for preparing anion exchange resins by superacid catalysis. The above-mentioned polymerization apparatus for preparing anion exchange resins by superacid catalysis is applied to reaction scenarios where highly corrosive chemical reagents are used as materials. The reaction scenario includes at least the superacid-catalyzed synthesis of anion exchange resins.

[0021] In a preferred embodiment of the present invention, the highly corrosive chemical reagent includes trifluoromethanesulfonic acid, chlorosulfonic acid, sulfuric acid, nitric acid, hydrochloric acid, dichloromethane, dimethylformamide, or dimethylacetamide.

[0022] Based on the above, the features and advantages of the polymerization apparatus and its application for the preparation of anion exchange resins by the superacid catalysis method of the present invention are as follows: By installing a rotor inside the stator outer cylinder, the rotation of the rotor provides driving force for the polymer material (including all materials for the polymerization reaction of anion exchange resin: monomers, solvents, and catalysts), which drives the polymer material to circulate between the mixing chamber, quenching component, and external circulation pipe within the stator outer cylinder, forming a closed-loop reaction process. During this process, due to the action of the superacid catalyst, the viscosity of the polymer material gradually increases as the polymerization reaction proceeds until it reaches the viscosity range required by the process, at which point it can be discharged through the outlet of the quenching component. Because the polymerization reaction is completed in a closed-loop circulation process and a sealed environment, the polymerization reaction can be ensured to proceed fully and stably, achieving the requirement of high product purity.

[0023] In addition, since a heat exchange jacket is installed around the outer periphery of the stator outer cylinder, and the stator outer cylinder is made of borosilicate glass, the high thermal conductivity of glass can be fully utilized during the entire reaction process. The cooling medium in the heat exchange jacket can quickly exchange heat with the mixing chamber to control the temperature of the reaction environment. The heat generated by the polymerization reaction (heat of polymerization) is quickly dissipated, and the polymerization temperature is controlled within a suitable range. This can effectively avoid branching and cross-linking in the monomer polymerization process, and provide reliable conditions for subsequent processes (such as the preparation of casting solution).

[0024] Because the stator outer cylinder is made of borosilicate glass, while the rotor, quenching components, and external circulation pipe are all made of polytetrafluoroethylene, the reaction process is free from the introduction of impurities such as metal ions due to the material selection of the polymerization device itself (trace amounts of metal ions and other impurities mixed into the anion exchange resin can catalyze resin degradation and directly affect the alkali resistance stability of the resin in actual use). This not only provides corrosion resistance but also eliminates the mixing of corrosion products into the anion exchange resin product, greatly improving the stability of the anion exchange resin.

[0025] In this invention, the structure of the quenching plate and quenching tube can disperse the polymerized anion exchange resin into a fine strip of viscous slurry, which can accelerate the termination of the polymerization reaction, effectively avoid the branching and cross-linking side reactions caused by over-polymerization, and also help maintain a narrower polymer molecular weight distribution. Attached Figure Description

[0026] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort. In the drawings: The accompanying drawings described herein are for illustrative purposes only and are not intended to limit the scope of the invention in any way. Furthermore, the shapes and proportions of the components in the drawings are merely illustrative to aid in understanding the invention and do not specifically limit the shapes and proportions of the components. Those skilled in the art, guided by the teachings of this invention, can select various possible shapes and proportions to implement the invention according to specific circumstances.

[0027] Figure 1 This is a schematic diagram of the polymerization apparatus for preparing anion exchange resins by the superacid catalysis method of the present invention. Figure 2 This is a perspective view of the polymerization apparatus for preparing anion exchange resins by the superacid catalysis method of the present invention; Figure 3 This is a front cross-sectional view of the polymerization apparatus for preparing anion exchange resins by the superacid catalysis method of the present invention. Figure 4 This is a top view of the quenching plate in the polymerization apparatus for preparing anion exchange resin by the superacid catalysis method of the present invention.

[0028] The reference numerals in the accompanying drawings of this invention are: 1. Stator outer cylinder; 101. Mixing chamber; 102. Feed inlet; 2. Rotor; 201. Blade; 3. Drive motor; 4. Quenching plate; 401. Discharge hole; 5. Quenching tube; 501. Return port; 502. Discharge port; 6. External circulation pipe; 7. Support; 8. Base; 9. Heat exchange jacket; 901. Heat exchange chamber; 10. Top cover; 11. Coupling; 12. Connecting shaft. Detailed Implementation

[0029] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions of the embodiments of this invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of this invention.

[0030] It should be noted that when an element is referred to as being "set on" another element, it can be directly on the other element or there may be an intervening element. When an element is referred to as being "connected to" another element, it can be directly connected to the other element or there may be an intervening element. The terms "vertical," "horizontal," "left," "right," and similar expressions used herein are for illustrative purposes only and do not represent the only embodiments.

[0031] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the specification of this invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0032] Implementation Method 1

[0033] like Figures 1 to 4 As shown, the present invention provides a polymerization apparatus for preparing anion exchange resins by a superacid catalysis method. This apparatus includes: The stator outer cylinder 1 is a cylindrical structure arranged vertically. The stator outer cylinder 1 has a mixing chamber 101 inside. The upper part of the stator outer cylinder 1 is provided with a feed port 102 communicating with the mixing chamber 101. Polymer material is injected into the mixing chamber 101 through the feed port 102. The polymer material includes all the materials of the polymerization reaction for preparing anion exchange resin: monomer, solvent and superacid catalyst. Rotor 2 is rotatably disposed in mixing chamber 101. The rotation of rotor 2 pushes the polymer material to move from top to bottom while mixing in mixing chamber 101. Quenching component, which is set at the bottom of stator outer cylinder 1, can quickly terminate the polymerization reaction and discharge the product after the polymerization reaction when the polymer material in the polymerization reaction reaches the viscosity range required by the process. The external circulation pipe 6 is connected between the quenching component and the stator outer cylinder 1. The external circulation pipe 6 is used to connect the quenching component and the upper part of the mixing chamber 101 so that the polymer material circulates between the mixing chamber 101, the quenching component and the external circulation pipe 6, and a polymerization reaction occurs during the circulation process. Heat exchange jacket 9 is sleeved on the outer periphery of stator outer cylinder 1 so as to exchange heat and control temperature of mixing chamber 101 through cooling medium in heat exchange jacket 9. In this invention, the stator outer cylinder 1 is made of borosilicate glass, and the rotor 2, quenching assembly and external circulation pipe 6 are all made of polytetrafluoroethylene.

[0034] This invention features a rotor 2 installed inside the stator outer cylinder 1. The rotation of the rotor 2 provides driving force to the polymer material, causing it to circulate between the mixing chamber 101, the quenching component, and the external circulation pipe 6 within the stator outer cylinder 1, forming a closed-loop reaction process. During this process, due to the action of the superacid catalyst, the viscosity of the polymer material gradually increases as the polymerization reaction proceeds until it reaches the viscosity range required by the process, at which point it can be discharged through the outlet 502 of the quenching component. Because the polymerization reaction is completed in a closed-loop circulation process and a sealed environment, the polymerization reaction can be ensured to proceed fully and stably, achieving the requirement of high product purity. In addition, since a heat exchange jacket 9 is provided around the outer periphery of the stator outer cylinder 1, and the stator outer cylinder 1 is made of borosilicate glass, the high thermal conductivity of glass can be fully utilized during the entire reaction process. The cooling medium in the heat exchange jacket 9 can quickly exchange heat with the mixing chamber 101 to achieve the purpose of controlling the temperature of the reaction environment. The heat generated by the polymerization reaction (heat of polymerization) is quickly dissipated, and the polymerization temperature is controlled within a suitable range. This can effectively avoid the branching and cross-linking of monomer polymerization process, and provide reliable conditions for subsequent processes (such as the preparation of casting solution).

[0035] In this invention, since the stator outer cylinder 1 is made of borosilicate glass, while the rotor 2, quenching components, and external circulation pipe 6 are all made of polytetrafluoroethylene, the mixing of impurities such as metal ions will not occur during the reaction process due to the material selection of the polymerization device itself (trace amounts of metal ions and other impurities mixed into the anion exchange resin will catalyze the degradation of the resin and directly affect the alkali resistance stability of the resin in actual use). It not only has the characteristics of corrosion resistance, but also eliminates the mixing of corrosion products into the anion exchange resin product, which greatly improves the stability of the anion exchange resin.

[0036] In this invention, the inner diameter of the stator outer cylinder 1 can be, but is not limited to, 50 mm to 132 mm, and the wall thickness of the stator outer cylinder 1 can be, but is not limited to, 4 mm to 7 mm. Preferably, the inner diameter of the stator outer cylinder 1 is 90 mm, and the wall thickness is preferably 6 mm. The maximum outer diameter of the rotor 2 can be, but is not limited to, 48 mm to 130 mm, and preferably 88 mm.

[0037] In an optional embodiment of the present invention, such as Figures 1 to 4 As shown, the quenching assembly includes a quenching plate 4 and a quenching tube 5. The quenching plate 4 is a horizontally arranged flat plate structure. The quenching plate 4 is sealed to the bottom of the stator outer cylinder 1, and the quenching plate 4 has multiple leakage holes 401 that communicate with the mixing chamber 101. The quenching tube 5 is sealed at the bottom of the quenching plate 4, and the interior of the quenching tube 5 communicates with the multiple leakage holes 401. The lower side wall of the quenching tube 5 has a return port 501, and the bottom wall of the quenching tube 5 has a discharge port 502. One end of the external circulation pipe 6 is connected to the return port 501, and the other end of the external circulation pipe 6 is connected to the upper part of the mixing chamber 101, so that the polymer material circulates sequentially between the mixing chamber 101, the interior of the quenching tube 5, and the external circulation pipe 6.

[0038] Furthermore, such as Figure 4 As shown, multiple discharge holes 401 are evenly and spaced apart in the central region of the quenching plate 4. The diameter of each discharge hole 401 is 2 mm to 4 mm, and the sum of the cross-sectional areas of the multiple discharge holes 401 in the horizontal direction accounts for 30% to 75% of the plate surface area of ​​the quenching plate 4. When the viscous polymer material passes through the discharge holes 401 on the quenching plate 4, it can be dispersed into fine strips or lines of viscous slurry and fall into the quenching tube 5, thereby increasing its contact area with the subsequent quenching solvent (such as alcohols, water, etc.), rapidly diluting the superacid catalyst, and quickly terminating the polymerization reaction. In practical use, the degree of dispersion of the polymer material can be controlled by adjusting the opening ratio and pore size of the discharge holes 401 on the quenching plate 4, thereby avoiding excessive local reaction and preventing branching or cross-linking side reactions. Preferably, the diameter of the discharge holes 401 is 3 mm, and the opening ratio of the discharge holes 401 on the quenching plate 4 is preferably 45%.

[0039] In this invention, the combination of the quenching plate 4 and the quenching tube 5 allows all polymer materials to stop reacting almost simultaneously, which helps maintain a narrow molecular weight distribution, improves product consistency and processability, and provides a linear polymer with controllable structure for the subsequent preparation of a soluble casting solution. The quenching plate 4, the quenching tube 5, the external circulation tube 6, and the connectors connecting the external circulation tube 6 are all made of polytetrafluoroethylene (PTFE).

[0040] In this invention, the diameter of the external circulation pipe 6 ranges from DN15 to DN32. Preferably, it is DN25.

[0041] In an optional embodiment of the present invention, such as Figure 1 and Figure 3 As shown, rotor 2 has a vertically extending columnar structure, and the outer wall of rotor 2 has helical grooves formed by cutting to push the polymer material from top to bottom when rotor 2 is rotating. The helical grooves can make the cross-section of rotor 2 trapezoidal or triangular.

[0042] Furthermore, the stator outer cylinder 1 is coaxially arranged with the rotor 2, and there is a gap of 1 mm to 1.5 mm between the interior of the stator outer cylinder 1 and the outer edge of the rotor 2. This gap arrangement has at least the following advantages: Effective shearing and mixing are achieved: When rotor 2 rotates at high speed, it causes the viscous polymer material in the gap to be subjected to strong shearing forces. This ensures that the reactants, catalysts and solvents are mixed uniformly, avoiding localized uneven concentrations; it also promotes heat exchange in the radial direction, allowing heat to be transferred more efficiently to the outer glass stator, and then carried away by the cooling medium in the heat exchange jacket 9.

[0043] Stable material transport is achieved: the spiral grooves on the surface of rotor 2 cooperate with the inner wall of stator outer cylinder 1. With a small gap, stable pressure can be established to push the polymer material to move axially from top to bottom, thus achieving continuous operation. Moreover, it can prevent the backflow of polymer material and ensure that all polymer materials have a basically consistent residence time, which is beneficial to obtaining polymers with a narrower molecular weight distribution.

[0044] Ensuring efficient heat transfer and temperature control: The tiny gaps mean the viscous material layer is very thin with low internal thermal resistance. Heat generated during polymerization can pass through the material layer via the shortest path, through the highly thermally conductive glass wall, and be rapidly removed by the cooling medium in the heat exchange jacket 9. This effectively prevents localized overheating and avoids side reactions (such as branching and cross-linking) caused by temperature runaway, ensuring the synthesis of the desired linear polymer and guaranteeing its subsequent solubility in solvents for casting.

[0045] In another alternative embodiment of the invention, such as Figure 2 As shown, the outer wall of the rotor 2 may also have blades 201 extending in a spiral or arranged in a spiral interval to push the polymer material from top to bottom when the rotor 2 is rotating. There should also be a gap of 1 mm to 1.5 mm between the interior of the stator outer cylinder 1 and the outer edge of the blades 201.

[0046] In an optional embodiment of the present invention, such as Figures 1 to 3As shown, the polymerization apparatus for preparing anion exchange resin by superacid catalysis also includes a drive motor 3. The drive motor 3 is located above the stator outer cylinder 1. The output shaft of the drive motor 3 passes through the stator outer cylinder 1 and is connected to the top of the rotor 2. The drive motor 3 provides driving force to the rotor 2 to ensure the stable and continuous rotation of the rotor 2.

[0047] Specifically, such as Figure 3 As shown, the top of the stator outer cylinder 1 is sealed with a top cover 10, and the output shaft of the drive motor 3 is connected to the top of the connecting shaft 12 through a coupling 11. The connecting shaft 12 is connected to the top of the rotor 2.

[0048] In an optional embodiment of the present invention, such as Figure 3 As shown, an annular heat exchange cavity 901 is formed between the heat exchange jacket 9 and the stator outer cylinder 1. The top of the heat exchange jacket 9 has a medium inlet communicating with the heat exchange cavity 901, and the bottom of the heat exchange jacket 9 has a medium outlet communicating with the heat exchange cavity 901. An external cold source can be introduced into the medium inlet and the medium outlet so that the cooling medium can circulate in the heat exchange cavity 901 to achieve the effect of continuous temperature control.

[0049] In an optional embodiment of the present invention, such as Figure 2 and Figure 3 As shown, the polymerization apparatus for preparing anion exchange resin by superacid catalysis also includes a support 7 and a base 8. The bottom of the support 7 is fixed to the top surface of the base 8, and the stator outer cylinder 1 or heat exchange jacket 9 is detachably mounted on the support 7 through a clamping structure.

[0050] The working process of the polymerization apparatus for preparing anion exchange resin by superacid catalysis of the present invention is as follows: First, an external cold source is activated, allowing the cooling medium to flow into the heat exchange chamber 901 between the heat exchange jacket 9 and the stator outer cylinder 1, forming a circulating heat exchange loop and starting to cool down. After the temperature in the mixing chamber 101 inside the stator outer cylinder 1 reaches the range specified by the process conditions, the polymer materials required for the polymerization reaction (including monomers, solvents, superacid catalysts, etc.) are metered according to the process sequence and injected into the mixing chamber 101 through the feed inlet 102. At the same time, the drive motor 3 is turned on, causing the rotor 2 to rotate at a certain speed. The rotation of the rotor 2 pushes the polymer material to move continuously from top to bottom within the mixing chamber 101, achieving the effect of stirring and mixing the polymer material. Simultaneously, the polymer material exchanges heat with the cooling medium in the heat exchange chamber 901, and the temperature of the polymer material gradually reaches the temperature range specified by the process conditions. In the above process, the polymer material is propelled by the rotor 2 through the mixing chamber 101, the discharge hole 401 on the quenching plate 4, and the interior of the quenching tube 5 before entering the external circulation pipe 6. In the external circulation pipe 6, it flows upwards back to the upper part of the mixing chamber 101 of the stator outer cylinder 1, forming a closed loop. Under the action of the superacid catalyst, as the polymerization reaction proceeds, the viscosity of the polymer material gradually increases. Once it reaches the viscosity range specified by the process, the outlet 502 at the bottom of the quenching tube 5 can be opened to discharge the polymer material into the external quenching solvent tank, thereby rapidly terminating the reaction.

[0051] Throughout the entire process, from adding the polymer material and initiating the polymerization reaction to quenching the reaction (entering the external quenching solvent tank), the polymer material only comes into contact with the polytetrafluoroethylene (PTFE) and borosilicate glass. This not only prevents corrosion of the equipment (especially preventing corrosion products from contaminating the anion exchange resin) and eliminates impurities from entering the polymer product, greatly improving the purity of the anion exchange resin and ensuring the alkali resistance stability of the prepared anion exchange membrane, but also, through the setting of the heat exchange jacket 9, the temperature of the polymerization reaction can be controlled within a suitable range, and the reaction can be quickly terminated by rapid quenching after completion, avoiding cross-linking reactions during the preparation of the anion exchange resin. This invention is applicable to superacid-catalyzed polymerization reactions, possesses high-viscosity flow and rapid heat exchange capabilities, solves the problem of handling highly corrosive and rapidly heat-exchange equipment in industrial scale-up processes, and can be used in the industrial production process of alkali-resistant anion exchange resins.

[0052] The features and advantages of the polymerization apparatus for preparing anion exchange resin by superacid catalysis in this invention are as follows: In the polymerization apparatus for preparing anion exchange resin by superacid catalysis, the stator outer cylinder 1 is made of borosilicate glass, while the rotor 2, quenching components, and external circulation pipe 6 are all made of polytetrafluoroethylene. During the reaction, the polymer apparatus itself will not be contaminated by impurities such as metal ions. It not only has the characteristics of corrosion resistance, but also eliminates the contamination of corrosion products into the anion exchange resin product, which greatly improves the stability of the anion exchange resin.

[0053] II. The polymerization apparatus for preparing anion exchange resin by superacid catalysis has a heat exchange jacket 9 on the outer periphery of the stator outer cylinder 1, and the stator outer cylinder 1 is made of borosilicate glass. During the entire reaction process, the high thermal conductivity of glass can be fully utilized. The cooling medium in the heat exchange jacket 9 can quickly exchange heat with the mixing chamber 101 to control the temperature of the reaction environment. The heat generated by the polymerization reaction is quickly dissipated, and the polymerization temperature is controlled within a suitable range. This can effectively avoid branching and cross-linking in the monomer polymerization process and provide reliable conditions for subsequent processes.

[0054] III. The polymerization apparatus for preparing anion exchange resin by superacid catalysis can disperse the polymerized anion exchange resin into a fine strip of viscous slurry through the cooperation of quenching plate 4 and quenching tube 5. After entering the non-solvent, the organic acid rapidly dilutes the slurry, and the polymerization reaction is quickly stopped. Since the polymerization reaction in the fine strip of viscous slurry stops at approximately the same time, it can effectively avoid the branching and cross-linking side reactions caused by overpolymerization, and it is also beneficial to maintain a narrower polymer molecular weight distribution.

[0055] Implementation Method 2

[0056] This invention provides an application of a polymerization apparatus for preparing anion exchange resins by superacid catalysis. The above-mentioned polymerization apparatus for preparing anion exchange resins by superacid catalysis is applied to reaction scenarios where highly corrosive chemical reagents are used as materials. Among them, the above-mentioned reaction scenarios include at least the superacid-catalyzed synthesis of anion exchange resins.

[0057] Furthermore, the aforementioned highly corrosive chemical reagents include trifluoromethanesulfonic acid, chlorosulfonic acid, sulfuric acid, nitric acid, hydrochloric acid, dichloromethane, dimethylformamide, or dimethylacetamide.

[0058] The application scenario of this invention is implemented using the polymerization apparatus for preparing anion exchange resin by the superacid catalysis method described above. It has the characteristics and advantages of the polymerization apparatus for preparing anion exchange resin by the superacid catalysis method described above, which will not be repeated here.

[0059] It should be noted that in the description of this application, the terms "first," "second," etc., are used only for descriptive purposes and to distinguish similar objects; there is no order between them, nor should they be construed as indicating or implying relative importance. Furthermore, in the description of this application, unless otherwise stated, "multiple" means two or more.

[0060] The various embodiments described in this specification are presented in a progressive manner. The same or similar parts between the embodiments can be referred to each other. Each embodiment focuses on the differences from other embodiments.

[0061] The above are merely a few embodiments of the present invention. Although the embodiments disclosed in this invention are as described above, the content is only for the purpose of facilitating understanding of the present invention and is not intended to limit the present invention. Any equivalent changes and modifications made by those skilled in the art without departing from the concept and principles of the present invention should fall within the scope of protection of the present invention.

Claims

1. A polymerization apparatus for preparing anion exchange resins by superacid catalysis, characterized in that, include: The stator outer cylinder is a vertically arranged cylindrical structure with a mixing chamber inside. The upper part of the stator outer cylinder is provided with a feed inlet communicating with the mixing chamber, through which polymer material is injected into the mixing chamber. A rotor is rotatably disposed within the mixing chamber, and the rotation of the rotor drives the polymer material to move downwards while being mixed within the mixing chamber; A quenching component is disposed at the bottom of the stator outer cylinder; An external circulation pipe is connected between the quenching component and the stator outer cylinder. The external circulation pipe is used to connect the quenching component and the upper part of the mixing chamber, so that the polymer material undergoes a polymerization reaction during the circulation flow between the mixing chamber, the quenching component and the external circulation pipe. A heat exchange jacket is fitted around the outer periphery of the stator outer cylinder to exchange heat and control the temperature of the mixing chamber through the cooling medium inside the heat exchange jacket. The stator outer cylinder is made of borosilicate glass, and the rotor, the quenching component, and the external circulation pipe are all made of polytetrafluoroethylene.

2. The polymerization apparatus for preparing anion exchange resin by superacid catalysis as described in claim 1, characterized in that, The quenching component includes: A quenching plate is disposed at the bottom of the stator outer cylinder, and the quenching plate has a plurality of material leakage holes communicating with the mixing chamber; A quenching tube is disposed at the bottom of the quenching plate, and the interior of the quenching tube is connected to a plurality of material leakage holes. The quenching tube has a return port and a discharge port. One end of the external circulation pipe is connected to the return port, and the other end of the external circulation pipe is connected to the upper part of the mixing chamber, so that the polymer material circulates sequentially between the mixing chamber, the interior of the quenching tube, and the external circulation pipe.

3. The polymerization apparatus for preparing anion exchange resin by superacid catalysis as described in claim 2, characterized in that, The plurality of the material leakage holes are evenly and spaced apart on the quenching plate, each of the material leakage holes having a diameter of 2 mm to 4 mm, and the sum of the cross-sectional areas of the plurality of material leakage holes in the horizontal direction accounting for 30% to 75% of the plate surface area of ​​the quenching plate.

4. The polymerization apparatus for preparing anion exchange resin by superacid catalysis as described in claim 1, characterized in that, The rotor has a vertically extending columnar structure, and the outer wall of the rotor has spirally extending grooves to push the polymer material from top to bottom when the rotor is rotating.

5. The polymerization apparatus for preparing anion exchange resin by superacid catalysis as described in claim 4, characterized in that, The rotor has a trapezoidal or triangular cross-section.

6. The polymerization apparatus for preparing anion exchange resin by superacid catalysis as described in claim 1 or 4, characterized in that, The stator outer cylinder is coaxially arranged with the rotor, and there is a gap of 1 mm to 1.5 mm between the inside of the stator outer cylinder and the outer edge of the rotor.

7. The polymerization apparatus for preparing anion exchange resin by superacid catalysis as described in claim 1, characterized in that, The polymerization apparatus for preparing anion exchange resin by superacid catalysis also includes a drive motor, which is located above the stator outer cylinder, and the output shaft of the drive motor passes through the stator outer cylinder and is connected to the top of the rotor.

8. The polymerization apparatus for preparing anion exchange resin by superacid catalysis as described in claim 7, characterized in that, The top of the stator outer cylinder is sealed with a top cover, and the output shaft of the drive motor is connected to the top of the connecting shaft via a coupling. The connecting shaft is connected to the top of the rotor.

9. The polymerization apparatus for preparing anion exchange resin by superacid catalysis as described in claim 1, characterized in that, A heat exchange cavity is formed between the heat exchange jacket and the stator outer cylinder. The top and bottom of the heat exchange jacket have a medium inlet and a medium outlet communicating with the heat exchange cavity, respectively, so that the cooling medium can circulate in the heat exchange cavity.

10. The polymerization apparatus for preparing anion exchange resin by superacid catalysis as described in claim 1, characterized in that, The polymerization apparatus for preparing anion exchange resin by superacid catalysis further includes a support and a base. The bottom of the support is fixed to the top surface of the base, and the stator outer cylinder or the heat exchange jacket is detachably mounted on the support.

11. An application of a polymerization apparatus for preparing anion exchange resins via a superacid catalysis method, characterized in that, The polymerization apparatus for preparing anion exchange resin by superacid catalysis according to any one of claims 1 to 10 is applicable to reaction scenarios where highly corrosive chemical reagents are used as materials; The reaction scenario includes at least the superacid-catalyzed synthesis of anion exchange resins.

12. The application of the polymerization apparatus for preparing anion exchange resin by superacid catalysis as described in claim 11, characterized in that, The highly corrosive chemical reagents include trifluoromethanesulfonic acid, chlorosulfonic acid, sulfuric acid, nitric acid, hydrochloric acid, dichloromethane, dimethylformamide, or dimethylacetamide.

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