Preparation method of polysulfone polymer

Abstract

The invention discloses a polysulfone polymer and a preparation method thereof, and relates to the technical field of high polymer materials. According to the technical scheme provided by the invention, the solid alkali is filled on the rotor of the rotating packed bed, and the liquid-phase mixture is placed in the reaction kettle, so that the use amount of a solvent can be effectively reduced, the concentration of the liquid-phase mixture is improved, the reaction time is shortened, and the cost is also reduced. In the salt forming reaction, the liquid phase in the reaction kettle is fed into the rotating packed bed, so that the liquid phase is in full contact with the solid alkali, and the reaction time can be effectively shortened. The method has no too high requirement for the particle size of the solid base catalyst, filtration treatment is carried out in the polymerization reaction process to filter out by-products such as solid salt, filtration treatment serves as a link of a polymerization reaction circulation section, filtration is facilitated, the filtration difficulty is reduced, the dilution step in the post-treatment stage is omitted, and the production cost is reduced. And the production period is shortened.

Description

Technical Field

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

[0002] As a type of special polymer material, polysulfone polymers are widely used in aerospace, food, medical equipment and other fields due to their good chemical stability, excellent heat resistance, and stable mechanical properties.

[0003] The raw materials used in polysulfone polymers include solid raw materials, solid base catalysts, and solvents. The solid raw materials include bisphenol monomers and 4,4'-dichlorodiphenyl sulfone. The polymerization reaction can be divided into two steps: the first step is the reaction of bisphenol monomers with solid base catalysts (strong bases) to generate bisphenol salts, that is, salt formation reaction. This step is the key preparatory stage for the subsequent polymerization reaction; the second step is the condensation reaction of bisphenol salts and 4,4'-dichlorodiphenyl sulfone in a solvent. In this process, the chemical bonds between monomer molecules are broken and recombined to form long-chain polysulfone molecules. Chloride salts, as by-products, have an important influence on the performance of polysulfone products and need to be removed by filtration and washing during the preparation process. Among them, the polymerization equation can be simplified as follows:

[0004] n(bisphenolate) + n(4,4'-dichlorodiphenyl sulfone) → polysulfone + 2n(chloride)

[0005] During the actual preparation process, solid raw materials and a solid base catalyst are added simultaneously to a solvent. The solid raw materials dissolve in the solvent, while the solid base catalyst remains in a solid state, resulting in a solid-liquid two-phase reaction system. To maximize the reaction efficiency, this two-phase reaction system requires the solid base catalyst to have a particle size as fine as possible. This increases the complexity of the filtration equipment in the post-processing stage, prolongs production time, and increases production costs. Summary of the Invention

[0006] The main purpose of the present invention is to provide a polysulfone polymer and a preparation method thereof, aiming to solve the problem that the existing production process of polysulfone polymers has high requirements on the particle size of the catalyst and increases the difficulty of filtering equipment.

[0007] To achieve the above object, the present invention provides a method for preparing a polysulfone polymer, comprising the following steps:

[0008] S10, adding bisphenol monomer, 4,4'-dichlorodiphenyl sulfone and solvent into a reaction kettle to dissolve and heat the solid material;

[0009] S20, raising the temperature of the mixture in the reactor to a salt-forming temperature, pumping the heated mixture to a rotating packed bed, loading a solid base on the rotor of the rotating packed bed, controlling the rotation of the rotor so that the mixture is fully in contact with the solid base, causing a salt-forming reaction to occur to generate bisphenolate, and the material after the salt-forming reaction in the rotating packed bed is refluxed into the reactor;

[0010] S30, circulating the materials between the reactor and the rotating packed bed until the salt formation reaction is completed;

[0011] S40, raising the temperature of the material in the reactor to the polymerization temperature, so that the material in the reactor undergoes a polymerization reaction;

[0012] S50, after the polymerization reaction is completed, the polymerization product is post-processed to obtain a polysulfone polymer product.

[0013] Optionally, in step S10, the sum of the masses of the bisphenol monomer and 4,4'-dichlorodiphenyl sulfone is m, the sum of the masses of the bisphenol monomer, 4,4'-dichlorodiphenyl sulfone and the solvent is M, and the value of m / M is 0.35 to 0.45.

[0014] Optionally, in step S40, the material after the polymerization reaction in the reactor is filtered through a filter and then refluxed into the reactor, and the material circulates between the reactor and the filter to remove solid salt by-products until the viscosity of the material in the reactor reaches the target value and the polymerization reaction ends.

[0015] Optionally, in step S10, the material in the reactor is heated under a nitrogen atmosphere and stirring until the temperature of the material in the reactor reaches 80-100° C. and kept warm for 20-40 minutes, so that the bisphenol monomer and 4,4'-dichlorodiphenyl sulfone are dissolved in the solvent.

[0016] Optionally, in step S20, under nitrogen atmosphere and stirring conditions, the temperature of the mixture in the reactor is controlled to be 120-150° C., and the mixture at a temperature of 120-150° C. is fed into the rotating packed bed; and / or,

[0017] In step S20, the rotor is controlled to rotate at a speed of 1000 to 3000 r / min so that the mixture is fully in contact with the solid alkali.

[0018] Optionally, in step S20, the ratio of the mass of the solid base to the mass of the bisphenol monomer in step S10 is (8-9): (16.0-18.9); and / or,

[0019] In step S20, the solid base is sodium carbonate or potassium carbonate.

[0020] Optionally, in step S40, under nitrogen atmosphere and stirring conditions, the temperature of the material after the salt-forming reaction in the reactor is controlled to be 160-230° C., so that the material in the reactor further undergoes a polymerization reaction.

[0021] Optionally, in step S10, the bisphenol monomer is selected from one of bisphenol A, bisphenol S and hydroquinone; and / or,

[0022] In step S10, the solvent is selected from one of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.

[0023] Optionally, in step S50, post-processing includes crushing, washing, drying and granulation.

[0024] In the technical solution of the present invention, bisphenol monomer and 4,4'-dichlorodiphenyl sulfone solid raw materials, as well as a solvent, are added to a reactor, and a solid base is loaded onto the rotor of a rotating packed bed, so that a liquid phase mixture is formed in the reactor and a solid phase is formed in the rotating packed bed, with the solid phase and the liquid phase being in two devices. After the liquid phase material in the reactor is heated to a salt-forming temperature, it is fed into the rotating packed bed, and the rotor is controlled to rotate at a high speed to generate a large shear force, so that the liquid phase forms liquid filaments or droplets, thereby improving the liquid-solid two-phase mass transfer efficiency. Therefore, the present application does not have excessively high requirements for the particle size of the solid base catalyst, effectively reducing the difficulty of the filtering equipment and the amount of solvent used. The bisphenol monomer in the liquid phase can react with the solid base to form a salt more fully to generate a bisphenol salt, thereby increasing the reaction speed and shortening the reaction time.

[0025] The bisphenol salt produced in the rotating packed bed is refluxed into the reactor, while the heated material in the reactor is continuously fed into the salt-forming rotating packing to participate in the salt-forming reaction. The material in the reactor and the material in the rotating packed bed circulate continuously until the salt-forming reaction is complete. The material in the reactor after the salt-forming reaction is further heated to the polymerization temperature, causing the salt-forming material to undergo a polymerization reaction to produce a high-molecular-weight polysulfone. The post-polymerization material is then post-processed to obtain a polysulfone polymer product.

[0026] The filtration link of the present invention can be arranged in the post-processing stage with reference to conventional steps, that is, after the polymerization reaction is completed, the polymerization reaction material is diluted and filtered to filter out by-products such as solid salts. In this way, the production cycle is extended. Therefore, the present invention performs filtration treatment in the polymerization reaction stage, pumps the material of the polymerization reaction in the reactor into the filter, and flows back into the reactor after filtering through the filter, while the material in the reactor is controlled at the polymerization reaction temperature. The material in the reactor is continuously undergoing polymerization reaction, so that the material in the reactor and the material in the filter are continuously circulated until the viscosity of the material in the reactor reaches the target value and the polymerization reaction ends. The present invention uses filtration treatment as a link in the polymerization reaction cycle section, which is convenient for filtration and omits the dilution operation in the post-processing stage, thereby shortening the production cycle. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying any creative work.

[0028] Figure 1 A schematic structural diagram of an embodiment of a polysulfone polymer production system provided by the present invention;

[0029] Figure 2 for Figure 1 Schematic diagram of the structure of the third rotor.

[0030] Description of Figure Numbers:

[0031] 1. Reactor; 11. Nitrogen inlet; 12. First feed port; 13. Return port; 14. Material outlet; 15. Working fluid extraction pipe; 16. Circulation pump; 17. Heating device; 18. Stirring device; 19. First exhaust port; 2. Filter; 21. First filtrate extraction pipe; 22. Second filtrate extraction pipe; 23. Control valve; 24. Second feed port; 3. Rotating packed bed; 31. Third housing; 32. Third rotor; 321. Accommodating chamber; 322 , through hole; 323, wire mesh; 33, third feed port; 34, rotating shaft; 35, third exhaust port; 36, salt-forming material extraction pipe; 4, first cooler; 5, gas-liquid separator; 51, exhaust pipe; 52, return pipe; 6, separation gravity bed; 61, fourth shell; 62, fourth rotor; 63, fourth feed port; 64, fourth exhaust port; 65, reflux port; 7, second cooler; 8, reflux controller; 81, discharge pipe; 82, reflux pipe; 9, liquid storage tank.

[0032] The purpose, features and advantages of the present invention will be further described with reference to the accompanying drawings and in conjunction with the embodiments. DETAILED DESCRIPTION

[0033] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0034] It should be noted that if the embodiments of the present invention involve directional indications (such as up, down, left, right, front, back, etc.), the directional indications are only used to explain the relative position relationship, movement status, etc. between the components under a certain specific posture. If the specific posture changes, the directional indications will also change accordingly.

[0035] In addition, if there are descriptions involving "first", "second", etc. in the embodiments of the present invention, the descriptions of "first", "second", etc. are only for descriptive purposes and cannot be understood as indicating or suggesting their relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features limited to "first" and "second" may explicitly or implicitly include at least one of such features. In addition, if "and / or" or "and / or" appears in the full text, its meaning includes three parallel solutions. Taking "A and / or B" as an example, it includes solution A, solution B, or solutions that satisfy both A and B. In addition, the technical solutions between the various embodiments can be combined with each other, but it must be based on the ability of ordinary technicians in this field to implement. When the combination of technical solutions is mutually contradictory or cannot be implemented, it should be deemed that such a combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0036] See also Figure 1 and Figure 2The present invention provides a polysulfone polymer production system, comprising: a reactor 1, a filter 2 and a rotating packed bed 3, wherein the upper portion of the reactor 1 is provided with a nitrogen inlet 11, a first feed inlet 12 and a return feed inlet 13, the bottom of the reactor 1 is provided with a working liquid extraction pipe 15, and the reactor 1 is provided with a heating device 17; the upper portion of the filter 2 is provided with a second feed inlet 24, the second feed inlet 24 is connected to the discharge end of the working liquid extraction pipe 15, the bottom of the filter 2 is provided with a first filtrate extraction pipe 21 and a second filtrate extraction pipe 22, the first filtrate extraction pipe 2 1 and the second filtrate extraction pipe 22 are both provided with a control valve 23, and the discharge end of the second filtrate extraction pipe 22 is connected to the return port 13; the rotating packed bed 3 includes a third shell 31, and a third rotor 32 arranged in the third shell 31, and the third rotor 32 is provided with a accommodating cavity 321 connected to the inner cavity of the third shell 31, and the top of the third shell 31 is provided with a third feed port 33 connected to the discharge end of the first filtrate extraction pipe 21, and the bottom of the third shell 31 is provided with a salt-forming material extraction pipe 36 connected to the return port 13.

[0037] In the technical solution of the present invention, bisphenol monomer, 4,4'-dichlorodiphenyl sulfone, and a solvent are added to reactor 1 through first feed port 12. Solid base is loaded into chamber 321. Nitrogen enters reactor 1 through nitrogen inlet 11, maintaining the entire system under nitrogen protection. Heating device 17 is activated to heat the materials in reactor 1. When the temperature reaches 80-100°C, the temperature is maintained for 20-40 minutes. During the heating and holding process, stirring is performed to fully dissolve the bisphenol monomer and 4,4'-dichlorodiphenyl sulfone in the solvent, forming a liquid mixture. The liquid mixture in reactor 1 is further heated and stirred until the temperature reaches 120-150°C.

[0038] The control valve 23 on the first filtrate extraction pipe 21 is controlled to be in an open state, and the control valve 23 on the second filtrate extraction pipe 22 is controlled to be in a closed state. The mixture with a temperature of 120-150°C in the reactor 1 is sent to the filter 2 through the working liquid extraction pipe 15. The filtrate obtained after filtration is sent to the rotating packed bed 3 through the first filtrate extraction pipe 21. The third rotor 32 is controlled to rotate at a speed of 1000-3000 r / min. The high-speed rotation of the rotor generates a large shear force, which causes the liquid phase mixture to be broken into fine liquid filaments and droplets, effectively improving the liquid-solid two-phase mass transfer efficiency, increasing the reaction speed, shortening the reaction time, and allowing the bisphenol monomer in the mixture to react more fully with the solid base to form a salt to generate bisphenol salt. The material after the salt-forming reaction in the rotating packed bed 3 is taken out through the salt-forming material taking-out pipe 36 and refluxed into the reactor 1, while the temperature of the material in the reactor 1 is controlled at 120-150°C. The heated material in the reactor 1 is sent to the filter 2, and after filtration, it is sent to the rotating packed bed 3, and then refluxed into the reactor 1. In this way, the material circulates between the reactor 1 and the rotating packed bed 3 until the salt-forming reaction is completed.

[0039] After the salt formation reaction is completed, the control valve 23 on the first filtrate extraction pipe 21 is controlled to be closed, while the control valve 23 on the second filtrate extraction pipe 22 is controlled to be open. The material after the salt formation reaction in the reactor 1 is heated with stirring during the heating process, so that the temperature of the material after the salt formation reaction in the reactor 1 is raised to 160-230°C, so that the bisphenol salt and 4,4'-dichlorodiphenyl sulfone undergo polymerization to form a polymer. The polymerized material is sent to the filter 2. The filtrate obtained after filtration is withdrawn through the second filtrate extraction pipe 22 and refluxed into the reactor 1. The temperature of the material in the reactor 1 is controlled at 160-230°C. The material after the salt formation reaction in the reactor 1 undergoes polymerization reaction. The material in the reactor 1 is sent to the filter 2, filtered, and then refluxed into the reactor 1. In this way, the material circulates between the reactor 1 and the filter 2 until the viscosity of the material in the reactor 1 reaches the target viscosity (2000-10000 mPa·s), and the polymerization reaction is completed.

[0040] The material after the polymerization reaction in the reactor 1 is taken out and subjected to post-processing, which includes crushing, washing, drying and granulation to obtain a polysulfone polymer product.

[0041] It is understandable that during the entire production process, the entire system is under nitrogen protection. The pore size of the filter pores in the filter 2 is 200 to 300 mesh. A stirring device 18 is provided in the reactor 1, and a material discharge port 14 is provided at the bottom of the reactor 1 to take out the material after the polymerization reaction is completed. Control valves are provided on the first feed port 12 and the material discharge port 14. When feeding and product removal are required, the corresponding control valves are opened. After the feeding is completed, or when there is no need to remove the product, the corresponding control valves are closed. A viscosity detection device is provided in the reactor 1 to detect in real time whether the viscosity of the polymerization reaction material in the reactor 1 reaches the target value.

[0042] Furthermore, the rotating packed bed 3 is located above the reactor 1 , and the filter 2 is located above the rotating packed bed 3 ; a circulating pump 16 is provided on the working fluid extraction pipe 15 .

[0043] By adopting the above technical solution, circulating pump 16 achieves material circulation during the salt formation reaction and polymerization reaction stages, thereby effectively achieving product production. Filter 2 is located above rotating packed bed 3, allowing the filtrate to flow smoothly back into rotating packed bed 3 during the salt formation reaction stage. Rotating packed bed 3 is located above reactor 1, allowing the material after the salt formation reaction in rotating packed bed 3 to flow smoothly back into reactor 1 during the salt formation reaction stage.

[0044] Furthermore, the polysulfone polymer production system also includes a salt-forming gas discharge section, which includes a first cooler 4 and a gas-liquid separator 5 connected to the first cooler 4; the feed port of the first cooler 4 is connected to the third exhaust port 35 at the top of the third shell 31 through a pipeline.

[0045] Specifically, the first cooler 4 is located above the rotating packed bed 3, and the gas-liquid separator 5 is located between the first cooler 4 and the rotating packed bed 3; an exhaust pipe 51 is provided at the top of the gas-liquid separator 5, and a return pipe 52 connected to the return port 13 is provided at the bottom.

[0046] By adopting the above technical solution, the solid base is sodium carbonate or potassium carbonate, and the carbon dioxide gas and a small amount of solvent generated during the salt-forming reaction are discharged through the third exhaust port 35. After being cooled by the first cooler 4, they enter the gas-liquid separator 5, and the separated carbon dioxide gas is discharged through the exhaust pipe 51. The liquid solvent obtained by separation is refluxed to the reactor 1 through the return pipe 52 to ensure the amount of solvent in the reaction system.

[0047] It is understandable that a carbon dioxide detector is provided on the exhaust pipe 51 to detect in real time whether carbon dioxide gas is generated in the rotating packed bed 3. When carbon dioxide gas is no longer discharged from the rotating packed bed 3, the salt formation reaction ends.

[0048] Furthermore, the third housing 31 is a hollow cylindrical structure, and the diameter of the third housing 31 is D1, 850mm≤D1≤950mm; the third rotor 32 is a hollow ring structure, and the hollow structure forms the accommodating cavity 321. The third rotor 32 is provided with a through hole 322, and a wire mesh 323 is provided in the through hole 322. The thickness of the third rotor 32 is d, the height of the accommodating cavity 321 is d0, and the outer ring diameter of the third rotor is D 2. The inner ring diameter is D3, 10 mm ≤ d ≤ 30 mm, 2 mm ≤ d0 ≤ 24 mm, 800 mm ≤ D2 ≤ 900 mm, and 20 mm ≤ D3 ≤ 50 mm; the through hole 322 is circular, the aperture of the through hole 322 is 5 to 10 mm, the aperture of the wire mesh is 200 mesh, and the particle size of the solid alkali filled in the accommodating cavity 321 is 80 to 120 mesh; there are 5 to 7 third rotors 32, and the multiple third rotors 32 are distributed along the axial direction of the third housing 31.

[0049] It will be appreciated that the rotating packed bed 3 also includes a shaft 34 rotatably mounted on the third housing. The inner ring of the third rotor 32 is mounted on the shaft 34. The shaft 34 is connected to a drive mechanism. Rotation of the rotor is achieved by driving the shaft 34. The porosity of all third rotors 32 is φ, where φ = V / V0, where V is the sum of the volumes of the through-holes 322 on all third rotors and V0 is the volume of all third rotors, with a value of 0.80 ≤ φ ≤ 0.95. The spacing between two adjacent third rotors 32 is H, with a value of 3 mm ≤ H ≤ 5 mm. The central axis of the third rotor 32 coincides with the central axis of the third housing 31.

[0050] Furthermore, the polysulfone polymer production system also includes a polymerization gas discharge section, which includes a separation gravity bed 6 arranged above the reactor 1, and the fourth feed port 63 at the bottom of the separation gravity bed 6 is connected to the first exhaust port 19 at the top of the reactor 1 through a pipeline, and the top of the separation gravity bed 6 is provided with a fourth exhaust port 64.

[0051] By adopting the above technical solution, when the material in the reactor 1 undergoes a polymerization reaction, the generated water vapor is discharged through the first exhaust port 19. When the water vapor is discharged, it carries a small amount of solvent. The water vapor containing a small amount of solvent enters the separation gravity bed 6. The rotor of the separation gravity bed 6 rotates at a speed of 800 to 1000 r / min, so that the gas and liquid are separated more fully. After separation, the water vapor is discharged through the fourth exhaust port 64, and the solvent can flow back to the reactor 1 through the first exhaust port 19.

[0052] It is understood that the separation gravity bed 6 includes a fourth shell 61 and a fourth rotor 62 disposed within the fourth shell 61. The spacing S1 between the outer wall of the fourth rotor 62 and the inner wall of the fourth shell 61 is 40 mm. The fourth rotor 62 comprises a corrugated plate with a plurality of through-hole structures to enhance gas-liquid separation.

[0053] It can be understood that there are multiple fourth rotors, and the multiple fourth rotors are installed on the shaft. The driving shaft rotates to drive the fourth rotors to rotate.

[0054] Furthermore, the polymerization gas discharge section also includes a second cooler 7, a reflux controller 8 and a liquid storage tank 9, the second cooler 7 is arranged above the separation gravity bed 6, the reflux controller 8 is located between the second cooler 7 and the separation gravity bed 6, and the liquid storage tank 9 is located below the reflux controller 8; the feed port of the second cooler 7 is connected to the fourth exhaust port 64 through a pipeline, and the discharge port of the second cooler 7 is connected to the feed end of the reflux controller 8 through a pipeline; the discharge end of the reflux controller 8 is provided with a reflux pipe 82 and a discharge pipe 81, the liquid storage tank 9 is connected to the discharge end of the discharge pipe 81, and the discharge end of the reflux pipe 82 is connected to the reflux port 65 at the top of the separation gravity bed 6.

[0055] By adopting the above technical solution, the water vapor discharged through the fourth exhaust port 64 enters the second cooler 7, and after cooling, forms liquid water. Part of the liquid water is transported to the liquid storage tank 9 through the discharge pipe 81, and the remaining liquid water flows back to the separation gravity bed 6 through the reflux pipe 82, countercurrently with the rising gas phase in the separation gravity bed 6, so as to improve the gas-liquid separation effect.

[0056] It will be appreciated that the reflux controller 8 facilitates adjustment of the liquid water reflux ratio, i.e., the mass of liquid water returning to the separation gravity bed 6, according to production needs. A vacuum is maintained in the liquid storage tank 9 to facilitate the entry of liquid water. The third rotor 32 and the fourth rotor 62 can be made of polyetheretherketone (PEEK), although other corrosion-resistant materials may also be used as needed.

[0057] The technical solutions of the present invention are further described in detail below in conjunction with specific embodiments and drawings. It should be understood that the following embodiments are only used to explain the present invention and are not used to limit the present invention.

[0058] In the following Examples 1 to 3, the parameters of the salt-forming rotating packed bed 3 are as follows: the diameter D1 of the third shell 31 is 900 mm; the thickness d of the third rotor 32 is 20 mm, the height d0 of the accommodating cavity 321 is 8 mm, the outer ring diameter D2 of the third rotor is 850 mm, the inner ring diameter D3 is 30 mm, the aperture of the through hole 322 is 8 mm, the aperture of the wire mesh is 200 mesh, and the particle size of the solid alkali (sodium carbonate or potassium carbonate) is 100 mesh; there are 7 third rotors 32, and the spacing H between two adjacent third rotors 32 is 4 mm; the porosity φ of the through hole 322 is 0.85.

[0059] Example 1

[0060] Combined with attachment Figure 1 , a method for preparing polyethersulfone, comprising the following steps:

[0061] S10. Add 183 kg of bisphenol S, 210 kg of 4,4'-dichlorodiphenyl sulfone, and 550 L of N-methylpyrrolidone into a 2500 L reactor, and load 90 kg of potassium carbonate onto the rotor of a rotating packed bed; under nitrogen protection and stirring (120 rpm), heat the contents of the reactor to 80° C. and maintain the temperature for 20 min to form a liquid mixture;

[0062] S20, under nitrogen protection and stirring (100r / min), the mixture in the reactor is heated to 145-150°C, the heated mixture is pumped into a filter, and after filtration, the filtrate obtained is fed into a rotating packed bed, the rotor of the rotating packed bed is controlled to rotate at a speed of 1500r / min, so that the mixture is fully in contact with potassium carbonate, a salt-forming reaction occurs, bisphenolate is generated and carbon dioxide gas is produced, and the material after the salt-forming reaction in the rotating packed bed is refluxed into the reactor;

[0063] S30, circulating the materials between the reactor and the rotating packed bed until no more carbon dioxide gas is generated in the rotating packed bed, and the salt-forming reaction is completed;

[0064] S40, under nitrogen protection and stirring (100 rpm), the temperature of the material after the salt-forming reaction in the reactor is raised to 215-220° C. to allow the material in the reactor to further undergo a polymerization reaction, and the material after the polymerization reaction is sent to a filter. After filtering, the obtained filtrate is refluxed into the reactor;

[0065] S50, the material circulates between the reactor and the filter until the viscosity of the material in the reactor reaches 5000 mPa·s, and the polymerization reaction is completed. The polymerization reaction product is taken out, crushed, washed, dried and granulated to obtain a polyethersulfone product.

[0066] It was measured that the ash content of the prepared polyethersulfone product was 0.006 wt % and the heat deformation temperature was 204° C. (1.82 MPa).

[0067] Example 2

[0068] Combined with attachment Figure 1 , a method for preparing polysulfone, comprising the following steps:

[0069] S10, adding 160 kg of bisphenol A, 201 kg of 4,4'-dichlorodiphenyl sulfone and 550 L of N,N-dimethylformamide into a 2500 L reactor, and loading 80 kg of sodium carbonate onto the rotor of a rotating packed bed; under nitrogen protection and stirring (120 r / min), heating the materials in the reactor to 80° C. and keeping the temperature for 20 min to form a liquid phase mixture;

[0070] S20, under nitrogen protection and stirring (100r / min), the mixture in the reactor is heated to 130-135°C, the heated mixture is pumped into a filter, and after filtration, the filtrate obtained is fed into a rotating packed bed, the rotor of the rotating packed bed is controlled to rotate at a speed of 1500r / min, so that the mixture is fully in contact with sodium carbonate, a salt-forming reaction occurs, bisphenolate is generated and carbon dioxide gas is produced, and the material after the salt-forming reaction in the rotating packed bed is refluxed into the reactor;

[0071] S30, circulating the materials between the reactor and the rotating packed bed until no more carbon dioxide gas is generated in the rotating packed bed, and the salt-forming reaction is completed;

[0072] S40, under nitrogen protection and stirring (100 rpm), heating the material after the salt-forming reaction in the reactor to 160-165° C. to allow the material in the reactor to further undergo a polymerization reaction, and sending the material after the polymerization reaction into a filter. After filtering, the obtained filtrate is refluxed into the reactor;

[0073] S50, the material circulates between the reactor and the filter until the viscosity of the material in the reactor reaches 5000 mPa·s, and the polymerization reaction is completed. The polymerization reaction product is taken out, crushed, washed, dried and granulated to obtain a polysulfone product.

[0074] It was measured that the ash content of the prepared polysulfone product was 0.01 wt % and the heat deformation temperature was 175° C. (1.82 MPa).

[0075] Example 3

[0076] Combined with attachment Figure 1 , a method for preparing polyphenylsulfone, comprising the following steps:

[0077] S10, adding 180.9 kg of hydroquinone, 211 kg of 4,4'-dichlorodiphenyl sulfone and 550 L of N,N-dimethylacetamide to a 2500 L reactor, and loading 80 kg of sodium carbonate on the rotor of a rotating packed bed; under nitrogen protection and stirring (120 r / min), the materials in the reactor were heated to 80° C. and kept warm for 20 min to form a liquid phase mixture;

[0078] S20, under nitrogen protection and stirring (100r / min), the temperature of the mixture in the reactor was raised to 130-135°C, the heated mixture was pumped into a filter, and after filtration, the filtrate obtained was fed into a rotating packed bed, the rotor of the rotating packed bed was controlled to rotate at a speed of 1500r / min, so that the mixture was fully contacted with sodium carbonate, a salt-forming reaction occurred, bisphenolate and carbon dioxide gas were generated, and the material after the salt-forming reaction in the rotating packed bed was refluxed into the reactor;

[0079] S30, circulating the materials between the reactor and the rotating packed bed until no more carbon dioxide gas is generated in the rotating packed bed, and the salt-forming reaction is completed;

[0080] S40, under nitrogen protection and stirring (100 rpm), heating the material after the salt-forming reaction in the reactor to 170-175° C. to allow the material in the reactor to further undergo a polymerization reaction, and sending the material after the polymerization reaction into a filter. After filtering, the obtained filtrate is refluxed into the reactor;

[0081] S50, the material circulates between the reactor and the filter until the viscosity of the material in the reactor reaches 5000 mPa·s, and the polymerization reaction is completed. The polymerization reaction product is taken out, crushed, washed, dried and granulated to obtain a polyphenylene sulfone product.

[0082] It was measured that the ash content of the prepared polyphenylsulfone product was 0.004 wt % and the heat deformation temperature was 207° C. (1.82 MPa).

[0083] The above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Those skilled in the art will readily appreciate that the present invention is susceptible to various modifications and variations. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention shall be included within the scope of the present invention.

Claims

1. A method for preparing a polysulfone polymer, characterized in that: The following steps are involved: S10, adding bisphenol monomer, 4,4'-dichlorodiphenyl sulfone and solvent into a reaction kettle to dissolve and heat the solid material; S20, raising the temperature of the mixture in the reactor to a salt-forming temperature, pumping the heated mixture to a rotating packed bed, loading a solid base on the rotor of the rotating packed bed, controlling the rotation of the rotor so that the mixture is fully in contact with the solid base, causing a salt-forming reaction to occur to generate bisphenolate, and the material after the salt-forming reaction in the rotating packed bed is refluxed into the reactor; S30, circulating the materials between the reactor and the rotating packed bed until the salt formation reaction is completed; S40, raising the temperature of the material in the reactor to the polymerization temperature, so that the material in the reactor undergoes a polymerization reaction; S50, after the polymerization reaction is completed, the polymerization product is post-processed to obtain a polysulfone polymer product.

2. The method for preparing a polysulfone polymer according to claim 1, wherein In step S10, the sum of the masses of the bisphenol monomer and 4,4'-dichlorodiphenyl sulfone is m, the sum of the masses of the bisphenol monomer, 4,4'-dichlorodiphenyl sulfone and the solvent is M, and the value of m / M is 0.35 to 0.

45.

3. The method for preparing a polysulfone polymer according to claim 1, wherein: In step S40, the materials of the polymerization reaction in the reactor are filtered through a filter and then flow back into the reactor. The materials circulate between the reactor and the filter to remove solid salt by-products until the viscosity of the materials in the reactor reaches the target value, and the polymerization reaction is terminated.

4. The method for preparing a polysulfone polymer according to claim 1, wherein: In step S10, the material in the reactor is heated under a nitrogen atmosphere and stirring until the temperature of the material in the reactor reaches 80-100° C. and kept warm for 20-40 minutes, so that the bisphenol monomer and 4,4'-dichlorodiphenyl sulfone are dissolved in the solvent.

5. The method for preparing a polysulfone polymer according to claim 1, wherein: In step S20, under nitrogen atmosphere and stirring conditions, the temperature of the mixture in the reactor is controlled to be 120-150° C., and the mixture at a temperature of 120-150° C. is fed into the rotating packed bed; and / or, In step S20, the rotor is controlled to rotate at a speed of 1000 to 3000 r / min so that the mixture is fully in contact with the solid alkali.

6. The method for preparing a polysulfone polymer according to claim 1, wherein: In the step S20, the ratio of the mass of the solid base to the mass of the bisphenol monomer in the step S10 is (8-9): (16.0-18.9); and / or, In step S20, the solid base is sodium carbonate or potassium carbonate.

7. The method for preparing a polysulfone polymer according to claim 1, wherein: In step S40, under nitrogen atmosphere and stirring conditions, the temperature of the material after the salt-forming reaction in the reactor is controlled to be 160-230° C., so that the material in the reactor further undergoes polymerization reaction.

8. The method for preparing a polysulfone polymer according to claim 1, wherein: In step S10, the bisphenol monomer is selected from one of bisphenol A, bisphenol S and hydroquinone; and / or, In step S10, the solvent is selected from one of N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.

9. The method for preparing a polysulfone polymer according to claim 1, wherein: In step S50, the post-processing includes crushing, washing, drying and granulation.

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