Device and method for preparing polysulfone polymer

Abstract

According to the polysulfone polymer preparation device and method provided by the invention, the bed type reactor is arranged in the reaction kettle, and the acid-binding agent powder is fixedly filled in the bed type reactor, so that on one hand, the contact area between an acid-binding agent and a circulating liquid is increased, and on the other hand, the insoluble acid-binding agent powder fixedly stays in the bed type reactor; according to the method, the separation step of the acid-binding agent and the polymerization liquid can be reduced, the time of the production process is shortened, the by-product and the unreacted acid-binding agent are separated after the reaction is finished, the by-product does not need to be further treated, the unreacted acid-binding agent can be continuously used, and the cost is saved. The multiple reaction bed layers are connected end to end to form a broken-line-shaped structure, the structure increases the specific surface area of the acid binding agent, and the reaction bed layers are obliquely arranged so that the flow speed of circulating liquid can be increased. Salifying and filtering are performed synchronously, so that the production time is greatly shortened, and the production cost is reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and in particular to a preparation device and method for polysulfone polymers. Background Art

[0002] As a special polymer material, polysulfones are widely used in various fields such as aerospace, food, and medical equipment due to their good chemical stability, excellent heat resistance and mechanical properties.

[0003] Currently, the most advanced production process for special polymer materials is the one-step synthesis method. The one-step synthesis method mainly includes a polymerization section and a post-treatment section.

[0004] In the polymerization section, solid raw materials such as 4,4'-dichlorodiphenyl sulfone, bisphenol A, bisphenol S, biphenyl diol, and acid-binding agents such as potassium carbonate or potassium bicarbonate are polymerized in a liquid solvent. Common solvents include dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. Toluene, xylene, etc. can be selected as dehydrating agents. During the reaction process, as the temperature rises, the main solid raw materials 4,4'-dichlorodiphenyl sulfone, bisphenol A, bisphenol S, and biphenyl diol dissolve in the solvent, while the acid-binding agents such as potassium carbonate or potassium bicarbonate are insoluble in the solvent, and the reaction system forms a solid-liquid two-phase reaction system. The two-phase reaction system requires the stirring form, rate, particle size of the solid catalyst, small aspect ratio of the reaction kettle diameter to height, solid-liquid ratio, viscosity of the polymerization liquid, etc., which increases the difficulty of the reaction kettle design and filtration equipment. After the reaction, the by-products and unreacted acid-binding agents are a mixture that needs further treatment: problems such as dissolution, acidification, concentration, crystallization, and drying, which increase the investment and raise the production cost. Summary of the Invention

[0005] The present invention provides a preparation device and method for polysulfone polymers to solve the technical problems raised in the background art.

[0006] The technical solution adopted by the present invention to solve the above technical problems is as follows: A preparation device for polysulfone polymers includes a reaction kettle. An upper layer of the reaction kettle is provided with a bed reactor. The bed reactor includes a porous support plate and a reaction bed layer located above the porous support plate. The reaction bed layer has at least one layer, and acid-binding agents are fixedly filled in each reaction bed layer; a circulating liquid outlet is provided at the bottom of the reaction kettle, a circulating liquid inlet is provided at the top of the reaction kettle, the circulating liquid outlet and the circulating liquid inlet are connected by a circulating pipeline, a circulating pump is installed on the circulating pipeline, and the circulating liquid inlet is communicated with the feeding end of the bed reactor.

[0007] Further, the reaction bed layer is inclined, and the inclination angle is 2 to 10°.

[0008] Furthermore, a filter cloth layer, an acid-binding agent layer, and a porous filter plate layer are sequentially arranged from top to bottom in the reaction bed layer. Specifically, the reaction bed layer includes a filter frame. A filter cloth is arranged at the top of the filter frame to form the filter cloth layer, a porous filter plate is arranged at the bottom of the filter frame to form the porous filter plate layer, and an acid-binding agent is filled between the filter cloth and the porous filter plate inside the filter frame to form the acid-binding agent layer.

[0009] Furthermore, when the bed reactor includes two or more reaction bed layers, the multiple reaction bed layers are arranged vertically, and the adjacent two reaction bed layers are connected end to end in a zigzag shape. The circulating liquid entering the bed reactor from the self-circulating liquid inlet can flow through each reaction bed layer in sequence under the action of gravity, contact the acid-binding agent in the reaction bed layer, fully salt and polymerize, and the obtained polymerized liquid falls to the bottom of the kettle.

[0010] Furthermore, a liquid distributor is arranged at the connection of the head and tail of adjacent reaction bed layers, so that the circulating liquid from the upper reaction bed layer can uniformly enter the next reaction bed layer.

[0011] Furthermore, the reaction kettle is equipped with a heating component, and the heating component provides heating and temperature increase for the solution at the bottom of the reaction kettle and / or the solution flowing through the circulation pipeline, and the heating temperature range is 100~200°C.

[0012] Furthermore, a pressure filtration device is arranged at the upper part of the bed reactor. When the reaction is over and the polymerized liquid is discharged out of the kettle, the residual reaction liquid in the bed reactor can be removed by pressure filtration.

[0013] Furthermore, when the bed reactor includes one reaction bed layer, the pressure filter plate of the pressure filtration device contacting the reaction bed layer can be set to an inclined state, and the inclination angle is the same as that of the reaction bed layer.

[0014] Furthermore, hanging ears are arranged at both ends of the reaction bed layer and the porous support plate. A support frame extending vertically downward is fixed at the top of the reaction kettle, and the reaction bed layer and the porous support plate are detachably fixed inside the support frame through the hanging ears.

[0015] Furthermore, a detachable buckle for fixing the hanging ears is arranged on the support frame.

[0016] Furthermore, a stirring device is arranged at the bottom of the reaction kettle. The stirring device includes a stirring motor, a rotating shaft, and stirring blades. The stirring motor is fixed outside the reaction kettle, the output shaft of the stirring motor is connected to the rotating shaft, the rotating shaft passes through the reaction kettle and is located below the fixed bed reaction mechanism, and a plurality of the stirring blades are connected to the rotating shaft.

[0017] Furthermore, the bottom of the reactor is arc-shaped, and a stirring space for the stirring blades to rotate is formed inside.

[0018] Furthermore, the stirring device is horizontally arranged below the bed reactor.

[0019] The present invention also provides a method for preparing a polysulfone polymer, comprising the following steps: S1. Dissolve bisphenol monomers, dihalobenzene compound monomers, and a low-boiling-point polar organic solvent, and then add them to the reactor; charge an acid-binding agent in the reaction bed layer and assemble the bed reactor; S2. Heat to make the temperature in the reactor reach above 120 °C, start the circulation pump to make the bottom solution enter the bed reactor from the circulating liquid inlet, the solution flows through the reaction bed layer and reacts with the acid-binding agent to complete salt formation and polymerization, and finally falls back to the bottom of the kettle. During this period, the insoluble salts generated are deposited on the porous support plate; the reaction temperature is controlled at 140 °C to 160 °C, and the reaction is carried out under nitrogen protection; S3. After the reaction is completed, turn off the circulation pump; S4. Open the bottom valve of the kettle, discharge the bottom solution, and pump it into a poor solvent to precipitate polysulfone.

[0020] Furthermore, it also includes a step for treating the by-products of the polymerization reaction: remove the polymerization liquid from the reaction by-products and the unreacted acid-binding agent in the bed reactor, wash to obtain the by-products and the unreacted acid-binding agent, directly dry and package the by-products, and the unreacted acid-binding agent can be recycled.

[0021] Furthermore, the bisphenol monomer is selected from any one or more of bisphenol S, bisphenol A, and hydroquinone.

[0022] Furthermore, the dihalobenzene compound monomer is 4,4'-dichlorodiphenyl sulfone.

[0023] Furthermore, the low-boiling-point polar organic solvent is selected from any one or more of dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0024] Furthermore, the acid-binding agent is a caustic alkali or a weak basic salt, and is further selected from any one or more of sodium carbonate, sodium hydroxide, and potassium carbonate.

[0025] Furthermore, the feeding ratio of the bisphenol monomer, the dihalobenzene compound monomer, and the low-boiling-point polar organic solvent is (80 - 200) kg : (180 - 220) kg : (800 - 1400) L.

[0026] Furthermore, the mass ratio of the acid-binding agent filled in the bed reactor to the total amount of reaction monomers is (70 - 100) : (250 - 450).

[0027] Further, S3 determines the reaction end point by detecting the viscosity of the solution at the bottom of the kettle. The target viscosity is determined by product classification, and the reaction is terminated by adding a capping agent. The reaction time is 6 - 12 h.

[0028] Further, the poor solvents include water, methanol, ethanol, acetone, etc.

[0029] Compared with the prior art, the present invention has the following advantages or technical effects: A bed - type reactor is provided inside the reaction kettle, and the acid - binding agent powder is fixedly filled in the bed - type reactor. On the one hand, it increases the contact area between the acid - binding agent and the circulating liquid. On the other hand, the insoluble acid - binding agent powder stays fixedly in the bed - type reactor, which can reduce the separation step of the acid - binding agent and the polymerization liquid, shorten the time of the production process. After the reaction, the by - product and the unreacted acid - binding agent are separated. The by - product does not need further treatment, and the unreacted acid - binding agent can be used continuously, saving costs. Multiple reaction bed layers are connected end to end to form a zigzag structure, which increases the specific surface area of the acid - binding agent. Setting the reaction bed layer obliquely can increase the flow rate of the circulating liquid. The salt formation and filtration are carried out simultaneously, greatly shortening the production time and reducing the production cost. Description of the Drawings

[0030] By reading the detailed description of the non - restrictive embodiments with reference to the following drawings, the present invention and its features, shape, and advantages will become more obvious. The same reference numerals indicate the same parts in all the drawings.

[0031] Figure 1 It is a schematic diagram of the internal structure of a polysulfone - type polymer preparation device; Figure 2 It is a schematic diagram of the structure of the porous filter plate of the reaction bed layer; In the figure, 1. Reaction kettle, 2. Circulating liquid outlet, 3. Circulating liquid inlet, 4. Circulation pump, 5. Non - condensable gas outlet, 6. Support frame, 7. Pressure filtration device, 8. Porous support plate, 9. Reaction bed layer, 91. Filter frame, 92. Porous filter plate, 93. Liquid distributor, 10. Hanging ear, 11. Under - bed overflow port, 12. Stirring device, 13. Condenser, 14. Gas - liquid separator, 15. Liquid storage tank. Detailed Embodiments

[0032] The following describes the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Therefore, the detailed description of the embodiments of the present invention provided in the following drawings is not intended to limit the scope of the claimed invention, but merely represents the selected embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative efforts fall within the protection scope of the present invention. Embodiment 1:

[0033] Please refer to the attached Figure 1 - Figure 2 , the present invention provides a preparation device for polysulfone polymers, including a reaction kettle 1. A bed reactor is arranged on the upper layer of the reaction kettle 1. The bed reactor includes a support frame 6, a porous support plate 8, and at least one reaction bed layer 9 located above the porous support plate 8. An acid-binding agent is fixedly filled in each reaction bed layer 9. A circulating liquid outlet 2 is arranged at the bottom of the reaction kettle 1, a circulating liquid inlet 3 and a non-condensable gas outlet 5 are arranged at the top of the reaction kettle 1. A circulating pipeline is connected between the circulating liquid outlet 2 and the circulating liquid inlet 3, and a circulating pump 4 is installed on the circulating pipeline. The circulating liquid inlet 3 is communicated with the feed end of the bed reactor, and the non-condensable gas outlet 5 is connected to a gas-liquid separation device. A bottom overflow port 11 is arranged between the bottom of the bed reactor and the porous support plate 8.

[0034] Hanging ears 10 are arranged at both ends of the reaction bed layer 9 and the porous support plate 8. The top end of the support frame 6 is fixed to the bottom of the upper cover of the reaction kettle 1 and extends vertically downward. The reaction bed layer 9 and the porous support plate 8 are detachably fixed inside the support frame 6 through the hanging ears 10. A plurality of detachable buckles for fixing the hanging ears 10 are arranged on the support frame 6. There is a certain margin between the hanging ears 10 and the buckles, which can meet the sequential inclined fixation of multiple reaction bed layers. When it is necessary to remove reaction by-products and acid-binding agents after the reaction, the reaction bed layer can also be simply disassembled and moved.

[0035] A plurality of reaction bed layers 9 are arranged along the vertical direction of the support frame 6, and adjacent reaction bed layers 9 are connected end to end in a zigzag shape. A liquid distributor 93 is arranged at the connection of the head and tail of adjacent reaction bed layers 9, so that the circulating liquid from the upper reaction bed layer can uniformly enter the next reaction bed layer. The multi-layer zigzag structure increases the specific surface area of the acid-binding agent, and the reaction bed layer 9 is inclined to accelerate the flow rate of the circulating liquid.

[0036] Each reaction bed layer 9 is sequentially provided with a filter cloth layer, an acid-binding agent layer, and a porous filter plate layer from top to bottom. Specifically, the reaction bed layer 9 includes a filter frame 91. A filter cloth is arranged at the top of the filter frame 91 to form a filter cloth layer, a porous filter plate 92 is arranged at the bottom of the filter frame 91 to form a porous filter plate layer, and an acid-binding agent is filled between the filter cloth and the porous filter plate 92 inside the filter frame 91 to form an acid-binding agent layer.

[0037] The reactor 1 is equipped with a heating component, which provides heating and temperature increase for the solution at the bottom of the reactor, and the heating temperature range is 100 - 200 °C.

[0038] A pressure filtration device 7 is arranged at the upper part of the bed reactor. When the reaction ends and the polymerization liquid is discharged out of the reactor, the residual reaction liquid in the bed reactor can be removed by pressure filtration.

[0039] A horizontal stirring device 12 is arranged at the bottom of the reactor 1. The stirring device includes a stirring motor, a rotating shaft and stirring blades. The stirring motor is fixed outside the reactor. The output shaft of the stirring motor is connected to the rotating shaft. The rotating shaft passes through the reactor and is located below the fixed bed reaction mechanism, and a plurality of the stirring blades are connected to the rotating shaft. The bottom of the reactor 1 is arc-shaped, and a stirring space for the stirring blades to rotate is formed inside.

[0040] It should be understood that the pressure filtration device and the stirring device are prior arts, and their structures have been disclosed, so they will not be elaborated here.

[0041] The gas-liquid separation device includes a condenser 13, a gas-liquid separator 14 and a liquid outlet storage tank 15. The liquid inlet of the condenser 13 is connected to the non-condensable gas outlet 5 through a pipeline. The liquid outlet of the condenser 13 is connected to the liquid inlet of the gas-liquid separator 14 through a pipeline. The liquid outlet of the gas-liquid separator 14 is connected to the liquid outlet storage tank 15 through a pipeline. Example 2:

[0042] Same as Example 1, the difference is that the bed reactor only includes one inclined reaction bed layer, and the inclination angle of the pressure filtration plate of the pressure filtration device is the same as that of the reaction bed layer. Example 3:

[0043] Using the polymerization reaction device described in Example 1, prepare the polysulfone polymer according to the following steps: In a 2500L reactor, add 210 kg of 4,4'-dichlorodiphenyl sulfone, 183 kg of bisphenol S, and 1200L of the solvent N-methylpyrrolidone. 90 kg of potassium carbonate is fixed on the reaction bed. After the entire system is purged with nitrogen three times, under nitrogen protection, start stirring and heating to bring the temperature in the reactor to 120°C. Start the circulation pump, and keep the temperature at 150°C after the reactor reaches this temperature. Bisphenol S contacts the acid-binding agent on the reaction bed to undergo a salt-forming reaction. The reaction liquid falls to the bottom of the reactor under the action of gravity, during which it condenses with 4,4'-dichlorodiphenyl sulfone and KCl salt is removed. Part of the KCl salt deposits on the perforated plate along with the polymerization reaction and the circulation of the feed liquid. When the reaction proceeds for 11 hours, the viscosity in the reactor reaches the target viscosity, and a capping agent is added to end the reaction. Turn off the circulation pump, open the valve at the bottom of the reactor, and discharge the polymer solution at the bottom into a poor solvent to precipitate polysulfone. At the same time, start the pressure filtration device to squeeze the reaction bed, and the remaining polymerization liquid flows into the bottom of the reactor, while the unreacted potassium carbonate remains in the reaction bed, realizing the separation of the acid-binding agent and the polymerization liquid. Wash the reaction bed twice with a hot solvent, and the unreacted potassium carbonate can be used continuously. The precipitated polysulfone is directly crushed, washed with water, dried, granulated, and packaged to obtain a polyethersulfone (PES) product. After testing, the ash content is 0.006%, and the heat distortion temperature is 204°C (1.82 MPa). The KCl in the mother liquor is recovered, washed, dried, and packaged. Example 4:

[0044] Using the polymerization reaction device described in Example 1, prepare a polysulfone polymer according to the following steps: In a 2500L reactor, add 900L of N,N-dimethylformamide, 160 kg of bisphenol A, and 201 kg of 4,4'-dichlorodiphenyl sulfone. 80 kg of sodium hydroxide is fixed on the reaction bed. After the entire system is purged with nitrogen three times, under nitrogen protection, start stirring and heating to bring the temperature in the reactor to 120°C. Start the circulation pump, and keep the temperature at 140°C after the reactor reaches this temperature. Bisphenol A contacts the acid-binding agent on the reaction bed to undergo a salt-forming reaction. The reaction liquid flows through the reaction bed and falls to the bottom of the reactor under the action of gravity, during which it undergoes a polycondensation reaction with 4,4'-dichlorodiphenyl sulfone, and NaCl salt is removed. Part of the NaCl salt generated during the polymerization reaction and the circulation of the feed liquid deposits on the perforated plate. When the reaction proceeds for 8 hours, the viscosity in the reactor reaches the target viscosity, and a capping agent is added to end the reaction. Turn off the circulation pump, open the valve at the bottom of the reactor, and discharge the polymer solution at the bottom into a poor solvent to precipitate polysulfone. At the same time, start the pressure filtration device to squeeze the reaction bed, and the remaining polymerization liquid flows into the bottom of the reactor, while the unreacted sodium hydroxide remains in the reaction bed, realizing the separation. Wash the reaction bed twice with a hot solvent, and the unreacted sodium hydroxide can be used continuously. The precipitated polysulfone is directly crushed, washed with water, dried, granulated, and packaged to obtain a polysulfone (PSU) product. The ash content is 0.01%, and the heat distortion temperature is 175°C (1.82 MPa). The NaCl in the mother liquor is recovered, washed, dried, and packaged. Example 5:

[0045] Using the polymerization reaction apparatus described in Example 1, prepare a polysulfone polymer according to the following steps: Add 211 kg of 4,4'-dichlorodiphenyl sulfone, 80.9 kg of hydroquinone, 1000 L of the solvent N,N-dimethylacetamide, and 80 kg of sodium carbonate fixed on the reaction bed in a 2500 L reaction kettle. After the entire system is purged with nitrogen three times, under nitrogen protection, start stirring and heating to raise the temperature in the kettle to 120 °C, start the circulation pump, and keep the temperature at 160 °C after the reaction kettle reaches this temperature. Hydroquinone undergoes a salt-forming reaction when contacting with the acid-binding agent on the reaction bed, and the reaction solution flows through the reaction bed under the action of gravity and falls to the bottom of the kettle, during which a polycondensation reaction occurs with 4,4'-dichlorodiphenyl sulfone, and NaCl salt is removed. When the reaction proceeds to the 7th hour, the viscosity in the reaction kettle reaches the target viscosity, and a capping agent is added to end the reaction. Turn off the circulation pump, open the valve at the bottom of the kettle, and discharge the polymer solution at the bottom of the kettle into a poor solvent to precipitate the polysulfone. At the same time, start the pressure filtration device to squeeze the reaction bed, and the remaining polymerization solution flows into the bottom of the kettle, and the unreacted sodium hydroxide remains in the reaction bed to achieve separation. Wash the reaction bed twice with a hot solvent, and the unreacted sodium hydroxide can be used continuously. The precipitated polysulfone is directly crushed, washed with water, dried, granulated, and packaged to obtain a polyphenylsulfone (PPSU) product. The NaCl in the mother liquor is recovered, washed, dried, and packaged. The measured ash content of PPSU is 0.004%, and the heat distortion temperature is 207 °C (1.82 MPa).

[0046] The above are only the preferred embodiments of the present invention, and do not limit the patent scope of the present invention accordingly. Any equivalent structural transformation made using the content of the specification and drawings of the present invention, or directly or indirectly applied in other related technical fields, shall be equally included in the patent protection scope of the present invention.

Claims

1. A preparation device for polysulfone polymers, characterized in that, It includes a reaction kettle (1). A bed reactor is arranged on the upper layer of the reaction kettle (1). The bed reactor includes a porous support plate (8) and a reaction bed layer (9) located above the porous support plate (8). At least one layer of the reaction bed layer (9) is provided, and an acid-binding agent is fixedly filled in each reaction bed layer (9). A circulating liquid outlet (2) is arranged at the bottom of the reaction kettle (1), and a circulating liquid inlet (3) is arranged at the top of the reaction kettle (1). The circulating liquid outlet (2) and the circulating liquid inlet (3) are connected through a circulating pipeline, and a circulating pump (4) is installed on the circulating pipeline. The circulating liquid inlet (3) is communicated with the feed end of the bed reactor.

2. The preparation device of the polysulfone polymer according to claim 1, characterized in that The reaction bed layer (9) is inclined.

3. The preparation device of the polysulfone polymer according to claim 1, characterized in that, The reaction bed layer (9) includes a filter frame (91). Filter cloth and a porous filter plate (92) are arranged at the top and bottom of the filter frame (91). An acid-binding agent is filled inside the filter frame (91) and between the filter cloth and the porous filter plate (92).

4. A preparation device for polysulfone polymers according to claim 1, characterized in that, When the bed reactor includes two or more reaction bed layers (9), the multiple reaction bed layers (9) are arranged in the vertical direction, and the adjacent two reaction bed layers (9) are connected end to end in a zigzag shape.

5. The preparation device of a polysulfone polymer according to claim 4, characterized in that, A liquid distributor (93) is arranged at the connection of the head and tail of the adjacent two reaction bed layers (9).

6. The preparation device of a polysulfone polymer according to claim 1, wherein A pressure filtration device (7) is arranged at the upper part of the bed reactor.

7. The preparation device of a polysulfone polymer according to claim 1, characterized in that, Hanging ears (10) are arranged at both ends of the reaction bed layer (9) and the porous support plate (8). A support frame (6) extending vertically downward is fixed at the top of the reaction kettle (1). The reaction bed layer (9) and the porous support plate (8) are detachably fixed inside the support frame (6) through the hanging ears (10).

8. The preparation device of the polysulfone polymer according to claim 1, characterized in that, A stirring device (12) is arranged at the bottom of the reaction kettle (1) and below the bed reactor.

9. A method for preparing a polysulfone polymer, based on any one of the polysulfone polymer preparation apparatuses described in claims 1-8, characterized in that, It includes the following steps: S1. Dissolve bisphenol monomers, dihalobenzene compound monomers, and a low-boiling-point polar organic solvent, and then add them to the reaction kettle; fill the acid-binding agent in the reaction bed layer and assemble the bed reactor. S2. Heat to make the temperature in the reaction kettle reach above 120 °C, start the circulating pump to make the solution at the bottom of the kettle enter the bed reactor from the circulating liquid inlet. The solution flows through the reaction bed layer and reacts with the acid-binding agent to complete salt formation and polymerization, and finally falls back to the bottom of the kettle. The insoluble salts generated during this period are deposited on the porous support plate. The reaction temperature is controlled at 140 °C to 160 °C, and the reaction is carried out under nitrogen protection. S3. After the reaction is completed, turn off the circulating pump. S4. Open the valve at the bottom of the kettle, discharge the solution at the bottom of the kettle, and pump it into a poor solvent to precipitate polysulfone.

10. A method for preparing a polysulfone polymer according to claim 9, characterized in that, It also includes a step for treating the by-products of the polymerization reaction: remove the polymerization liquid in the reaction by-products and the unreacted acid-binding agent in the bed reactor, wash to obtain the by-products and the unreacted acid-binding agent. The by-products are directly dried and packaged, and the unreacted acid-binding agent can be recycled.

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