A device for continuously preparing large-size polymer balls with controllable size and a method for using the same

Abstract

A device capable of continuously preparing large-sized polymer spheres with controllable sizes and a method for using the same relate to a device for preparing large-sized polymer spheres and a method for using the same. The present invention aims to solve the current technical problems of low monomer utilization and uncontrollable size when preparing large-sized polymer spheres. The present invention utilizes the method of adjusting the surface tension and the density of the organic phase to form spherical droplets of fixed and controllable size in the aqueous phase from the organic phase; the size of the polymer spheres can be controlled by selecting quantitative channels of different volumes to fix the volume of the organic phase entering the aqueous phase according to needs, thereby achieving the preparation of large-sized polymer spheres; the organic phase spherical droplets are separated by the aqueous phase in the serpentine polymerization tube, thereby greatly improving the utilization rate of raw materials; the serpentine tube polymerization structure is utilized to enable the spherical droplets to move in the serpentine polymerization tube and complete polymerization, thereby achieving the continuous preparation of polymer spheres.

Description

Technical Field

[0001] The present invention relates to a device for preparing large-sized polymer balls and a method for using the device. Background Art

[0002] High molecular weight polymers have a wide range of applications in daily necessities, engineering, and other fields, and the application of polymer materials with a defined shape in the field of chemical engineering is becoming increasingly diverse. Styrene and divinylbenzene copolymers (SDB) have a wide range of applications in ion exchange resins, catalyst supports, and other fields. Currently, spherical SDB is usually obtained by methods such as aqueous suspension polymerization. The size of the spheres is relatively small, with a diameter generally ranging from 0.8mm to 3mm. SDB of uniform size needs to be obtained by screening, which has two major disadvantages. First, the small particle size leads to unstable hydraulic properties of the ion exchange bed or catalyst bed, high bed resistance, and prone to flooding when used for gas-liquid exchange. Second, the wide particle size distribution leads to low raw material utilization due to screening. Large-sized SDB polymer spheres are expected to solve the above problems. Due to the disadvantages of low monomer utilization and a wide range of sphere size distribution, improved preparation methods are constantly being proposed. Dan Guiping (Dan Guiping, Lu Yaozhang, Qiu Yongmei, Ma Junge, Zeng Junhui, Preparation of large-particle hydrophobic catalysts and performance research of tritium hydrogen oxide (HT), Atomic Energy Science and Technology, 1999, 1 (33), 12-17) used a two-stage polymerization and screening method to obtain SDB polymer spheres with a particle size of 3 mm. This method not only limited the improvement of the size of the polymer spheres, but also led to a significant reduction in the utilization rate of the raw monomers. Dan Guiping et al. (Dan Guiping, Du Yang, Yang Yong, Development of 6mm Pt-PTFE hydrophobic catalysts, Nuclear Chemistry and Radiochemistry, 2004, 26 (3), 166-170) used pressing, sintering and dissolution porogen method to prepare porous PTFE hydrophobic supports. Due to the low porosity of polytetrafluoroethylene (PTFE) polymer, the specific surface area of the support is low, only 5 to 8 m 2 / g, and the Pt loading on the carrier surface is relatively large, reaching 1.2%. In order to increase the size of SDB carrier spheres, Gou Kezhen (Gou Kezhen, Synthesis and Performance Research of Large-Particle SDB Hydrophobic Catalyst Carriers [D], 2014) used suspension polymerization to prepare SDB carriers. The disadvantages of this method are: (1) the aqueous suspension polymerization method requires product screening; (2) the particle size distribution range is large, and after screening, the particle size is 2-5 mm, and it is impossible to obtain a single particle size sphere carrier; (3) the raw material utilization rate is low, only 35%-40%. Patent CN114682203A discloses a device and method for the continuous production of polymer microspheres. The device utilizes a tubular structure with a heating section, a cooling section, a heat preservation section, and a buffer section that are interconnected to form a cavity. The advantage of this device is that it overcomes the low efficiency of intermittent production. The use of a stirring paddle to break up the monomer droplets inevitably results in small polymer microspheres with a wide particle size distribution. To obtain polymer microspheres of uniform size, screening is necessary. Patent CN115178198A couples a microfluidic chip with electrospray technology to prepare polymer microspheres using ultraviolet light-induced polymerization. This solves the problem of a wide particle size distribution range and enables continuous polymer microsphere preparation. However, the fundamental principle of this method is that the liquid contracts under the action of an electric field to form a sharp-ended Taylor cone. The cone tip ejects a micro-nanoscale liquid jet. Its advantage is that it can easily complete the transition from millimeter scale to nanometer scale. Taylor cones use capillaries as nozzles, making it difficult to produce polymer microspheres with millimeter-scale diameters. Furthermore, Li Xiuchun (Li Xiuchun, Preparation of Large-Sized SDB Hydrophobic Catalyst Supports and Their Effect on Exchange Column Bed Resistance [D], Southwest University of Science and Technology, 2016) used suspension polymerization to produce SDB spheres with sizes of 1.3 mm, 2.4 mm, and 3.3 mm by controlling the rotational speed. While the diameter of the SDB spheres increased, it did not significantly improve upon the traditional SDB granular support diameters of 0.8 mm to 1.5 mm, and achieving uniform size also required sieving. Summary of the Invention

[0003] The present invention aims to solve the technical problems of low monomer utilization and uncontrollable size in the current preparation of large-sized polymer balls, and to provide a device for continuously preparing large-sized polymer balls with controllable size and a method for using the device.

[0004] The device for continuously preparing large-sized polymer spheres with controllable size of the present invention comprises a prepolymerization tank 1, a first pump 2, a second pump 3, a metering device 4, a hot water circulation pump 5, a serpentine polymerization pipe 6, a hydrothermal tank 7, a maturation tank 8, a first hydrothermal tank 9, a second hydrothermal tank 10, an organic phase reflux pipe 11, a second organic phase delivery pipe 12, a first aqueous phase delivery pipe 13, a polymerization delivery pipe 14, a second aqueous phase delivery pipe 15, and a first organic phase delivery pipe 16.

[0005] The water outlet of the prepolymerization tank 1 is connected to one end of the first pump 2 through the first organic phase delivery pipe 16, and the other end of the first pump 2 is connected to the organic phase input pipe of the quantitative device 4 through the second organic phase delivery pipe 12. The organic phase output pipe of the quantitative device 4 is refluxed to the prepolymerization tank 1 through the organic phase reflux pipe 11; the two ends of the hot water circulation pump 5 are respectively connected to the inlet and outlet of the hydrothermal tank 7; the serpentine polymerization pipe 6 is vertically arranged in the hydrothermal tank 7, and the lower end of the serpentine polymerization pipe 6 passes through the hydrothermal tank 7 and is connected to the maturation tank 8, and the serpentine A spherical tube 6-1 is provided on top of the shaped polymerization tube 6 and is connected to the spherical tube 6-1. The spherical tube 6-1 is disposed within the hydrothermal tank 7. The outlet of the maturation tank 8 is connected to one end of the second pump 3 via a second aqueous phase delivery pipe 15. The other end of the second pump 3 is connected to the aqueous phase input pipe of the metering device 4 via a first aqueous phase delivery pipe 13. The aqueous phase output pipe of the metering device 4 is connected to the spherical tube 6-1 via a polymerization delivery pipe 14. A first hydrothermal tank 9 is provided outside the maturation tank 8. A second hydrothermal tank 10 is provided outside the prepolymerization tank 1.

[0006] The quantitative device 4 has three structures, and you can choose one when using it. The specific structures are as follows:

[0007] The first structure is composed of a first sleeve 4-1, a first organic phase input pipe 4-3, a first aqueous phase input pipe 4-4, a first bypass pipe 4-5, a second bypass pipe 4-6, a first organic phase output pipe 4-7, a first aqueous phase output pipe 4-8 and a first rotary piston 4-9; the first rotary piston 4-9 is provided with a first quantitative channel 4-2 of a straight pipe structure, and the first rotary piston 4-9 is arranged in the first sleeve 4-1 and is in a sliding connection relationship; the upper end and the lower end of the first sleeve 4-1 are respectively connected to the first aqueous phase input pipe 4-4 and the first aqueous phase output pipe 4-8, and the horizontal ends of the first sleeve 4-1 are respectively connected to the first organic phase input pipe 4-3 and the first organic phase output pipe 4-7; when the first rotary piston 4-9 rotates to the first quantitative channel 4-2, the first rotary piston 4-9 is provided with a first quantitative channel 4-2 of a straight pipe structure, and the first rotary piston 4-9 is arranged in the first sleeve 4-1 and is in a sliding connection relationship; the upper end and the lower end of the first sleeve 4-1 are respectively connected to the first aqueous phase input pipe 4-4 and the first aqueous phase output pipe 4-8, and the horizontal ends of the first sleeve 4-1 are respectively connected to the first organic phase input pipe 4-3 and the first organic phase output pipe 4-7; 2 is in a horizontal position, the two ends of the first quantitative channel 4-2 are connected to the first organic phase input pipe 4-3 and the first organic phase output pipe 4-7 respectively; when the first rotating piston 4-9 rotates to the first quantitative channel 4-2 is in a vertical position, the two ends of the first quantitative channel 4-2 are connected to the first aqueous phase input pipe 4-4 and the first aqueous phase output pipe 4-8 respectively; a second bypass pipe 4-6 is further provided between the first organic phase input pipe 4-3 and the first organic phase output pipe 4-7; a first bypass pipe 4-5 is further provided between the first aqueous phase input pipe 4-4 and the first aqueous phase output pipe 4-8; the first bypass pipe 4-5 and the second bypass pipe 4-6 ensure that the organic phase solution and the aqueous phase are always in a flowing state during the process of collecting and releasing the organic phase and rotating the piston through the quantitative channel;

[0008] The second structure is composed of a second organic phase output pipe 4-10, a second sleeve 4-11, a second organic phase input pipe 4-12, a second rotary piston 4-14, a three-way pipe 4-15, a second aqueous phase output pipe 4-16, a third sleeve 4-17, a third rotary piston 4-18, a vertical connecting pipe 4-20, a fourth rotary piston 4-21, a fourth sleeve 4-23 and a second aqueous phase input pipe 4-24; the three-way pipe 4-15 has three openings, one is located at the top and opens vertically upward, and the other two are located at the bottom and open horizontally; the second quantitative channel 4-13 of a straight pipe structure is provided in the second rotary piston 4-14, and the second rotary piston 4-14 is provided in the second sleeve 4-11 and is connected for sliding. connection relationship; the horizontal ends of the second sleeve 4-11 are respectively connected to the second organic phase input pipe 4-12 and the second organic phase output pipe 4-10; the lower end of the second sleeve 4-11 is connected to the top opening of the tee pipe 4-15, and the other two horizontal openings of the tee pipe 4-15 are respectively connected to the horizontal ends of the fourth sleeve 4-23 and the third sleeve 4-17; the fourth sleeve 4-23 is arranged directly above the third sleeve 4-17; when the second rotary piston 4-14 rotates to the second quantitative channel 4-13 is in a horizontal position, the two ends of the second quantitative channel 4-13 are respectively connected to the second organic phase input pipe 4-12 and the second organic phase output pipe 4-10; when the second rotary piston 4-14 rotates to the second quantitative channel 4-13 is in a vertical position When the third rotary piston 4-18 is in the vertical position, the lower end of the second quantitative channel 4-13 is connected to the top opening of the three-way pipe 4-15; a third quantitative channel 4-19 of T-shaped structure is provided in the third rotary piston 4-18, and the third rotary piston 4-18 is provided in the third sleeve 4-17 and is in a sliding connection relationship; the upper and lower ends of the third sleeve 4-17 are respectively connected to the lower end of the vertical connecting pipe 4-20 and the second water phase output pipe 4-16; the horizontal end of the third sleeve 4-17 is connected to a horizontal opening of the three-way pipe 4-15; when the third rotary piston 4-18 rotates to the opposite ends in the third quantitative channel 4-19 and is in a vertical position, the upper and lower ends of the third quantitative channel 4-19 are respectively connected to the lower part of the vertical connecting pipe 4-20 and the second water phase output pipe The third rotary piston 4-18 is connected to the third quantitative channel 4-19; when the third rotary piston 4-18 rotates to the point where the two opposite ends of the third quantitative channel 4-19 are in a horizontal position, the bottom opening of the third quantitative channel 4-19 is connected to the second water phase output pipe 4-16, and the horizontal end of the third quantitative channel 4-19 is connected to a horizontal opening of the three-way pipe 4-15; the fourth rotary piston 4-21 is provided with a fourth quantitative channel 4-22 of a T-shaped structure, and the fourth rotary piston 4-21 is arranged in a fourth sleeve 4-23 and is in a sliding connection relationship; the upper and lower ends of the fourth sleeve 4-23 are respectively connected to the second water phase input pipe 4-24 and the upper end of the vertical connecting pipe 4-20; the horizontal end of the fourth sleeve 4-23 is connected to a horizontal opening of the three-way pipe 4-15;When the fourth rotary piston 4-21 rotates until the opposite ends of the fourth metering channel 4-22 are in a vertical position, the upper and lower ends of the fourth metering channel 4-22 are respectively connected to the second water phase input pipe 4-24 and the upper part of the vertical connecting pipe 4-20; when the fourth rotary piston 4-21 rotates until the opposite ends of the fourth metering channel 4-22 are in a horizontal position, the top opening of the fourth metering channel 4-22 is connected to the second water phase input pipe 4-24, and the horizontal end of the fourth metering channel 4-22 is connected to a horizontal opening of the tee pipe 4-15;

[0009] The third structure is composed of a third organic phase input pipe 4-25, a third organic phase output pipe 4-26, a third aqueous phase input pipe 4-27, a fifth rotary piston 4-28, a fifth sleeve 4-30, a third aqueous phase output pipe 4-31, an obtuse angle connecting pipe 4-32, a sixth sleeve 4-34, a sixth rotary piston 4-35 and a right angle connecting pipe 4-36; a fifth quantitative channel 4-29 of a straight pipe structure is provided in the fifth rotary piston 4-28, and the fifth rotary piston 4-28 is provided in the fifth The upper end and lower end of the fifth sleeve 4-30 are connected to the third aqueous phase input pipe 4-27 and the third aqueous phase output pipe 4-31 respectively, and the horizontal ends of the first sleeve 4-1 are connected to the third organic phase input pipe 4-25 and the third organic phase output pipe 4-26 respectively; when the fifth rotating piston 4-28 rotates to the fifth quantitative channel 4-29 in a horizontal position, the ends of the fifth quantitative channel 4-29 are connected to the third organic phase input pipe 4-25 and the third organic phase output pipe 4-26 respectively. The first and second water phase output pipes 4-26 are connected; when the fifth rotating piston 4-28 rotates to the fifth quantitative channel 4-29 in a vertical position, the two ends of the fifth quantitative channel 4-29 are respectively connected to the third water phase input pipe 4-27 and the third water phase output pipe 4-31; the sixth rotating piston 4-35 is provided with a sixth quantitative channel 4-33 of a straight pipe structure, and the sixth rotating piston 4-35 is provided in a sixth sleeve 4-34 and is in a sliding connection relationship; the upper end and the lower end of the sixth sleeve 4-34 are respectively at right angles to each other. The lower end of the connecting pipe 4-36 is connected to the upper end of the obtuse-angle connecting pipe 4-32, and the other end of the right-angle connecting pipe 4-36 is connected to the third water phase input pipe 4-27; the lower part of the obtuse-angle connecting pipe 4-32 gradually tilts downward and is connected to the third water phase output pipe 4-31; when the sixth rotating piston 4-35 rotates to the point where the sixth quantitative channel 4-33 is in a vertical position, the two ends of the sixth quantitative channel 4-33 are respectively connected to the lower end of the right-angle connecting pipe 4-36 and the upper end of the obtuse-angle connecting pipe 4-32.

[0010] The method for using the device for continuously preparing large-sized polymer spheres with controllable size of the present invention is as follows:

[0011] 1. Add tap water to the hot water circulation pump 5, turn on the heating switch for preheating, and set the circulation temperature to 82°C to 85°C; transfer the aqueous phase to the maturation tank 8, and then the maturation tank 8 is heated to 82°C to 85°C through the first hydrothermal tank 9 and then maintained at a constant temperature; transfer the organic phase to the prepolymerization tank 1, pass through the second hydrothermal tank 10 to heat it to 40°C to 60°C and then maintain a constant temperature, and prepolymerize the organic phase in the prepolymerization tank 1 for 40min to 45min; the density of the organic phase is greater than that of the aqueous phase;

[0012] 2. Turn on the circulation button of the hot water circulation pump 5, and hot water enters the water heating tank 7 and fills it; when the quantitative device 4 is the first structure, rotate the first rotary piston 4-9 so that the first quantitative channel 4-2 is in a horizontal position, that is, it is connected with the first organic phase input pipe 4-3 and the first organic phase output pipe 4-7; turn on the second pump 3 so that the water in the serpentine polymerization tube 6 flows from bottom to top, the purpose is to fill the serpentine polymerization tube 6 as soon as possible, and the aqueous phase enters the second aqueous phase delivery pipe 15 through the first bypass pipe 4-5. When the second aqueous phase delivery pipe 15 is full of aqueous phase, turn off the second pump 3; turn on the first pump 2, and turn off the first pump 2 after the organic phase liquid fills the first quantitative channel 4-2. The first rotary piston 4-9 is rotated 90° until the first metering channel 4-2 is connected to the first aqueous phase inlet pipe 4-4 and the first aqueous phase outlet pipe 4-8. The second pump 3 is turned on so that the water in the serpentine polymer tube 6 flows from top to bottom. The water flow rate is controlled by the second pump 3. The organic phase flows along the first aqueous phase outlet pipe 4-8 to the spherical tube 6-1 and coalesces into spherical droplets. The organic phase droplets slowly roll along the serpentine polymer tube 6 under the action of their own gravity and the flow of the aqueous phase. After 0.5 to 2.5 hours, the organic phase droplets are completely solidified and enter the maturation tank 8 from the serpentine polymer tube 6 for the maturation stage. After maturation in the maturation tank 8 for 2 to 2.5 hours, the SDB spheres are removed.

[0013] When the quantitative device 4 is the second structure, the second rotary piston 4-14 is rotated so that the second quantitative channel 4-13 is in a horizontal position, that is, it is connected to the second organic phase input pipe 4-12 and the second organic phase output pipe 4-10; the third rotary piston 4-18 is rotated so that the two opposite ends of the third quantitative channel 4-19 are in a vertical position, and the upper and lower ends of the third quantitative channel 4-19 are respectively connected to the lower part of the vertical connecting pipe 4-20 and the second aqueous phase output pipe 4-16; the fourth rotary piston 4-21 is rotated so that the fourth quantitative channel 4 -22 is in a vertical position, the upper and lower ends of the fourth metering channel 4-22 are respectively connected to the second aqueous phase input pipe 4-24 and the upper part of the vertical connecting pipe 4-20; the second pump 3 is turned on so that the water in the serpentine polymerization tube 6 flows from bottom to top, and the second pump 3 is turned off when the second aqueous phase delivery pipe 15 is filled with aqueous phase; the first pump 2 is turned on, and the first pump 2 is turned off after the organic phase liquid fills the second metering channel 4-13, and the second rotary piston 4-14 is rotated 90 degrees until the second metering channel 4-13 is connected to the top opening of the tee pipe 4-15; The fourth rotating piston 4-21 is rotated until the two opposite ends of the fourth quantitative channel 4-22 are in a horizontal position, the top opening of the fourth quantitative channel 4-22 is connected to the second water phase input pipe 4-24, and the horizontal end of the fourth quantitative channel 4-22 is connected to a horizontal opening of the three-way pipe 4-15; the third rotating piston 4-18 is rotated until the two opposite ends of the third quantitative channel 4-19 are in a horizontal position, the bottom opening of the third quantitative channel 4-19 is connected to the second water phase output pipe 4-16, and the horizontal end of the third quantitative channel 4-19 is connected to the three-way pipe 4-15. A horizontal opening of the through pipe 4-15 is connected; the second pump 3 is turned on so that the water in the serpentine polymerization tube 6 flows from top to bottom. The water flow rate is controlled by the second pump 3, and the organic phase flows along the second aqueous phase output pipe 4-16 to the spherical tube 6-1 to gather and form spherical droplets. The organic phase droplets slowly roll along the serpentine polymerization tube 6 under the action of their own gravity and the flow of the aqueous phase. In 0.5h to 2.5h, the organic phase droplets are completely solidified and enter the maturation tank 8 from the serpentine polymerization tube 6 for the maturation stage. After maturation in the maturation tank 8 for 2h to 2.5h, the SDB spheres are removed;

[0014] When the selected quantitative device 4 is the third structure, the fifth rotary piston 4-28 is rotated to rotate until the fifth quantitative channel 4-29 is in a vertical position, and the two ends of the fifth quantitative channel 4-29 are respectively connected to the third water phase input pipe 4-27 and the third water phase output pipe 4-31; the sixth rotary piston 4-35 is rotated to rotate until the sixth quantitative channel 4-33 is in a vertical position, and the two ends of the sixth quantitative channel 4-33 are respectively connected to the lower end of the right-angle connecting pipe 4-36 and the upper end of the obtuse-angle connecting pipe 4-32; the second pump 3 is turned on so that the water in the serpentine polymerization tube 6 flows from bottom to top, and the second pump 3 is closed when the second water phase delivery pipe 15 is full of water phase; the fifth rotary piston 4-28 is rotated to rotate until the fifth quantitative channel 4-29 is in a horizontal position, and the two ends of the fifth quantitative channel 4-29 are respectively connected to the third organic phase input pipe 4-25 and the third organic phase output pipe 4-26; the first pump 2 is turned on, and wait After the organic phase liquid fills the fifth metering channel 4-29, the first pump 2 is closed, and the fifth rotary piston 4-28 is rotated 90 degrees until the fifth metering channel 4-29 is connected to the third aqueous phase inlet pipe 4-27 and the third aqueous phase outlet pipe 4-31; the sixth rotary piston 4-35 is rotated until the sixth metering channel 4-33 is in a horizontal position, thereby stopping the flow of the sixth metering channel 4-33; the second pump 3 is turned on so that the water in the serpentine polymerization tube 6 flows from top to bottom. The water flow rate is controlled by the second pump 3, and the organic phase will flow along the third aqueous phase outlet pipe 4-31 to the spherical tube 6-1 to gather and form spherical droplets. The organic phase droplets slowly roll along the serpentine polymerization tube 6 under the action of their own gravity and the flow of the aqueous phase. In 0.5h to 2.5h, the organic phase droplets are completely solidified and enter the maturation tank 8 from the serpentine polymerization tube 6 for the maturation stage. After maturation in the maturation tank 8 for 2h to 2.5h, the SDB spheres are removed;

[0015] 3. The SDB spheres taken out from the maturation tank 8 are transferred to the extraction equipment, extracted with acetone for 18 to 19 hours, taken out and rinsed with anhydrous ethanol, and finally the SDB spheres are placed in an oven at 40 to 45 degrees Celsius for 5 to 6 hours to obtain large-sized SDB spheres with good sphericity.

[0016] The present invention discloses a device and method for continuously preparing large-sized polymer spheres with controllable size, wherein the quantitative device can be implemented in three ways (any one of the three is optional), wherein the quantitative channel has a certain volume; and the quantitative device ensures that the organic phase forms an uninterrupted continuous organic phase liquid column in the aqueous phase; the function of the spherical tube 6-1 is to provide a large-sized aqueous solution space so that the prepolymerized monomer can form spherical droplets here under the action of surface tension; the function of the serpentine polymerization tube 6 is to ensure that the spherical droplets can achieve sufficient polymerization reaction under the premise of ensuring that the shape does not change and the organic phase does not lose any By adding a density modifier to the organic phase, the density of the organic phase solution is made slightly greater than that of the aqueous solution, thereby ensuring that the spherical organic phase droplets do not float and can slowly sink in the static aqueous solution. Therefore, the speed or time of the spherical droplets moving from the top of the serpentine polymerization tube 6 to the bottom and entering the maturation tank 8 during the polymerization process is determined by the density difference between the organic phase and the aqueous phase, the flow rate of the aqueous phase, and the length of the serpentine polymerization tube 6. During the polymerization process, the hot water circulation pump 5 controls the polymerization temperature of the organic phase spherical droplets in the serpentine polymerization tube 6. The maturation tank 8 contains a surfactant aqueous solution of a certain concentration, which has stirring and temperature control functions.

[0017] In the present invention, a liquid separation device is further provided on the organic phase reflux pipe 11 between the prepolymerization tank 1 and the quantitative device 4 to separate the aqueous phase and the organic phase in the quantitative channel and return the organic phase to the prepolymerization tank 1 .

[0018] Compared with the prior art, the present invention has the following technical features:

[0019] 1. The present invention uses the method of adjusting the surface tension and density of the organic phase to form spherical droplets of fixed and controllable size in the aqueous phase, overcoming the disadvantage of droplet formation by strong mechanical stirring;

[0020] 2. The present invention can adjust the size of the polymer spheres by selecting quantitative channels of different volumes to fix the volume of the organic phase entering the aqueous phase according to needs, thereby realizing the preparation of large-sized polymer spheres;

[0021] 3. The present invention utilizes a water phase to partition the organic phase spherical droplets in the serpentine polymerization tube 6, thereby avoiding the disadvantage that the organic phase droplets are broken by mechanical stirring and the polymer product particles must be screened, thereby greatly improving the raw material utilization rate;

[0022] 4. The present invention utilizes a serpentine tube polymerization structure to allow the spherical droplets to move and complete polymerization within the serpentine polymerization tube 6, thereby achieving continuous preparation of polymer spheres. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 Schematic diagram of a device for continuously preparing large-sized polymer spheres with controllable size according to a first embodiment;

[0024] Figure 2 This is a schematic diagram of the first structure of the quantitative device 4 in the specific embodiment;

[0025] Figure 3 This is a first schematic diagram of the second structure of the quantitative device 4 in the specific embodiment 1;

[0026] Figure 4 This is a second schematic diagram of the second structure of the quantitative device 4 in the specific embodiment 1;

[0027] Figure 5 This is a first schematic diagram of the third structure of the quantitative device 4 in the specific embodiment 1;

[0028] Figure 6 This is a second schematic diagram of the third structure of the quantitative device 4 in the specific embodiment 1;

[0029] Figure 7 This is a third schematic diagram of the third structure of the quantitative device 4 in the first specific embodiment. DETAILED DESCRIPTION

[0030] Specific embodiment 1: This embodiment is a device for continuously preparing large-sized polymer balls with controllable size, such as Figure 1-Figure 7 As shown, it specifically consists of a prepolymerization tank 1, a first pump 2, a second pump 3, a dosing device 4, a hot water circulation pump 5, a serpentine polymerization pipe 6, a hydrothermal tank 7, a maturation tank 8, a first hydrothermal tank 9, a second hydrothermal tank 10, an organic phase reflux pipe 11, a second organic phase delivery pipe 12, a first aqueous phase delivery pipe 13, a polymerization delivery pipe 14, a second aqueous phase delivery pipe 15 and a first organic phase delivery pipe 16;

[0031] The water outlet of the prepolymerization tank 1 is connected to one end of the first pump 2 through the first organic phase delivery pipe 16, and the other end of the first pump 2 is connected to the organic phase input pipe of the quantitative device 4 through the second organic phase delivery pipe 12. The organic phase output pipe of the quantitative device 4 is refluxed to the prepolymerization tank 1 through the organic phase reflux pipe 11; the two ends of the hot water circulation pump 5 are respectively connected to the inlet and outlet of the hydrothermal tank 7; the serpentine polymerization pipe 6 is vertically arranged in the hydrothermal tank 7, and the lower end of the serpentine polymerization pipe 6 passes through the hydrothermal tank 7 and is connected to the maturation tank 8, and the serpentine A spherical tube 6-1 is provided on top of the shaped polymerization tube 6 and is connected to the spherical tube 6-1. The spherical tube 6-1 is disposed within the hydrothermal tank 7. The outlet of the maturation tank 8 is connected to one end of the second pump 3 via a second aqueous phase delivery pipe 15. The other end of the second pump 3 is connected to the aqueous phase input pipe of the metering device 4 via a first aqueous phase delivery pipe 13. The aqueous phase output pipe of the metering device 4 is connected to the spherical tube 6-1 via a polymerization delivery pipe 14. A first hydrothermal tank 9 is provided outside the maturation tank 8. A second hydrothermal tank 10 is provided outside the prepolymerization tank 1.

[0032] The quantitative device 4 has three structures, and you can choose one when using it. The specific structures are as follows:

[0033] like Figure 2 As shown, the first structure is composed of a first sleeve 4-1, a first organic phase input pipe 4-3, a first aqueous phase input pipe 4-4, a first bypass pipe 4-5, a second bypass pipe 4-6, a first organic phase output pipe 4-7, a first aqueous phase output pipe 4-8 and a first rotary piston 4-9; the first rotary piston 4-9 is provided with a first quantitative channel 4-2 of a straight pipe structure, and the first rotary piston 4-9 is provided in the first sleeve 4-1 and is in a sliding connection relationship; the upper end and the lower end of the first sleeve 4-1 are respectively connected to the first aqueous phase input pipe 4-4 and the first aqueous phase output pipe 4-8, and the horizontal ends of the first sleeve 4-1 are respectively connected to the first organic phase input pipe 4-3 and the first organic phase output pipe 4-7; when the first rotary piston 4-9 rotates to the first quantitative channel When 4-2 is in a horizontal position, the two ends of the first quantitative channel 4-2 are connected to the first organic phase input pipe 4-3 and the first organic phase output pipe 4-7 respectively; when the first rotating piston 4-9 rotates to the first quantitative channel 4-2 and is in a vertical position, the two ends of the first quantitative channel 4-2 are connected to the first aqueous phase input pipe 4-4 and the first aqueous phase output pipe 4-8 respectively; a second bypass pipe 4-6 is further provided between the first organic phase input pipe 4-3 and the first organic phase output pipe 4-7; a first bypass pipe 4-5 is further provided between the first aqueous phase input pipe 4-4 and the first aqueous phase output pipe 4-8; the first bypass pipe 4-5 and the second bypass pipe 4-6 ensure that the organic phase solution and the aqueous phase are always in a flowing state during the process of collecting and releasing the organic phase and rotating the piston through the quantitative channel;

[0034] like Figure 3 and 4As shown, the second structure is composed of a second organic phase output pipe 4-10, a second sleeve 4-11, a second organic phase input pipe 4-12, a second rotary piston 4-14, a three-way pipe 4-15, a second aqueous phase output pipe 4-16, a third sleeve 4-17, a third rotary piston 4-18, a vertical connecting pipe 4-20, a fourth rotary piston 4-21, a fourth sleeve 4-23 and a second aqueous phase input pipe 4-24; the three-way pipe 4-15 has three openings, one is located at the top and the opening is vertically upward, and the other two are located at the bottom and both open in the horizontal direction; the second quantitative channel 4-13 of the straight pipe structure is provided in the second rotary piston 4-14, and the second rotary piston 4-14 is provided in the second sleeve 4-11 and is a sliding dynamic connection relationship; the horizontal ends of the second sleeve 4-11 are respectively connected to the second organic phase input pipe 4-12 and the second organic phase output pipe 4-10; the lower end of the second sleeve 4-11 is connected to the top opening of the tee pipe 4-15, and the other two horizontal openings of the tee pipe 4-15 are respectively connected to the horizontal ends of the fourth sleeve 4-23 and the third sleeve 4-17; the fourth sleeve 4-23 is arranged directly above the third sleeve 4-17; when the second rotary piston 4-14 rotates to the second quantitative channel 4-13 is in a horizontal position, the two ends of the second quantitative channel 4-13 are respectively connected to the second organic phase input pipe 4-12 and the second organic phase output pipe 4-10; when the second rotary piston 4-14 rotates to the second quantitative channel 4-13 is in a horizontal position When in the vertical position, the lower end of the second quantitative channel 4-13 is communicated with the top opening of the tee pipe 4-15; the third quantitative channel 4-19 of T-shaped structure is provided in the third rotary piston 4-18, and the third rotary piston 4-18 is provided in the third sleeve 4-17 and is in a sliding connection relationship; the upper and lower ends of the third sleeve 4-17 are respectively communicated with the lower end of the vertical connecting pipe 4-20 and the second water phase output pipe 4-16; the horizontal end of the third sleeve 4-17 is communicated with a horizontal opening of the tee pipe 4-15; when the third rotary piston 4-18 rotates to the point where the opposite ends in the third quantitative channel 4-19 are in the vertical position, the upper and lower ends of the third quantitative channel 4-19 are respectively communicated with the lower end of the vertical connecting pipe 4-20 and the second water phase output pipe 4-16 The outlet pipe 4-16 is connected; when the third rotating piston 4-18 rotates to the point where the two opposite ends in the third quantitative channel 4-19 are in a horizontal position, the bottom opening of the third quantitative channel 4-19 is connected to the second water phase output pipe 4-16, and the horizontal end of the third quantitative channel 4-19 is connected to a horizontal opening of the three-way pipe 4-15; the fourth rotating piston 4-21 is provided with a fourth quantitative channel 4-22 of a T-shaped structure, and the fourth rotating piston 4-21 is arranged in a fourth sleeve 4-23 and is in a sliding connection relationship; the upper and lower ends of the fourth sleeve 4-23 are respectively connected to the second water phase input pipe 4-24 and the upper end of the vertical connecting pipe 4-20; the horizontal end of the fourth sleeve 4-23 is connected to a horizontal opening of the three-way pipe 4-15;When the fourth rotary piston 4-21 rotates until the opposite ends of the fourth metering channel 4-22 are in a vertical position, the upper and lower ends of the fourth metering channel 4-22 are respectively connected to the second water phase input pipe 4-24 and the upper part of the vertical connecting pipe 4-20; when the fourth rotary piston 4-21 rotates until the opposite ends of the fourth metering channel 4-22 are in a horizontal position, the top opening of the fourth metering channel 4-22 is connected to the second water phase input pipe 4-24, and the horizontal end of the fourth metering channel 4-22 is connected to a horizontal opening of the tee pipe 4-15;

[0035] like Figure 5-7 As shown, the third structure is composed of a third organic phase input pipe 4-25, a third organic phase output pipe 4-26, a third aqueous phase input pipe 4-27, a fifth rotary piston 4-28, a fifth sleeve 4-30, a third aqueous phase output pipe 4-31, an obtuse angle connecting pipe 4-32, a sixth sleeve 4-34, a sixth rotary piston 4-35 and a right angle connecting pipe 4-36; the fifth rotary piston 4-28 is provided with a fifth quantitative channel 4-29 of a straight pipe structure, and the fifth rotary piston 4-28 is provided with a The fifth sleeve 4-30 is in a sliding connection relationship; the upper end and the lower end of the fifth sleeve 4-30 are respectively connected to the third aqueous phase input pipe 4-27 and the third aqueous phase output pipe 4-31, and the horizontal ends of the first sleeve 4-1 are respectively connected to the third organic phase input pipe 4-25 and the third organic phase output pipe 4-26; when the fifth rotating piston 4-28 rotates to the fifth quantitative channel 4-29 is in a horizontal position, the two ends of the fifth quantitative channel 4-29 are respectively connected to the third organic phase input pipe 4-25 and the third organic phase output pipe. The machine phase output pipe 4-26 is connected; when the fifth rotating piston 4-28 rotates to the fifth quantitative channel 4-29 is in a vertical position, the two ends of the fifth quantitative channel 4-29 are respectively connected to the third water phase input pipe 4-27 and the third water phase output pipe 4-31; the sixth rotating piston 4-35 is provided with a sixth quantitative channel 4-33 of a straight pipe structure, and the sixth rotating piston 4-35 is provided in the sixth sleeve 4-34 and is in a sliding connection relationship; the upper end and the lower end of the sixth sleeve 4-34 are respectively connected to the straight pipe. The lower end of the right-angle connecting tube 4-36 is connected to the upper end of the obtuse-angle connecting tube 4-32, and the other end of the right-angle connecting tube 4-36 is connected to the third water phase input tube 4-27; the lower part of the obtuse-angle connecting tube 4-32 gradually tilts downward and is connected to the third water phase output tube 4-31; when the sixth rotating piston 4-35 rotates to the point where the sixth quantitative channel 4-33 is in a vertical position, the two ends of the sixth quantitative channel 4-33 are respectively connected to the lower end of the right-angle connecting tube 4-36 and the upper end of the obtuse-angle connecting tube 4-32.

[0036] Specific embodiment 2: This embodiment differs from specific embodiment 1 in that the volumes of the first quantitative channel 4-2, the second quantitative channel 4-13, and the fifth quantitative channel 4-29 are all 0.1 mL to 2 mL; the lengths of the three channels are all 10 mm to 20 mm, and the diameters are all 3.6 mm to 11.3 mm. Other aspects are the same as specific embodiment 1.

[0037] Specific embodiment 3: This embodiment differs from specific embodiment 1 or 2 in that the angle between the obtuse-angle connecting pipe 4 - 32 and the horizontal direction is 3° to 10°. Other aspects are the same as specific embodiment 1 or 2.

[0038] Specific embodiment 4: This embodiment differs from specific embodiments 1 to 3 in that the inner diameter of the spherical tube 6 - 1 is 10 mm to 25 mm. Other aspects are the same as specific embodiments 1 to 3.

[0039] Specific embodiment 5: This embodiment differs from specific embodiment 4 in that the inner diameter of the serpentine polymer tube 6 is 5 mm to 20 mm and is smaller than the inner diameter of the spherical tube 6-1; the height of the serpentine polymer tube 6 is 200 mm to 1000 mm, and the diameter of the tube coil of the serpentine polymer tube 6 is 100 mm to 1500 mm. Other aspects are the same as specific embodiment 4.

[0040] Specific embodiment 6: This embodiment differs from specific embodiment 5 in that a liquid separation device is further provided on the organic phase reflux pipe 11 between the prepolymerization tank 1 and the quantitative device 4 to separate the aqueous phase and the organic phase in the quantitative channel and then return the organic phase to the prepolymerization tank 1. Other aspects are the same as specific embodiment 5.

[0041] Specific embodiment 7: This embodiment differs from specific embodiment 6 in that the first pump 2 and the second pump 3 are both peristaltic pumps. Other aspects are the same as specific embodiment 6.

[0042] Specific embodiment eight: This embodiment is a method for using the device for continuously preparing large-sized polymer balls with controllable size according to specific embodiment one, specifically:

[0043] 1. Add tap water to the hot water circulation pump 5, turn on the heating switch for preheating, and set the circulation temperature to 82°C to 85°C; transfer the aqueous phase to the maturation tank 8, and then the maturation tank 8 is heated to 82°C to 85°C through the first hydrothermal tank 9 and then maintained at a constant temperature; transfer the organic phase to the prepolymerization tank 1, pass through the second hydrothermal tank 10 to heat it to 40°C to 60°C and then maintain a constant temperature, and prepolymerize the organic phase in the prepolymerization tank 1 for 40min to 45min; the density of the organic phase is greater than that of the aqueous phase;

[0044] 2. Turn on the circulation button of the hot water circulation pump 5, and hot water enters the water heating tank 7 and fills it; when the quantitative device 4 is the first structure, rotate the first rotary piston 4-9 so that the first quantitative channel 4-2 is in a horizontal position, that is, it is connected with the first organic phase input pipe 4-3 and the first organic phase output pipe 4-7; turn on the second pump 3 so that the water in the serpentine polymerization tube 6 flows from bottom to top, and the aqueous phase enters the second aqueous phase delivery pipe 15 through the first bypass pipe 4-5. When the second aqueous phase delivery pipe 15 is full of aqueous phase, turn off the second pump 3; turn on the first pump 2, and wait until the organic phase liquid fills the first quantitative channel 4-2, turn off the first pump 2, and rotate the first rotary piston 4-9. Plug 4-9 is rotated 90 degrees until the first metering channel 4-2 is connected to the first aqueous phase inlet pipe 4-4 and the first aqueous phase outlet pipe 4-8. The second pump 3 is turned on so that the water in the serpentine polymer tube 6 flows from top to bottom. The water flow rate is controlled by the second pump 3. The organic phase flows along the first aqueous phase outlet pipe 4-8 to the spherical tube 6-1 and coalesces into spherical droplets. The organic phase droplets slowly roll along the serpentine polymer tube 6 under the action of their own gravity and the flow of the aqueous phase. After 0.5 to 2.5 hours, the organic phase droplets are completely solidified and enter the maturation tank 8 for the maturation stage. After maturation in the maturation tank 8 for 2 to 2.5 hours, the SDB spheres are removed.

[0045] When the quantitative device 4 is the second structure, the second rotary piston 4-14 is rotated so that the second quantitative channel 4-13 is in a horizontal position, that is, it is connected to the second organic phase input pipe 4-12 and the second organic phase output pipe 4-10; the third rotary piston 4-18 is rotated so that the two opposite ends of the third quantitative channel 4-19 are in a vertical position, and the upper and lower ends of the third quantitative channel 4-19 are respectively connected to the lower part of the vertical connecting pipe 4-20 and the second aqueous phase output pipe 4-16; the fourth rotary piston 4-21 is rotated so that the fourth quantitative channel 4 -22 is in a vertical position, the upper and lower ends of the fourth metering channel 4-22 are respectively connected to the second aqueous phase input pipe 4-24 and the upper part of the vertical connecting pipe 4-20; the second pump 3 is turned on so that the water in the serpentine polymerization tube 6 flows from bottom to top, and the second pump 3 is turned off when the second aqueous phase delivery pipe 15 is filled with aqueous phase; the first pump 2 is turned on, and the first pump 2 is turned off after the organic phase liquid fills the second metering channel 4-13, and the second rotary piston 4-14 is rotated 90 degrees until the second metering channel 4-13 is connected to the top opening of the tee pipe 4-15; The fourth rotating piston 4-21 is rotated until the two opposite ends of the fourth quantitative channel 4-22 are in a horizontal position, the top opening of the fourth quantitative channel 4-22 is connected to the second water phase input pipe 4-24, and the horizontal end of the fourth quantitative channel 4-22 is connected to a horizontal opening of the three-way pipe 4-15; the third rotating piston 4-18 is rotated until the two opposite ends of the third quantitative channel 4-19 are in a horizontal position, the bottom opening of the third quantitative channel 4-19 is connected to the second water phase output pipe 4-16, and the horizontal end of the third quantitative channel 4-19 is connected to the three-way pipe 4-15. A horizontal opening of the through pipe 4-15 is connected; the second pump 3 is turned on so that the water in the serpentine polymerization tube 6 flows from top to bottom. The water flow rate is controlled by the second pump 3, and the organic phase flows along the second aqueous phase output pipe 4-16 to the spherical tube 6-1 to gather and form spherical droplets. The organic phase droplets slowly roll along the serpentine polymerization tube 6 under the action of their own gravity and the flow of the aqueous phase. In 0.5h to 2.5h, the organic phase droplets are completely solidified and enter the maturation tank 8 from the serpentine polymerization tube 6 for the maturation stage. After maturation in the maturation tank 8 for 2h to 2.5h, the SDB spheres are removed;

[0046] When the selected quantitative device 4 is the third structure, the fifth rotary piston 4-28 is rotated to rotate until the fifth quantitative channel 4-29 is in a vertical position, and the two ends of the fifth quantitative channel 4-29 are respectively connected to the third aqueous phase input pipe 4-27 and the third aqueous phase output pipe 4-31; the sixth rotary piston 4-35 is rotated to rotate until the sixth quantitative channel 4-33 is in a vertical position, and the two ends of the sixth quantitative channel 4-33 are respectively connected to the lower end of the right-angle connecting pipe 4-36 and the upper end of the obtuse-angle connecting pipe 4-32; the second pump 3 is turned on so that the water in the serpentine polymerization tube 6 flows from bottom to top, and the second pump 3 is turned off when the second aqueous phase delivery pipe 15 is full of aqueous phase; the fifth rotary piston 4-28 is rotated to rotate until the fifth quantitative channel 4-29 is in a horizontal position, and the two ends of the fifth quantitative channel 4-29 are respectively connected to the third organic phase input pipe 4-25 and the third organic phase output pipe 4-26; the first pump 2 is turned on, After the organic phase liquid fills the fifth quantitative channel 4-29, the first pump 2 is closed, and the fifth rotary piston 4-28 is rotated 90 degrees until the fifth quantitative channel 4-29 is connected to the third aqueous phase inlet pipe 4-27 and the third aqueous phase outlet pipe 4-31; the sixth rotary piston 4-35 is rotated until the sixth quantitative channel 4-33 is in a horizontal position, thereby stopping the flow of the sixth quantitative channel 4-33; the second pump 3 is turned on so that the water in the serpentine polymerization tube 6 flows from top to bottom. The water flow rate is controlled by the second pump 3, and the organic phase will flow along the third aqueous phase outlet pipe 4-31 to the spherical tube 6-1 to gather and form spherical droplets. The organic phase droplets slowly roll along the serpentine polymerization tube 6 under the action of their own gravity and the flow of the aqueous phase. In 0.5h to 2.5h, the organic phase droplets are completely solidified and enter the maturation tank 8 from the serpentine polymerization tube 6 for the maturation stage. After maturation in the maturation tank 8 for 2h to 4h, the SDB spheres are removed;

[0047] 3. The SDB spheres taken out from the maturation tank 8 are transferred to the extraction equipment, extracted with acetone for 18 to 19 hours, taken out and rinsed with anhydrous ethanol, and finally the SDB spheres are placed in an oven at 40 to 45 degrees Celsius for 5 to 6 hours to obtain large-sized SDB spheres with good sphericity.

[0048] The present invention is verified by the following test:

[0049] Experiment 1: This experiment is a device that can continuously prepare large-sized polymer balls with controllable size, such as Figure 1-Figure 7 As shown, it specifically consists of a prepolymerization tank 1, a first pump 2, a second pump 3, a dosing device 4, a hot water circulation pump 5, a serpentine polymerization pipe 6, a hydrothermal tank 7, a maturation tank 8, a first hydrothermal tank 9, a second hydrothermal tank 10, an organic phase reflux pipe 11, a second organic phase delivery pipe 12, a first aqueous phase delivery pipe 13, a polymerization delivery pipe 14, a second aqueous phase delivery pipe 15 and a first organic phase delivery pipe 16;

[0050] The water outlet of the prepolymerization tank 1 is connected to one end of the first pump 2 through the first organic phase delivery pipe 16, and the other end of the first pump 2 is connected to the organic phase input pipe of the quantitative device 4 through the second organic phase delivery pipe 12. The organic phase output pipe of the quantitative device 4 is refluxed to the prepolymerization tank 1 through the organic phase reflux pipe 11; the two ends of the hot water circulation pump 5 are respectively connected to the inlet and outlet of the hydrothermal tank 7; the serpentine polymerization pipe 6 is vertically arranged in the hydrothermal tank 7, and the lower end of the serpentine polymerization pipe 6 passes through the hydrothermal tank 7 and is connected to the maturation tank 8, and the serpentine A spherical tube 6-1 is provided on top of the shaped polymerization tube 6 and is connected to the spherical tube 6-1. The spherical tube 6-1 is disposed within the hydrothermal tank 7. The outlet of the maturation tank 8 is connected to one end of the second pump 3 via a second aqueous phase delivery pipe 15. The other end of the second pump 3 is connected to the aqueous phase input pipe of the metering device 4 via a first aqueous phase delivery pipe 13. The aqueous phase output pipe of the metering device 4 is connected to the spherical tube 6-1 via a polymerization delivery pipe 14. A first hydrothermal tank 9 is provided outside the maturation tank 8. A second hydrothermal tank 10 is provided outside the prepolymerization tank 1.

[0051] The quantitative device 4 has three structures, and you can choose one when using it. The specific structures are as follows:

[0052] The first structure is composed of a first sleeve 4-1, a first organic phase input pipe 4-3, a first aqueous phase input pipe 4-4, a first bypass pipe 4-5, a second bypass pipe 4-6, a first organic phase output pipe 4-7, a first aqueous phase output pipe 4-8 and a first rotary piston 4-9; the first rotary piston 4-9 is provided with a first quantitative channel 4-2 of a straight pipe structure, and the first rotary piston 4-9 is arranged in the first sleeve 4-1 and is in a sliding connection relationship; the upper end and the lower end of the first sleeve 4-1 are respectively connected to the first aqueous phase input pipe 4-4 and the first aqueous phase output pipe 4-8, and the horizontal ends of the first sleeve 4-1 are respectively connected to the first organic phase input pipe 4-3 and the first organic phase output pipe 4-7; when the first rotary piston 4-9 rotates to the first quantitative channel 4-2, the first rotary piston 4-9 is provided with a first quantitative channel 4-2 of a straight pipe structure, and the first rotary piston 4-9 is arranged in the first sleeve 4-1 and is in a sliding connection relationship; the upper end and the lower end of the first sleeve 4-1 are respectively connected to the first aqueous phase input pipe 4-4 and the first aqueous phase output pipe 4-8, and the horizontal ends of the first sleeve 4-1 are respectively connected to the first organic phase input pipe 4-3 and the first organic phase output pipe 4-7; 2 is in a horizontal position, the two ends of the first quantitative channel 4-2 are connected to the first organic phase input pipe 4-3 and the first organic phase output pipe 4-7 respectively; when the first rotating piston 4-9 rotates to the first quantitative channel 4-2 is in a vertical position, the two ends of the first quantitative channel 4-2 are connected to the first aqueous phase input pipe 4-4 and the first aqueous phase output pipe 4-8 respectively; a second bypass pipe 4-6 is further provided between the first organic phase input pipe 4-3 and the first organic phase output pipe 4-7; a first bypass pipe 4-5 is further provided between the first aqueous phase input pipe 4-4 and the first aqueous phase output pipe 4-8; the first bypass pipe 4-5 and the second bypass pipe 4-6 ensure that the organic phase solution and the aqueous phase are always in a flowing state during the process of collecting and releasing the organic phase and rotating the piston through the quantitative channel;

[0053] The second structure is composed of a second organic phase output pipe 4-10, a second sleeve 4-11, a second organic phase input pipe 4-12, a second rotary piston 4-14, a three-way pipe 4-15, a second aqueous phase output pipe 4-16, a third sleeve 4-17, a third rotary piston 4-18, a vertical connecting pipe 4-20, a fourth rotary piston 4-21, a fourth sleeve 4-23 and a second aqueous phase input pipe 4-24; the three-way pipe 4-15 has three openings, one is located at the top and opens vertically upward, and the other two are located at the bottom and open horizontally; the second quantitative channel 4-13 of a straight pipe structure is provided in the second rotary piston 4-14, and the second rotary piston 4-14 is provided in the second sleeve 4-11 and is connected for sliding. connection relationship; the horizontal ends of the second sleeve 4-11 are respectively connected to the second organic phase input pipe 4-12 and the second organic phase output pipe 4-10; the lower end of the second sleeve 4-11 is connected to the top opening of the tee pipe 4-15, and the other two horizontal openings of the tee pipe 4-15 are respectively connected to the horizontal ends of the fourth sleeve 4-23 and the third sleeve 4-17; the fourth sleeve 4-23 is arranged directly above the third sleeve 4-17; when the second rotary piston 4-14 rotates to the second quantitative channel 4-13 is in a horizontal position, the two ends of the second quantitative channel 4-13 are respectively connected to the second organic phase input pipe 4-12 and the second organic phase output pipe 4-10; when the second rotary piston 4-14 rotates to the second quantitative channel 4-13 is in a vertical position When the third rotary piston 4-18 is in the vertical position, the lower end of the second quantitative channel 4-13 is connected to the top opening of the three-way pipe 4-15; a third quantitative channel 4-19 of T-shaped structure is provided in the third rotary piston 4-18, and the third rotary piston 4-18 is provided in the third sleeve 4-17 and is in a sliding connection relationship; the upper and lower ends of the third sleeve 4-17 are respectively connected to the lower end of the vertical connecting pipe 4-20 and the second water phase output pipe 4-16; the horizontal end of the third sleeve 4-17 is connected to a horizontal opening of the three-way pipe 4-15; when the third rotary piston 4-18 rotates to the opposite ends in the third quantitative channel 4-19 and is in a vertical position, the upper and lower ends of the third quantitative channel 4-19 are respectively connected to the lower part of the vertical connecting pipe 4-20 and the second water phase output pipe The third rotary piston 4-18 is connected to the third quantitative channel 4-19; when the third rotary piston 4-18 rotates to the point where the two opposite ends of the third quantitative channel 4-19 are in a horizontal position, the bottom opening of the third quantitative channel 4-19 is connected to the second water phase output pipe 4-16, and the horizontal end of the third quantitative channel 4-19 is connected to a horizontal opening of the three-way pipe 4-15; the fourth rotary piston 4-21 is provided with a fourth quantitative channel 4-22 of a T-shaped structure, and the fourth rotary piston 4-21 is arranged in a fourth sleeve 4-23 and is in a sliding connection relationship; the upper and lower ends of the fourth sleeve 4-23 are respectively connected to the second water phase input pipe 4-24 and the upper end of the vertical connecting pipe 4-20; the horizontal end of the fourth sleeve 4-23 is connected to a horizontal opening of the three-way pipe 4-15;When the fourth rotary piston 4-21 rotates until the opposite ends of the fourth metering channel 4-22 are in a vertical position, the upper and lower ends of the fourth metering channel 4-22 are respectively connected to the second water phase input pipe 4-24 and the upper part of the vertical connecting pipe 4-20; when the fourth rotary piston 4-21 rotates until the opposite ends of the fourth metering channel 4-22 are in a horizontal position, the top opening of the fourth metering channel 4-22 is connected to the second water phase input pipe 4-24, and the horizontal end of the fourth metering channel 4-22 is connected to a horizontal opening of the tee pipe 4-15;

[0054] The third structure is composed of a third organic phase input pipe 4-25, a third organic phase output pipe 4-26, a third aqueous phase input pipe 4-27, a fifth rotary piston 4-28, a fifth sleeve 4-30, a third aqueous phase output pipe 4-31, an obtuse angle connecting pipe 4-32, a sixth sleeve 4-34, a sixth rotary piston 4-35 and a right angle connecting pipe 4-36; a fifth quantitative channel 4-29 of a straight pipe structure is provided in the fifth rotary piston 4-28, and the fifth rotary piston 4-28 is provided in the fifth The upper end and lower end of the fifth sleeve 4-30 are connected to the third aqueous phase input pipe 4-27 and the third aqueous phase output pipe 4-31 respectively, and the horizontal ends of the first sleeve 4-1 are connected to the third organic phase input pipe 4-25 and the third organic phase output pipe 4-26 respectively; when the fifth rotating piston 4-28 rotates to the fifth quantitative channel 4-29 in a horizontal position, the ends of the fifth quantitative channel 4-29 are connected to the third organic phase input pipe 4-25 and the third organic phase output pipe 4-26 respectively. The first and second water phase output pipes 4-26 are connected; when the fifth rotating piston 4-28 rotates to the fifth quantitative channel 4-29 in a vertical position, the two ends of the fifth quantitative channel 4-29 are respectively connected to the third water phase input pipe 4-27 and the third water phase output pipe 4-31; the sixth rotating piston 4-35 is provided with a sixth quantitative channel 4-33 of a straight pipe structure, and the sixth rotating piston 4-35 is provided in a sixth sleeve 4-34 and is in a sliding connection relationship; the upper end and the lower end of the sixth sleeve 4-34 are respectively at right angles to each other. The lower end of the connecting pipe 4-36 is connected to the upper end of the obtuse-angle connecting pipe 4-32, and the other end of the right-angle connecting pipe 4-36 is connected to the third water phase input pipe 4-27; the lower part of the obtuse-angle connecting pipe 4-32 gradually tilts downward and is connected to the third water phase output pipe 4-31; when the sixth rotating piston 4-35 rotates to the point where the sixth quantitative channel 4-33 is in a vertical position, the two ends of the sixth quantitative channel 4-33 are respectively connected to the lower end of the right-angle connecting pipe 4-36 and the upper end of the obtuse-angle connecting pipe 4-32.

[0055] The volume of the first quantitative channel 4-2, the second quantitative channel 4-13 and the fifth quantitative channel 4-29 are all 0.5 mL; the length of the three channels is 10 mm and the diameter is 10 mm;

[0056] The inner diameter of the spherical tube 6-1 is 20 mm;

[0057] The inner diameter of the serpentine polymer tube 6 is 15 mm; the height of the serpentine polymer tube 6 is 500 mm, and the diameter of the tube coil of the serpentine polymer tube 6 is 800 mm;

[0058] On the organic phase reflux pipe 11, a liquid separation device is also provided between the prepolymerization tank 1 and the quantitative device 4 to separate the aqueous phase and the organic phase in the quantitative channel, and then return the organic phase to the prepolymerization tank 1;

[0059] The first pump 2 and the second pump 3 are both peristaltic pumps.

[0060] Experiment 2: This experiment is a method for using the device for continuously preparing large-sized polymer spheres with controllable size in Experiment 1, specifically:

[0061] 1. Taking the continuous preparation of large-sized SDB thermosetting polymer spheres as an example, 3 g of styrene, 3 g of divinylbenzene, 0.15 g of benzoyl peroxide, 6 g of p-dichlorobenzene (which acts as a density regulator to make the density of the organic phase greater than that of the aqueous phase), 3 g of toluene, and 0.225 g of sorbitan oleate were added to the same beaker and fully dissolved and mixed until the mixture was clear. The organic phase was prepared and the density of the organic phase was 1.02 g / cm 3 ;

[0062] Take 10g of perfluorooctanoic acid and 5L of distilled water, stir the perfluorooctanoic acid until it is completely dissolved, and the aqueous phase is prepared. The density of the aqueous phase is 1g / cm 3 ;

[0063] 2. Add tap water to the hot water circulation pump 5, turn on the heating switch for preheating, and set the circulation temperature to 82°C; transfer the aqueous phase to the maturation tank 8, and then the maturation tank 8 is heated to 82°C through the first hydrothermal tank 9 and then maintained at a constant temperature; transfer the organic phase to the prepolymerization tank 1, pass through the second hydrothermal tank 10 to heat to 50°C and then maintain a constant temperature, and prepolymerize the organic phase in the prepolymerization tank 1 for 40 minutes;

[0064] 3. Turn on the circulation button of the hot water circulation pump 5, and hot water enters the water heating tank 7 and fills it;

[0065] like Figure 3As shown, the selected quantitative device 4 is of the second structure. The second rotary piston 4-14 is rotated to make the second quantitative channel 4-13 in a horizontal position, that is, connected with the second organic phase input pipe 4-12 and the second organic phase output pipe 4-10; the third rotary piston 4-18 is rotated to rotate until the two opposite ends of the third quantitative channel 4-19 are in a vertical position, and the upper and lower ends of the third quantitative channel 4-19 are respectively connected with the lower part of the vertical connecting pipe 4-20 and the second aqueous phase output pipe 4-16; the fourth rotary piston 4-21 is rotated to rotate until the fourth quantitative channel 4- When the two opposite ends of 22 are in a vertical position, the upper and lower ends of the fourth quantitative channel 4-22 are respectively connected to the second water phase input pipe 4-24 and the upper part of the vertical connecting pipe 4-20; the second pump 3 is turned on so that the water in the serpentine polymerization tube 6 flows from bottom to top, and the second pump 3 is turned off when the second water phase delivery pipe 15 is filled with water phase; the first pump 2 is turned on, and the first pump 2 is turned off after the organic phase liquid fills the second quantitative channel 4-13, and the second rotary piston 4-14 is rotated 90 degrees until the second quantitative channel 4-13 is connected to the top opening of the tee pipe 4-15 (as shown in FIG. Figure 4 The fourth rotating piston 4-21 is rotated until the two opposite ends of the fourth quantitative channel 4-22 are in a horizontal position, the top opening of the fourth quantitative channel 4-22 is connected to the second water phase input pipe 4-24, and the horizontal end of the fourth quantitative channel 4-22 is connected to a horizontal opening of the three-way pipe 4-15; the third rotating piston 4-18 is rotated until the two opposite ends of the third quantitative channel 4-19 are in a horizontal position, the bottom opening of the third quantitative channel 4-19 is connected to the second water phase output pipe 4-16, and the third quantitative channel 4-19 is connected to the horizontal opening of the three-way pipe 4-15. One horizontal end is connected to a horizontal opening of the tee pipe 4-15; the second pump 3 is turned on so that the water in the serpentine polymerization tube 6 flows from top to bottom. The water flow rate is controlled by the second pump 3, and the organic phase flows along the second aqueous phase output pipe 4-16 to the spherical tube 6-1 to coalesce into spherical droplets. The organic phase droplets slowly roll along the serpentine polymerization tube 6 under the action of their own gravity and the flow of the aqueous phase. After 40 minutes, the organic phase droplets are completely solidified and enter the maturation tank 8 from the serpentine polymerization tube 6 for the maturation stage. After maturation in the maturation tank 8 for 2 hours, the SDB spheres are removed;

[0066] 4. The SDB spheres taken out from the maturation tank 8 were transferred to the extraction equipment, extracted with acetone for 18 hours, taken out and rinsed with anhydrous ethanol, and finally the SDB spheres were placed in a 40°C oven to dry for 5 hours to obtain large-sized SDB spheres with good sphericity. The diameter of the SDB spheres was about 6 mm.

[0067] Experiment 3: This experiment is a method for using the device for continuously preparing large-sized polymer spheres with controllable size in Experiment 1, specifically:

[0068] 1. Taking the continuous preparation of large-sized SDB thermosetting polymer spheres as an example, 2.4 g of styrene, 3.6 g of divinylbenzene, 0.12 g of benzoyl peroxide, 6 g of p-dichlorobenzene, 3 g of toluene, and 0.225 g of sorbitan oleate were added to the same beaker. The beaker was placed in an ultrasonic cleaner and ultrasonicated for 20 minutes. The solution was mixed until it was clear, and the organic phase was prepared.

[0069] Take 10g of perfluorooctanoic acid and 5L of distilled water, stir until the perfluorooctanoic acid is completely dissolved, and the aqueous phase is prepared;

[0070] 2. Add tap water to the hot water circulation pump 5, turn on the heating switch for preheating, and set the circulation temperature to 82°C; transfer the aqueous phase to the maturation tank 8, and then the maturation tank 8 is heated to 82°C through the first hydrothermal tank 9 and then maintained at a constant temperature; transfer the organic phase to the prepolymerization tank 1, pass through the second hydrothermal tank 10 to heat to 50°C and then maintain a constant temperature, and prepolymerize the organic phase in the prepolymerization tank 1 for 40 minutes;

[0071] 3. Turn on the circulation button of the hot water circulation pump 5, and hot water enters the water heating tank 7 and fills it;

[0072] like Figure 4 As shown, when the quantitative device 4 is the first structure, the first rotary piston 4-9 is rotated so that the first quantitative channel 4-2 is in a horizontal position, that is, it is connected to the first organic phase input pipe 4-3 and the first organic phase output pipe 4-7; the second pump 3 is turned on so that the water in the serpentine polymerization tube 6 flows from bottom to top, and the aqueous phase enters the second aqueous phase delivery pipe 15 through the first bypass pipe 4-5. When the second aqueous phase delivery pipe 15 is filled with aqueous phase, the second pump 3 is turned off; the first pump 2 is turned on, and the organic phase liquid is turned off after filling the first quantitative channel 4-2, and the first rotary piston 4-9 is rotated 90 degrees. The first quantitative channel 4-2 is connected to the first aqueous phase inlet pipe 4-4 and the first aqueous phase outlet pipe 4-8; the second pump 3 is turned on so that the water in the serpentine polymer tube 6 flows from top to bottom. The water flow rate is controlled by the second pump 3, and the organic phase flows along the first aqueous phase outlet pipe 4-8 to the spherical tube 6-1 to coalesce into spherical droplets. The organic phase droplets slowly roll along the serpentine polymer tube 6 under the action of their own gravity and the flow of the aqueous phase. After 40 minutes, the organic phase droplets are completely solidified and enter the maturation tank 8 from the serpentine polymer tube 6 for the maturation stage. After maturation in the maturation tank 8 for 4 hours, the SDB spheres are removed;

[0073] 4. The SDB spheres taken out from the maturation tank 8 were transferred to the extraction equipment, extracted with acetone for 18 hours, taken out and rinsed with anhydrous ethanol, and finally dried in a 40°C oven for 5 hours to obtain large-sized SDB spheres with good sphericity.

[0074] Experiment 4: This experiment is a method for using the device for continuously preparing large-sized polymer spheres with controllable size in Experiment 1, specifically:

[0075] 1. Taking the continuous preparation of large-sized SDB thermosetting polymer spheres as an example, 2 g of styrene, 4 g of divinylbenzene, 0.1 g of benzoyl peroxide, 6 g of p-dichlorobenzene, 3 g of toluene, and 0.225 g of sorbitan oleate were added to the same beaker. The beaker was placed in an ultrasonic cleaner and ultrasonicated for 20 minutes. The solution was mixed until it was clear, and the organic phase was prepared.

[0076] Take 10g of perfluorooctanoic acid and 5L of distilled water, stir until the perfluorooctanoic acid is completely dissolved, and the aqueous phase is prepared;

[0077] 2. Add tap water to the hot water circulation pump 5, turn on the heating switch for preheating, and set the circulation temperature to 82°C; transfer the aqueous phase to the maturation tank 8, and then the maturation tank 8 is heated to 82°C through the first hydrothermal tank 9 and then maintained at a constant temperature; transfer the organic phase to the prepolymerization tank 1, pass through the second hydrothermal tank 10 to heat to 50°C and then maintain a constant temperature, and prepolymerize the organic phase in the prepolymerization tank 1 for 40 minutes;

[0078] 3. Turn on the circulation button of the hot water circulation pump 5, and hot water enters the water heating tank 7 and fills it;

[0079] like Figure 5 As shown, the selected quantitative device 4 is a third structure, the fifth rotary piston 4-28 is rotated until the fifth quantitative channel 4-29 is in a vertical position, and the two ends of the fifth quantitative channel 4-29 are respectively connected to the third water phase input pipe 4-27 and the third water phase output pipe 4-31; the sixth rotary piston 4-35 is rotated until the sixth quantitative channel 4-33 is in a vertical position, and the two ends of the sixth quantitative channel 4-33 are respectively connected to the lower end of the right-angle connecting pipe 4-36 and the upper end of the obtuse-angle connecting pipe 4-32; the second pump 3 is turned on so that the water in the serpentine polymer tube 6 flows from bottom to top, and the second pump 3 is turned off when the second water phase delivery pipe 15 is filled with water phase; Figure 6 As shown, the fifth rotating piston 4-28 is rotated until the fifth quantitative channel 4-29 is in a horizontal position, and both ends of the fifth quantitative channel 4-29 are connected to the third organic phase input pipe 4-25 and the third organic phase output pipe 4-26 respectively; the first pump 2 is turned on, and the first pump 2 is turned off after the organic phase liquid fills the fifth quantitative channel 4-29; Figure 7As shown, the fifth rotary piston 4-28 is rotated 90 degrees until the fifth quantitative channel 4-29 is connected to the third water phase input pipe 4-27 and the third water phase output pipe 4-31; the sixth rotary piston 4-35 is rotated until the sixth quantitative channel 4-33 is in a horizontal position, that is, the flow of the sixth quantitative channel 4-33 is stopped; the second pump 3 switch is turned on so that the water in the serpentine polymerization tube 6 flows from top to bottom, and the water flow rate is controlled by the second pump 3. The organic phase will flow along the third water phase output pipe 4-31 to the spherical tube 6-1 and gather into spherical droplets. The organic phase droplets slowly roll along the serpentine polymerization tube 6 under the action of their own gravity and the flow of the water phase. In 40 minutes, the organic phase droplets are completely solidified and enter the maturation tank 8 from the serpentine polymerization tube 6 for the maturation stage. After maturation for 4 hours in the maturation tank 8, the SDB spheres are taken out; the sixth quantitative channel 4-33 acts as a bypass;

[0080] 4. The SDB spheres taken out from the maturation tank 8 were transferred to the extraction equipment, extracted with acetone for 18 hours, taken out and rinsed with anhydrous ethanol, and finally dried in a 40°C oven for 5 hours to obtain large-sized SDB spheres with good sphericity.

[0081] Experiments 5-7 were the same as Experiment 1 except that the amounts of benzoyl peroxide added in Step 1 were 0.225 g, 0.3 g, and 0.45 g, respectively.

[0082] Experiments 8-10 were the same as Experiment 1 except that the amounts of sorbitan oleate added in Step 1 were 0.15 g, 0.3 g, and 0.45 g, respectively.

[0083] Tests 11-13 were the same as Test 1 except that the circulation temperature and maturation tank temperature in step 2 were set to 75°C, 78°C, and 80°C.

[0084] Tests 14-16 were the same as in Example 1 except that the samples were matured in the maturation tank for 2.5 h, 3 h, and 4 h in step 3.

[0085] Table 1 shows the BET specific surface area, pore size, wetting angle and compressive strength data of the SDB carrier products of experiments 2-15.

[0086]

[0087]

[0088] The data in Table 1 demonstrate that the present invention can produce a hydrophobic SDB carrier with excellent performance. The carrier's performance is related to the ratio of the carrier to the stock solution, the curing temperature, and the curing time. This invention is applicable not only to the production of SDB carriers but also to the production of other large-scale spherical thermosetting polymers.

[0089] During operation, the time the organic phase stays in the serpentine polymerization tube 6 can be changed by adjusting the speed and direction of the second pump 3. This time needs to be determined according to the solidification time of the organic phase. The speed and direction of the second pump 3 can be adjusted at any time while waiting for solidification, as long as the organic phase is ensured to complete solidification in the serpentine polymerization tube 6.

Claims

1. A device for continuously preparing large-sized polymer balls with controllable size, characterized in that The device for continuously preparing large-sized polymer spheres with controllable size comprises a prepolymerization tank (1), a first pump (2), a second pump (3), a metering device (4), a hot water circulation pump (5), a serpentine polymerization pipe (6), a hydrothermal tank (7), a maturation tank (8), a first hydrothermal tank (9), a second hydrothermal tank (10), an organic phase reflux pipe (11), a second organic phase delivery pipe (12), a first aqueous phase delivery pipe (13), a polymerization delivery pipe (14), a second aqueous phase delivery pipe (15) and a first organic phase delivery pipe (16); The water outlet of the prepolymerization tank (1) is connected to one end of the first pump (2) through the first organic phase delivery pipe (16), and the other end of the first pump (2) is connected to the organic phase input pipe of the quantitative device (4) through the second organic phase delivery pipe (12), and the organic phase output pipe of the quantitative device (4) is refluxed to the prepolymerization tank (1) through the organic phase reflux pipe (11); the two ends of the hot water circulation pump (5) are respectively connected to the inlet and outlet of the hydrothermal tank (7); the serpentine polymerization pipe (6) is vertically arranged in the hydrothermal tank (7), and the lower end of the serpentine polymerization pipe (6) passes through the hydrothermal tank (7) and is connected to the maturation tank (8), and the serpentine polymerization pipe (6) is connected to the slaking tank (8). A spherical tube (6-1) is provided on the top of the combining pipe (6) and is in communication with the spherical tube (6-1), and the spherical tube (6-1) is provided in the hydrothermal tank (7); the outlet of the maturation tank (8) is in communication with one end of the second pump (3) through the second water phase delivery pipe (15), the other end of the second pump (3) is in communication with the water phase input pipe of the quantitative device (4) through the first water phase delivery pipe (13), and the water phase output pipe of the quantitative device (4) is connected to the spherical tube (6-1) through the polymerization delivery pipe (14); a first hydrothermal pool (9) is provided outside the maturation tank (8); and a second hydrothermal pool (10) is provided outside the prepolymerization tank (1); The quantitative device (4) has three structures, and you can choose one when using it. The specific structures are as follows: The first structure is composed of a first sleeve (4-1), a first organic phase input pipe (4-3), a first aqueous phase input pipe (4-4), a first bypass pipe (4-5), a second bypass pipe (4-6), a first organic phase output pipe (4-7), a first aqueous phase output pipe (4-8) and a first rotary piston (4-9); a first quantitative channel (4-2) of a straight pipe structure is provided in the first rotary piston (4-9), and the first rotary piston (4-9) is provided in the first sleeve (4-1) and is in a sliding connection relationship; the upper end and the lower end of the first sleeve (4-1) are respectively communicated with the first aqueous phase input pipe (4-4) and the first aqueous phase output pipe (4-8), and the horizontal ends of the first sleeve (4-1) are respectively communicated with the first organic phase input pipe (4-3) and the first organic phase output pipe (4-7); when the first rotary piston (4-9) rotates to the first quantitative channel When the first rotating piston (4-9) is in a horizontal position, the two ends of the first quantitative channel (4-2) are respectively connected to the first organic phase input pipe (4-3) and the first organic phase output pipe (4-7); when the first rotating piston (4-9) rotates to the first quantitative channel (4-2) and is in a vertical position, the two ends of the first quantitative channel (4-2) are respectively connected to the first aqueous phase input pipe (4-4) and the first aqueous phase output pipe (4-8); a second bypass pipe (4-6) is further provided between the first organic phase input pipe (4-3) and the first organic phase output pipe (4-7); a first bypass pipe (4-5) is further provided between the first aqueous phase input pipe (4-4) and the first aqueous phase output pipe (4-8); the first bypass pipe (4-5) and the second bypass pipe (4-6) ensure that the organic phase solution and the aqueous phase are always in a flowing state during the process of the quantitative channel collecting the organic phase, releasing the organic phase and rotating the piston; The second structure is composed of a second organic phase output pipe (4-10), a second sleeve (4-11), a second organic phase input pipe (4-12), a second rotary piston (4-14), a three-way pipe (4-15), a second aqueous phase output pipe (4-16), a third sleeve (4-17), a third rotary piston (4-18), a vertical connecting pipe (4-20), a fourth rotary piston (4-21), a fourth sleeve (4-23) and a second aqueous phase input pipe (4-24); the three-way pipe (4-15) has three openings, one located at the top and opening vertically upward, and the other two located at the bottom and opening horizontally; the second quantitative straight pipe structure is provided in the second rotary piston (4-14). The second sleeve (4-11) is provided with a second rotary piston (4-14) and is in a sliding connection relationship; the horizontal ends of the second sleeve (4-11) are respectively connected to the second organic phase input pipe (4-12) and the second organic phase output pipe (4-10); the lower end of the second sleeve (4-11) is connected to the top opening of the three-way pipe (4-15), and the other two horizontal openings of the three-way pipe (4-15) are respectively connected to the horizontal ends of the fourth sleeve (4-23) and the third sleeve (4-17); the fourth sleeve (4-23) is arranged just above the third sleeve (4-17); when the second rotary piston (4-14) rotates until the second quantitative channel (4-13) is in a horizontal position, the fourth sleeve (4-23) is provided with a second rotary piston (4-14) and is in a sliding connection relationship; the second organic phase input pipe (4-12) and the second organic phase output pipe (4-10) are respectively connected; ... second organic phase input pipe (4-12) and the second organic phase output pipe (4-10) are respectively connected; the second organic phase input pipe (4-12) and the second organic phase output pipe (4-10) are respectively connected; the second organic phase input The two ends of the second quantitative channel (4-13) are respectively connected to the second organic phase input pipe (4-12) and the second organic phase output pipe (4-10); when the second rotary piston (4-14) rotates to the second quantitative channel (4-13) in a vertical position, the lower end of the second quantitative channel (4-13) is connected to the top opening of the three-way pipe (4-15); a third quantitative channel (4-19) of a T-shaped structure is provided in the third rotary piston (4-18), and the third rotary piston (4-18) is provided in the third sleeve (4-17) and is in a sliding connection relationship; the upper and lower ends of the third sleeve (4-17) are respectively connected to the lower end of the vertical connecting pipe (4-20) and the second aqueous phase output pipe (4-16); the third One horizontal end of the three-tube (4-17) is in communication with a horizontal opening of the three-way pipe (4-15); when the third rotating piston (4-18) rotates until the two opposite ends of the third quantitative channel (4-19) are in a vertical position, the upper and lower ends of the third quantitative channel (4-19) are in communication with the lower part of the vertical connecting pipe (4-20) and the second water phase output pipe (4-16) respectively; when the third rotating piston (4-18) rotates until the two opposite ends of the third quantitative channel (4-19) are in a horizontal position, the bottom opening of the third quantitative channel (4-19) is in communication with the second water phase output pipe (4-16), and one horizontal end of the third quantitative channel (4-19) is in communication with a horizontal opening of the three-way pipe (4-15);The fourth rotating piston (4-21) is provided with a fourth quantitative channel (4-22) of a T-shaped structure. The fourth rotating piston (4-21) is provided in a fourth sleeve (4-23) and is in a sliding connection relationship. The upper and lower ends of the fourth sleeve (4-23) are respectively connected to the second water phase input pipe (4-24) and the upper end of the vertical connecting pipe (4-20). The horizontal end of the fourth sleeve (4-23) is connected to a horizontal opening of the three-way pipe (4-15). When the fourth rotating piston (4-21) rotates to the fourth quantitative channel (4- When the two opposite ends of the fourth quantitative channel (4-22) are in a vertical position, the upper and lower ends of the fourth quantitative channel (4-22) are respectively connected to the second water phase input pipe (4-24) and the upper part of the vertical connecting pipe (4-20); when the fourth rotating piston (4-21) rotates until the two opposite ends of the fourth quantitative channel (4-22) are in a horizontal position, the top opening of the fourth quantitative channel (4-22) is connected to the second water phase input pipe (4-24), and the horizontal end of the fourth quantitative channel (4-22) is connected to a horizontal opening of the tee pipe (4-15); The third structure is composed of a third organic phase input pipe (4-25), a third organic phase output pipe (4-26), a third aqueous phase input pipe (4-27), a fifth rotary piston (4-28), a fifth sleeve (4-30), a third aqueous phase output pipe (4-31), an obtuse angle connecting pipe (4-32), a sixth sleeve (4-34), a sixth rotary piston (4-35) and a right angle connecting pipe (4-36); the fifth rotary piston (4-28) is provided with a fifth quantitative channel (4-29) of a straight pipe structure, and the fifth rotary piston (4-28) is provided with a The fifth sleeve (4-30) is in a sliding connection relationship; the upper end and the lower end of the fifth sleeve (4-30) are respectively connected to the third water phase input pipe (4-27) and the third water phase output pipe (4-31), and the horizontal ends of the first sleeve (4-1) are respectively connected to the third organic phase input pipe (4-25) and the third organic phase output pipe (4-26); when the fifth rotating piston (4-28) rotates to the fifth quantitative channel (4-29) is located in a horizontal position, the two ends of the fifth quantitative channel (4-29) are respectively connected to the third organic phase input pipe (4-25) and the third organic phase output pipe (4-26). The organic phase output pipe (4-26) is connected; when the fifth rotating piston (4-28) rotates to the fifth quantitative channel (4-29) is located in a vertical position, the two ends of the fifth quantitative channel (4-29) are respectively connected to the third water phase input pipe (4-27) and the third water phase output pipe (4-31); the sixth rotating piston (4-35) is provided with a sixth quantitative channel (4-33) of a straight pipe structure, and the sixth rotating piston (4-35) is provided in a sixth sleeve (4-34) and is in a sliding connection relationship; the upper end and the lower end of the sixth sleeve (4-34) are respectively connected to the straight pipe. The lower end of the right-angle connecting pipe (4-36) is connected to the upper end of the obtuse-angle connecting pipe (4-32), and the other end of the right-angle connecting pipe (4-36) is connected to the third water phase input pipe (4-27); the lower part of the obtuse-angle connecting pipe (4-32) gradually tilts downward and is connected to the third water phase output pipe (4-31); when the sixth rotating piston (4-35) rotates until the sixth quantitative channel (4-33) is in a vertical position, the two ends of the sixth quantitative channel (4-33) are respectively connected to the lower end of the right-angle connecting pipe (4-36) and the upper end of the obtuse-angle connecting pipe (4-32).

2. The device for continuously preparing large-sized polymer balls with controllable size according to claim 1, characterized in that The volumes of the first quantitative channel (4-2), the second quantitative channel (4-13) and the fifth quantitative channel (4-29) are all 0.1 mL to 2 mL; the lengths of the three channels are all 10 mm to 20 mm, and the diameters are all 3.6 mm to 11.3 mm.

3. The device for continuously preparing large-sized polymer balls with controllable size according to claim 1, characterized in that The obtuse angle connecting pipe (4-32) is 3 degrees to the horizontal direction. o ~10 o .

4. The device for continuously preparing large-sized polymer balls with controllable size according to claim 1, characterized in that The inner diameter of the spherical tube (6-1) is 10mm-25mm.

5. The device for continuously preparing large-sized polymer balls with controllable size according to claim 1, characterized in that The inner diameter of the serpentine polymer tube (6) is 5mm~20mm and is smaller than the inner diameter of the spherical tube (6-1); the height of the serpentine polymer tube (6) is 200mm~1000mm, and the tube coil diameter of the serpentine polymer tube (6) is 100mm~1500mm.

6. The device for continuously preparing large-sized polymer balls with controllable size according to claim 1, characterized in that On the organic phase reflux pipe (11), a liquid separation device is provided between the prepolymerization tank (1) and the quantitative device (4) for separating the aqueous phase and the organic phase in the quantitative channel, and then returning the organic phase to the prepolymerization tank (1).

7. A method for using the device for continuously preparing large-sized polymer balls with controllable size according to claim 1, characterized in that The method for using the device for continuously preparing large-size polymer spheres with controllable size is as follows:

1. Add tap water to the hot water circulation pump (5), turn on the heating switch for preheating, and set the circulation temperature to 82°C~85°C; transfer the aqueous phase to the maturation tank (8), and then the maturation tank (8) is heated to 82°C~85°C through the first hydrothermal tank (9) and then kept at a constant temperature; transfer the organic phase to the prepolymerization tank (1), and pass through the second hydrothermal tank (10) to heat to 40°C~60°C and then keep the temperature constant, and prepolymerize the organic phase in the prepolymerization tank (1) for 40min~45min; the density of the organic phase is greater than that of the aqueous phase; 2. Turn on the circulation button of the hot water circulation pump (5), and hot water enters the water heating tank (7) and fills it up; When the quantitative device (4) is the first structure, the first rotary piston (4-9) is rotated so that the first quantitative channel (4-2) is in a horizontal position, that is, it is connected with the first organic phase input pipe (4-3) and the first organic phase output pipe (4-7); the second pump (3) is turned on so that the water in the serpentine polymerization tube (6) flows from bottom to top, and the aqueous phase enters the second aqueous phase delivery pipe (15) through the first bypass pipe (4-5); when the second aqueous phase delivery pipe (15) is filled with aqueous phase, the second pump (3) is turned off; the first pump (2) is turned on, and after the organic phase liquid fills the first quantitative channel (4-2), the first pump (2) is turned off, and the first rotary piston (4-9) is rotated 90 degrees until the first quantitative channel (4-2) is connected with the first organic phase output pipe (4-7). The first aqueous phase input pipe (4-4) is connected to the first aqueous phase output pipe (4-8); the second pump (3) is turned on so that the water in the serpentine polymer tube (6) flows from top to bottom, and the water flow rate is controlled by the second pump (3). The organic phase flows along the first aqueous phase output pipe (4-8) to the spherical tube (6-1) and aggregates into spherical droplets. The organic phase droplets slowly roll along the serpentine polymer tube (6) for 0.5h to 2.5h under the action of their own gravity and the flow of the aqueous phase. After the organic phase droplets are completely solidified, they enter the aging tank (8) from the serpentine polymer tube (6) for the aging stage. After aging in the aging tank (8) for 2h to 2.5h, the SDB spheres are taken out; the SDB is a copolymer of styrene and divinylbenzene; When the quantitative device (4) is the second structure, the second rotary piston (4-14) is rotated so that the second quantitative channel (4-13) is in a horizontal position, that is, it is connected with the second organic phase input pipe (4-12) and the second organic phase output pipe (4-10); the third rotary piston (4-18) is rotated until the two opposite ends of the third quantitative channel (4-19) are in a vertical position, and the upper and lower ends of the third quantitative channel (4-19) are respectively connected with the lower part of the vertical connecting pipe (4-20) and the second aqueous phase output pipe (4-16); the fourth rotary piston (4-21) is rotated until the fourth quantitative channel (4- When the two opposite ends of the fourth quantitative channel (4-22) are in a vertical position, the upper and lower ends of the fourth quantitative channel (4-22) are respectively connected to the second water phase input pipe (4-24) and the upper part of the vertical connecting pipe (4-20); the second pump (3) is turned on so that the water in the serpentine polymer tube (6) flows from bottom to top, and the second pump (3) is turned off when the second water phase delivery pipe (15) is filled with water phase; the first pump (2) is turned on, and the first pump (2) is turned off after the organic phase liquid fills the second quantitative channel (4-13), and the second rotary piston (4-14) is rotated 90 degrees until the second quantitative channel (4-13) and the top of the three-way pipe (4-15) are opened. The fourth rotating piston (4-21) is rotated until the two opposite ends of the fourth quantitative channel (4-22) are in a horizontal position, the top opening of the fourth quantitative channel (4-22) is in communication with the second water phase input pipe (4-24), and the horizontal end of the fourth quantitative channel (4-22) is in communication with a horizontal opening of the tee pipe (4-15); the third rotating piston (4-18) is rotated until the two opposite ends of the third quantitative channel (4-19) are in a horizontal position, the bottom opening of the third quantitative channel (4-19) is in communication with the second water phase output pipe (4-16), and the horizontal end of the third quantitative channel (4-19) is in communication with the horizontal opening of the tee pipe (4-15). The end is connected to a horizontal opening of the three-way pipe (4-15); the second pump (3) is turned on so that the water in the serpentine polymer tube (6) flows from top to bottom, and the water flow rate is controlled by the second pump (3). The organic phase will flow along the second water phase output pipe (4-16) to the spherical tube (6-1) and aggregate into spherical droplets. The organic phase droplets slowly roll along the serpentine polymer tube (6) for 0.5h to 2.5h under the action of their own gravity and the flow of the water phase. After the organic phase droplets are completely solidified, they enter the maturation tank (8) from the serpentine polymer tube (6) for the maturation stage. After maturation for 2h to 2.5h in the maturation tank (8), the SDB spheres are taken out; When the metering device (4) is the third structure, the fifth rotary piston (4-28) is rotated until the fifth metering channel (4-29) is in a vertical position, and the two ends of the fifth metering channel (4-29) are respectively connected to the third water phase input pipe (4-27) and the third water phase output pipe (4-31); the sixth rotary piston (4-35) is rotated until the sixth metering channel (4-33) is in a vertical position, and the two ends of the sixth metering channel (4-33) are respectively connected to the right-angle connecting pipe (4-36). ) is connected to the upper end of the obtuse angle connecting pipe (4-32); the second pump (3) is turned on so that the water in the serpentine polymerization pipe (6) flows from bottom to top, and the second pump (3) is turned off when the second aqueous phase delivery pipe (15) is filled with aqueous phase; the fifth rotary piston (4-28) is rotated until the fifth quantitative channel (4-29) is in a horizontal position, and the two ends of the fifth quantitative channel (4-29) are respectively connected to the third organic phase input pipe (4-25) and the third organic phase output pipe (4-26); the first pump ( 2), after the organic phase liquid fills the fifth quantitative channel (4-29), the first pump (2) is closed, the fifth rotary piston (4-28) is rotated 90 degrees until the fifth quantitative channel (4-29) is connected to the third water phase input pipe (4-27) and the third water phase output pipe (4-31); the sixth rotary piston (4-35) is rotated until the sixth quantitative channel (4-33) is in a horizontal position, thus stopping the flow of the sixth quantitative channel (4-33); the second pump (3) is turned on so that the serpentine polymerization tube The water in (6) flows from top to bottom, and the water flow rate is controlled by the second pump (3). The organic phase will flow along the third water phase output pipe (4-31) to the spherical tube (6-1) and aggregate into spherical droplets. Under the action of its own gravity and the flow of the water phase, the organic phase droplets slowly roll along the serpentine polymerization tube (6) for 0.5h~2.5h. After the organic phase droplets are completely solidified from the serpentine polymerization tube (6) into the maturation tank (8) for the maturation stage, the SDB spheres are taken out after maturation for 2h~4h in the maturation tank (8); 3. The SDB spheres taken out from the maturation tank (8) are transferred to the extraction equipment, extracted with acetone for 18h~19h, taken out and rinsed with anhydrous ethanol, and finally the SDB spheres are placed in an oven at 40℃~45℃ to dry for 5h~6h to obtain large-sized SDB spheres with good sphericity.

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