Continuous polymerization production method and device for carbon dioxide-based polycarbonate

Abstract

The invention discloses a continuous polymerization production method and device for carbon dioxide-based polycarbonate. The continuous polymerization production method of the carbon dioxide-based polycarbonate comprises the following steps: aromatic ring block synthesis, carbonate block introduction, molecular structure setting and polymerization termination. The synthesis of the aromatic ring block and the synthesis of the carbonate block are separately carried out, and the reaction heat release process is milder, so that the stability of process control is improved. The polycarbonate prepared by the method provided by the invention has a stable monomer block structure, no homopolymer is generated, and the molecular weight distribution is narrow; and moreover, the method can realize continuous production of products and improve the stability of unit operation and process control, so that the product quality is more stable.

Description

Technical Field

[0001] The invention relates to the field of high molecular polymer synthesis, and more specifically to a method and a device for continuous polymerization of carbon dioxide-based polycarbonate. Background Art

[0002] Carbon dioxide-based polycarbonate is polymerized from carbon dioxide and comonomers, which include one or more of epoxy compounds and phthalic anhydride. Among them, copolymers with phthalic anhydride as a monomer have a higher glass transition temperature and a wider range of applications due to the introduction of a benzene ring structure into its molecular chain.

[0003] The production method can generally be divided into a continuous method and an intermittent method. The so-called continuous method means that for each device in the production process, the material is fed and discharged at the same time, and the process conditions are controlled to be stable. On the contrary, the so-called intermittent method means that for each device in the polymerization production process, the material is not fed and discharged at the same time, and the process conditions are not constant. In the prior art, the production method of carbon dioxide-based high molecular copolymers containing phthalic anhydride as a monomer is mostly an intermittent method. In a production cycle of the intermittent method, the same equipment needs to be subjected to process change operations, such as intermittent feeding, increasing or decreasing temperature, pressure and liquid level, etc. These unstable process operations will cause the monomer block structure in the copolymer molecules to differ between batches, so the polymer product has a production cycle and batch, and the quality fluctuations will occur between batches, resulting in unstable product quality. In addition, since the intermittent process requires the equipment to be cleaned, a large amount of waste liquid will be generated and needs to be recycled, resulting in increased production energy consumption, extended production cycle, and reduced production efficiency.

[0004] CN113845649A discloses a method for synthesizing a random carbon dioxide-based polyester-polycarbonate copolymer by step-by-step feeding. Although the monomer raw materials are added to the reactor step by step, it is still an intermittent polymerization in the laboratory test stage, and still has all the disadvantages of the above-mentioned intermittent polymerization. More importantly, due to the presence of carbon dioxide in the first step of the feeding reaction, aromatic ring blocks and carbonate blocks will occur randomly, resulting in instability of the aromatic ring block structure sequence; and due to the increase in the feeding steps, the fluctuation between batches is more difficult to control, and has a very obvious amplification effect, and cannot be realized in industrial production.

[0005] CN103214666A discloses a method for preparing aliphatic polycarbonate by continuous solution polymerization, which uses a loop reactor and a tubular reactor in series for continuous polymerization reaction, wherein the conversion rate in the loop reactor is only 10%-20%, and in the tubular reactor, the liquid reaction material runs in the full tube, there is no phase interface between carbon dioxide gas and liquid, and carbon dioxide monomer is not provided to the tubular reactor, resulting in that the polymerization stage can hardly produce molecular segments containing carbon dioxide monomer, and the products are mainly homopolymers and copolymers of other monomers. In addition, a large amount of carbon dioxide and other monomers are discharged in the loop reactor stage, and condensing equipment and compressors are required for recovery, resulting in a large amount of energy consumption. In addition, the technical solution provided by the patent cannot remove the catalyst, which seriously affects the performance and quality of the product and cannot meet the needs of more application scenarios. Summary of the invention

[0006] In view of the problems existing in the prior art, the purpose of the present invention is to provide a continuous polymerization production method and device for carbon dioxide-based polycarbonate, so that the monomer block structure in the copolymer molecule is stable and the quality of the copolymer product is stable. At the same time, no cleaning equipment is required, production energy consumption is reduced, and production efficiency is improved.

[0007] Based on this, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides a method for continuous polymerization production of carbon dioxide-based polycarbonate, comprising the following steps:

[0009] (1) Aromatic ring block synthesis: Phthalic anhydride, epoxy compound and catalyst are continuously transported to the aromatic ring block polymerization reactor through the inlet, respectively, so that the phthalic anhydride and the epoxy compound undergo anionic copolymerization to generate a block containing an aromatic ring. After the reaction is completed, the material enters the inlet of the carbonate block reactor through the outlet of the aromatic ring block polymerization reactor;

[0010] (2) Introducing carbonate blocks: in a carbonate block reactor, the blocks containing aromatic rings in the material from the aromatic ring block polymerization reactor are copolymerized with carbon dioxide to embed carbonate blocks between the blocks containing aromatic rings to form copolymerized block segments. After the reaction is completed, the materials enter the inlet of the molecular structure setting reactor through the outlet of the carbonate block reactor; the reaction pressure is controlled by the introduction of carbon dioxide;

[0011] (3) Molecular structure adjustment: In the molecular structure adjustment reactor, the copolymer block segments in the material from the carbonate block reactor are subjected to a redistribution reaction with the input regulator and catalyst to adjust the structure. After the reaction is completed, the material enters the inlet of the polymerization termination reactor through the outlet of the molecular structure adjustment reactor; the reaction pressure is controlled by the introduction of carbon dioxide;

[0012] (4) Polymerization termination: In the polymerization termination reactor, the material from the molecular structure adjustment reactor is subjected to a termination reaction with the input terminator. After the reaction is completed, the material flow enters the inlet of the cleaning equipment through the outlet of the polymerization termination reactor.

[0013] The purpose of step (1) of the above-mentioned continuous polymerization production method is to obtain a relatively stable aromatic ring segment sequence, without the need to control the reaction pressure, thereby reducing a manipulated variable and improving the stability of unit operation and process control.

[0014] In some embodiments, in step (1), in the aromatic ring block polymerization reactor, the conversion rate of phthalic anhydride is 70-100%.

[0015] In some embodiments, in step (1), the epoxy compound is selected from one or more of propylene oxide, cyclohexene oxide and epichlorohydrin.

[0016] In some embodiments, in step (1), the phthalic anhydride accounts for 0.5 to 60 wt % of the total feed, preferably 10 to 40 wt %.

[0017] In some embodiments, in step (1), the catalyst is a metal catalyst or a non-metal catalyst. The metal catalyst refers to a catalyst containing a metal element, such as one or more combinations of salen-type cobalt-based catalysts, piperazine-bridged bimetallic cobalt complex catalysts, and hexacyanometallic zinc catalysts, preferably a salen-type cobalt-based catalyst; the non-metal catalyst refers to a catalyst that does not contain a metal element, such as one or more combination catalysts of triethyl boron, triphenyl boron, bis(triphenylphosphine) ammonium chloride, and tri(pentafluorophenyl) boron, preferably a triethyl boron type, or a combination of triethyl boron and bis(triphenylphosphine) ammonium chloride in a molar ratio of 2:1; the catalyst is fed in the form of a solution, and its solvent is selected from one or more combinations of tetrahydrofuran, dimethyl ether, and petroleum ether, preferably tetrahydrofuran; in the catalyst solution, the catalyst concentration is 10 to 40 wt%.

[0018] In some embodiments, in step (1), the catalyst accounts for 0.005 to 0.5 wt % of the total feed, preferably 0.01 to 0.15 wt %.

[0019] In some embodiments, in step (1), the reaction temperature is any value between 20 and 90°C, preferably 50 to 70°C, which can be controlled by a medium; the average residence time of the material in the aromatic ring block polymerization reactor is any value between 0.5 and 3 hours, preferably 0.5-2 hours, which can be controlled by balancing the flow rate and the liquid level. Under these process conditions, the block containing the benzene ring formed by phthalic anhydride and the epoxy compound is in an oligomer state, which is conducive to the next step.

[0020] In step (2) of the above-mentioned continuous polymerization production method, since the reaction of embedding carbonate segments with the participation of carbon dioxide mainly occurs, the instantaneous heat release is much lower than the copolymerization reaction of all monomers together. That is, the present invention separates the synthesis of the aromatic ring block from the synthesis of the carbonate block, which is more gentle from the perspective of heat release, thereby improving the stability of process control.

[0021] In some embodiments, in step (2), the reaction temperature is any value between 30 and 95° C., preferably 60 to 80° C., and is controlled by a medium; the reaction pressure is 0.1 to 2.1 MPa, preferably 0.9 to 1.2 MPa; and the average residence time of the material in the carbonate block reactor is 0.5 to 10 h, preferably 1 to 5 h, which can be controlled by balancing the flow rate and the liquid level.

[0022] The purpose of step (3) of the above-mentioned continuous polymerization production method is to fine-tune the sequence of the aromatic ring block or carbonate block in the molecule to meet the needs of different application scenarios of the product.

[0023] In some embodiments, in step (3), the regulator is a propylene oxide solution of one or more of phthalic anhydride, cyclohexene oxide, and tetracarboxylic anhydride, wherein the tetracarboxylic anhydride is a combination of one or more of 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride, and cyclohexanetetracarboxylic dianhydride.

[0024] In some embodiments, in step (3), the phthalic anhydride in the regulator accounts for 1 to 50 wt % of the total amount of the regulator, the cyclohexene oxide accounts for 1 to 70 wt % of the total amount of the regulator, and the tetracarboxylic anhydride accounts for 0.1 to 10 wt % of the total amount of the regulator.

[0025] In some embodiments, in step (3), the catalyst is the same as the catalyst in step (1); the catalyst accounts for 0.005-0.5 wt% of the mass of the regulator, and the regulator accounts for 1-100 wt% of the mass of the material from the carbonate block reactor entering the molecular structure adjustment reactor.

[0026] In some embodiments, in step (3), the reaction temperature is any value between 30 and 95°C, preferably 65 to 80°C, and is controlled by a medium; the reaction pressure is any value between 0.1 and 2 MPa, preferably 1.2 to 1.5 MPa; the average residence time of the material in the molecular structure setting reactor is any value between 0.5 and 10 h, preferably 1 to 3 h, and is controlled by balancing the flow rate and the liquid level.

[0027] In some embodiments, in step (4), the terminator is one or more of water, methanol and ethanol.

[0028] In some embodiments, in step (4), the mass ratio of the terminator to the material entering the polymerization termination reactor is any value between 0.001 and 0.1.

[0029] In some embodiments, in step (4), the reaction temperature is any value between 30 and 90°C, preferably 65 to 75°C, and is controlled by a medium; the average residence time of the material in the polymerization termination reactor is any value between 0.1 and 1 h, and is controlled by balancing the flow rate and the liquid level.

[0030] In some embodiments, the continuous polymerization production method further comprises the following steps:

[0031] (5) Cleaning: In the cleaning device, the material from the polymerization termination reactor interacts with the input steam and cleaning liquid, so that the catalyst and by-products in the material enter the water phase and are discharged, the residual epoxy compound becomes the gas phase and is discharged, and the solid phase polymer is transported to the extrusion granulation unit;

[0032] (6) Extrusion granulation: The solid polymer from the cleaning equipment is pelletized in the extrusion equipment.

[0033] In some embodiments, in step (5), the cleaning solution is water with a pH value of 6 to 8.

[0034] In some embodiments, in step (5), the mass ratio of the cleaning liquid to the material from the polymerization termination reactor is any value between 0.1 and 5, preferably 1 to 2.5.

[0035] In some embodiments, in step (5), the mass ratio of the steam to the material from the polymerization termination reactor is any value between 0.01 and 1.5, preferably between 0.1 and 0.5.

[0036] In some embodiments, in step (5), in the cleaning equipment, the temperature of material interaction is any value between 35 and 120°C, preferably between 80 and 90°C, which can be controlled by the medium; the pressure is 0.02 to 0.05 MPa, which can be controlled by exhaust; the average residence time of the material in the cleaning equipment is 0.5 to 3 hours, which can be controlled by the liquid level.

[0037] In some embodiments, in step (6), the temperature of the extrusion equipment is any value between 60 and 210° C., preferably between 100 and 140° C., and can be controlled by the temperature control system of the extrusion equipment itself; the pressure is any value between 0 and 0.1 MPa, preferably between 0.001 and 0.007 MPa, and is controlled by an external pressure system.

[0038] In a second aspect, the present invention also provides a continuous polymerization production device for carbon dioxide-based polycarbonate, the main equipment of which includes multiple, for example, 4-6 reactors. Preferably, it mainly includes 4 reactors, namely, an aromatic ring block polymerization reactor, a carbonate block reactor, a molecular structure adjustment reactor, and a polymerization termination reactor;

[0039] The aromatic ring block polymerization reactor has material mixing function and external heat exchange function, including a monomer inlet, a catalyst inlet, a material outlet and an instrument port;

[0040] The carbonate block reactor has material mixing function and external heat exchange function, including material inlet, carbon dioxide gas inlet, material outlet and instrument port, and preferably adopts a horizontal and radial mixing axial non-back mixing reactor;

[0041] The molecular structure adjustment reactor has material mixing function and external heat exchange function, including material inlet, regulator inlet, catalyst inlet, material outlet and instrument port;

[0042] The polymerization termination reactor has a material mixing function, including a material inlet, a terminator inlet, a material outlet and an instrument port;

[0043] The material outlet and the material inlet of the reactor are connected in sequence through a connecting pipeline;

[0044] The pressures of the carbonate block reactor and the molecular structure setting reactor are controlled by the introduction of carbon dioxide, and there is a gas-liquid interface in the reactor.

[0045] In some embodiments, the continuous polymerization production device may further include a cleaning device and an extrusion device;

[0046] The cleaning equipment can be any equipment that can achieve solid-liquid-gas three-phase separation, has a material inlet, a cleaning liquid inlet, a solid material outlet, a liquid material outlet, a gas outlet and an instrument port, has pressure and temperature control functions, and is preferably a double-axis self-cleaning equipment (SCP);

[0047] The extrusion equipment can be any screw extruder (TSD) with the function of adjusting pressure and temperature;

[0048] The material inlet and the solid material outlet of the cleaning device are respectively connected to the material outlet of the polymerization termination reactor and the extrusion device through connecting pipelines.

[0049] In some embodiments, multiple reactors may be configured to achieve each function, such as multiple cleaning devices for removing catalysts, by-products and residual monomers; or multiple extrusion granulation devices for devolatilization, stranding and pelletizing of polymers.

[0050] In some embodiments, the above-mentioned pipelines for material transportation are all provided with metering pumps, and instruments for detecting and regulating temperature, pressure or liquid level are provided in the equipment if necessary.

[0051] Beneficial Effects

[0052] The continuous polymerization production method and device of carbon dioxide-based polycarbonate of the present invention have the following advantages:

[0053] 1. The monomer block structure of the prepared polycarbonate is stable, no homopolymer is produced, and the molecular weight distribution is narrow;

[0054] 2. The catalyst and by-products are removed cleanly, the product quality is high, and the application scenarios are expanded;

[0055] 3. Realize continuous production of products, improve the stability of unit operation and process control, and thus make product quality more stable;

[0056] 4. No carbon dioxide or other monomers are emitted during the polymerization reaction, and no carbon dioxide gas recovery equipment is required;

[0057] 5. No need to clean the polymerization equipment;

[0058] 6. Reduced production equipment investment and production energy consumption, and improved production efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] Figure 1 The present invention is a simplified flow chart of the continuous polymerization production method of carbon dioxide based polycarbonate implemented in the continuous polymerization production device of carbon dioxide based polycarbonate.

[0060] Figure symbols: 1, phthalic anhydride; 2, epoxy compound; 3, catalyst; 4-6, 8, 11, 14, 15, 18, 20, 22, 25, 27, 28, metering pumps; 7, aromatic ring block polymerization reactor; 9, carbonate block reactor; 10, 17, carbon dioxide; 12, regulator; 13, catalyst; 16, molecular structure adjustment reactor; 19, terminator; 21, termination reactor; 23, steam; 24, cleaning liquid; 26, cleaning equipment; 29, pressure regulating pipeline; 30, extrusion granulation equipment; 31, granular product logistics; S1-S23, inlet or outlet. DETAILED DESCRIPTION

[0061] The embodiments of the present invention will be described in detail below based on the embodiments and in conjunction with the accompanying drawings, but the embodiments of the present invention are not limited to the following embodiments.

[0062] The following examples use a continuous polymerization production device for carbon dioxide-based polycarbonate, the main equipment of which includes 6 reactors, namely, an aromatic ring block polymerization reactor 7, a carbonate block reactor 9, a molecular structure adjustment reactor 16, a polymerization termination reactor 21, a cleaning device 26 and an extrusion device 30; wherein,

[0063] The aromatic ring block polymerization reactor 7 has a material mixing function and an external heat exchange function, including a phthalic anhydride monomer inlet S1, an epoxy compound monomer inlet S2, a catalyst inlet S3, a material outlet S4 and an instrument port;

[0064] The carbonate block reactor 9 is a horizontal, radially mixed, axially non-back-mixed reactor, having a material mixing function and an external heat exchange function, and includes a material inlet S5, a carbon dioxide gas inlet S7, a material outlet S6 and an instrument port; the material inlet S5 is connected to the material outlet S4 of the aromatic ring block polymerization reactor 7 through a connecting pipeline;

[0065] The molecular structure setting reactor 16 has a material mixing function and an external heat exchange function, including a material inlet S8, a regulator inlet S10, a catalyst inlet S11, a material outlet S9, a carbon dioxide gas inlet S12 and an instrument port; the material inlet S8 is connected to the material outlet S6 of the carbonate block reactor 9 through a connecting pipeline;

[0066] The polymerization termination reactor 21 has a material mixing function, including a material inlet S13, a terminator inlet S14, a material outlet S15 and an instrument port; the material inlet S13 is connected to the material outlet S9 of the molecular structure setting reactor 16 through a connecting pipeline;

[0067] The pressure of the carbonate block reactor 9 and the molecular structure setting reactor 21 is controlled by the introduction of carbon dioxide, and there is a gas-liquid interface in the reactor;

[0068] The cleaning device 26 is a double-axis self-cleaning device (SCP), which can achieve solid-liquid-gas three-phase separation, has a material inlet S16, a cleaning liquid inlet S18, a solid material outlet S21, a liquid material outlet S20, a gas outlet S19 and an instrument port, and has a pressure and temperature control function; the material inlet S16 of the cleaning device 26 is connected to the material outlet S15 of the polymerization termination reactor 21 through a connecting pipeline;

[0069] The extrusion device 30 is a screw extruder (TSD) with pressure and temperature adjustment functions, having a material inlet S22 and a material outlet S23; the material inlet S22 of the extrusion device 30 is connected to the solid material outlet S21 of the cleaning device through a connecting pipeline;

[0070] The material pipelines connected to the inlets or outlets S1, S2, S3, S5, S8, S10, S11, S13, S14, S16, S17, S20, S22 are respectively provided with metering pumps 4, 5, 6, 8, 11, 14, 15, 18, 20, 22, 25, 28, 27.

[0071] pass Figure 1 The specific implementation of the technical solution of the present invention is described. Specifically, the continuous polymerization production method of carbon dioxide-based polycarbonate provided by the present invention comprises the following steps:

[0072] (1) Aromatic ring block synthesis: Phthalic anhydride 1, epoxy compound 2 and catalyst 3 (wherein the phthalic anhydride feed amount accounts for 0.5% to 60% of the total feed mass; the catalyst accounts for 0.005 to 0.5 wt% of the total feed mass) are respectively continuously transported to the aromatic ring block polymerization reactor 7 through inlets S1 to S3 by metering pumps 4 to 6 for polymerization reaction, and the process variables reaction temperature and average residence time are controlled to be appropriate values ​​(for example, the reaction temperature is controlled to be any value between 20 and 90° C., and the average residence time is controlled to be any value between 0.5 and 3 hours), so that phthalic anhydride and the epoxy compound undergo anionic copolymerization to generate a block containing an aromatic ring, and the phthalic anhydride conversion rate is controlled to be 70-100%; the materials after the reaction are discharged through outlet S4 and enter the carbonate block reactor 9. Here, the reaction temperature is controlled by a medium; the average residence time is controlled by the discharge flow rate and the liquid level.

[0073] (2) Introducing carbonate blocks: The logistics leaving the aromatic ring block polymerization reactor 7 is transported to the carbonate block reactor 9 through the metering pump 8 via the inlet S5, and the process variables reaction temperature, pressure and average residence time are controlled to appropriate values ​​(for example, the reaction temperature is controlled to be any value between 30 and 95°C; the pressure is controlled by the carbon dioxide 10 entering the reactor through the inlet S7, for example, the reaction pressure is controlled to be any value between 0.1 and 2.1 MPa; for example, the average residence time is controlled to be any value between 0.5 and 10 hours), so that the aromatic ring-containing blocks and carbon dioxide are copolymerized to embed carbonate blocks between the aromatic ring-containing blocks to form copolymer block segments; the materials after the reaction are completed leave through the outlet S6. Here, the reaction temperature is controlled by the medium; the average residence time is controlled by the discharge flow rate and the liquid level.

[0074] (3) Molecular structure setting: The material flow leaving the carbonate block reactor 9 is transported to the molecular structure setting reactor 16 via the metering pump 11 through the inlet S8, and the process variables reaction temperature, pressure and average residence time are controlled to be suitable constant values ​​(for example, the reaction temperature is controlled to be any value between 30 and 95° C.; the pressure is controlled by the carbon dioxide 17 entering the reactor through the inlet S12, for example, the reaction pressure is controlled to be 0.1 to 2 MPa; for example, the average residence time is controlled to be any value between 0.5 and 10 h), so that the copolymerized block segments in the material flow and the regulator 12 and catalyst 13 input from the inlets S10 and S11 through the metering pumps 14 and 15 are redistributed and reacted to set the structure (wherein the catalyst accounts for 0.005 to 0.5 wt% of the mass of the regulator, and the regulator accounts for 1 to 100 wt% of the mass of the material from the carbonate block reactor entering the molecular structure setting reactor). After the reaction is completed, the material leaves through the outlet S9 and enters the polymerization termination reactor 21. Here, the temperature is controlled by the medium; the average residence time is controlled by the discharge flow rate and the liquid level.

[0075] (4) Polymerization termination: The material leaving the molecular structure setting reactor 16 is transported to the polymerization termination reactor 21 by the metering pump 18, and undergoes a termination reaction with the terminator 19 input by the metering pump 20 through the inlet S14 (the mass ratio of the terminator to the material entering the reactor is an arbitrary value between 0.001 and 0.1), and the process variables reaction temperature and average residence time are controlled to be appropriate values ​​(for example, the reaction temperature is controlled to be an arbitrary value between 30 and 90° C., and the average residence time is controlled to be an arbitrary value between 0.1 and 1 h). The material after the reaction is completed leaves through the outlet S15 and enters the cleaning device 26. Here, the temperature is controlled by the medium, and the average residence time is controlled by the discharge flow rate and the liquid level.

[0076] (5) Cleaning: The material leaving the polymerization termination reactor 21 is transported to the cleaning device 26 through the inlet S16 by the metering pump 22, and interacts with the steam 23 input through the inlet S17 and the cleaning liquid 24 input from the inlet S18 by the metering pump 25 (the mass ratio of the cleaning liquid to the inflowing material is any value between 0.1 and 5; the mass ratio of the steam to the logistics from the polymerization termination reactor 21 is any value between 0.01 and 1.5), and the process variables temperature, pressure and average residence time are controlled to be appropriate values ​​(for example, the reaction temperature is controlled to be any value between 35 and 120° C., for example, the pressure is controlled to be 0.02 to 0.05 MPa, for example, the average residence time of the material in the cleaning device is controlled to be 0.5 to 3 hours), so that the catalyst and by-products in the material enter the water phase and are discharged through the outlet S20 by the metering pump 28; the residual propylene oxide becomes the gas phase and is discharged from the pressure regulating pipeline 29 through the outlet S19; the polymer product becomes the solid phase and leaves through the outlet S21, wherein the solid phase polymer enters the granulation device 30. Here, the temperature is controlled by the medium, the pressure is controlled by exhausting the pressure regulating line 29, and the average residence time is controlled by the liquid level.

[0077] (6) Extrusion granulation: The solid polymer flow leaving the cleaning device 26 is transported to the extrusion granulation device 30 through the metering pump 27 for granulation. Here, the process variables temperature and pressure are controlled. The temperature is any value between 60 and 210°C and is controlled by the temperature control system of the extrusion device itself; the pressure is any value between 0 and 0.1 MPa and is controlled by the external pressure system. The obtained granular product is sent out from the outlet S23 through the granular product flow 31.

[0078] Example 1 A continuous polymerization production method for carbon dioxide-based polycarbonate

[0079] This embodiment uses Figure 1 The continuous polymerization production device of carbon dioxide-based polycarbonate shown in the figure, the method for continuously polymerizing and producing carbon dioxide-based polycarbonate comprises the following steps:

[0080] (1) Aromatic ring block synthesis: Phthalic anhydride 1, epoxy compound 2 (propylene oxide) and catalyst 3 (a tetrahydrofuran solution containing 20 wt% triethylboron and bis(triphenylphosphine)ammonium chloride in a molar ratio of 2:1) are continuously transported to an aromatic ring block polymerization reactor 7 with a volume of 120 L through inlets S1-S3 by metering pumps 4-6 at flow rates of 10 kg / h, 79.5 kg / h and 0.5 kg / h, respectively, for anionic copolymerization to generate aromatic ring-containing blocks. The feed liquid temperature is controlled to 50° C. and the average residence time is 0.8 h. At this time, the phthalic anhydride conversion rate is 85%, and the reacted materials leave through outlet S4.

[0081] (2) Introducing carbonate blocks: The material leaving the aromatic ring block polymerization reactor 7 is transported to a carbonate block reactor 9 with a volume of 320 L by a metering pump 8 through an inlet S5 for polymerization reaction. The process temperature is controlled to be 60° C., the pressure is 0.9 MPa (the pressure is controlled by passing carbon dioxide 10 into an inlet S7), and the average residence time is 3 h. The blocks containing aromatic rings are copolymerized with carbon dioxide to embed carbonate blocks between the blocks containing aromatic rings to form copolymer block segments. The reacted materials leave through an outlet S6.

[0082] (3) Molecular structure setting: The logistics leaving the carbonate block reactor 9 is transported to a molecular structure setting reactor 16 with a volume of 210 L by a metering pump 11 through an inlet S8, and undergoes a redistribution reaction with a regulator 12 (20 wt% of phthalic anhydride, 30 wt% of cyclohexene oxide, 1 wt% of pyromellitic dianhydride, and 49 wt% of propylene oxide) and a catalyst 13 (a tetrahydrofuran solution of 10 wt% triethylboron and bis(triphenylphosphine)ammonium chloride in a molar ratio of 2:1) introduced through metering pumps 14 and 15 at a rate of 1.5 kg / h and 0.01 kg / h, respectively. The temperature is controlled at 65° C., the pressure is 1.5 MPa (the pressure is controlled by passing carbon dioxide 17 into the inlet S12), and the average residence time is 2 h for structure setting. The logistics after the reaction leaves through the outlet S9.

[0083] (4) Polymerization termination: The material leaving the molecular structure setting reactor 16 is transported to the polymerization termination reactor 21 with a volume of 60 L through the inlet S13 by the metering pump 18, and the terminator 19 (water) is input through the inlet S14 by the metering pump 20 at a flow rate of 1.8 kg / h to terminate the polymerization reaction (the mass ratio of the terminator 19 to the material entering the polymerization termination reactor is 0.018). The reaction temperature is controlled at 65°C and the average residence time is 0.3 h. After the reaction is completed, the material leaves through the outlet S15.

[0084] (5) Cleaning: The material leaving the polymerization termination reactor 21 is transported to the SCP cleaning device 26 through the inlet S16 by the metering pump 22, and interacts with the steam 23 (the mass ratio of steam to the material from the polymerization termination reactor is 0.12) input through the inlet S17 at a flow rate of 1.2 kg / h and the cleaning liquid 24 (the cleaning liquid is water with a pH of 6 to 8, and the mass ratio of the cleaning liquid to the material from the polymerization termination reactor is 1.6) input through the metering pump 25 through the inlet S18 at a flow rate of 160 kg / h. The process variables temperature, pressure and average residence time are controlled to be 90° C., 0.05 MPa and 1 h, so that the catalyst and by-products in the material enter the water phase and are discharged through the outlet S20 by the metering pump 28; the residual propylene oxide becomes the gas phase and is discharged from the pressure regulating pipeline 29 through the outlet S19; the polymer product becomes the solid phase and leaves through the outlet S21, wherein the solid phase polymer enters the granulation device 30.

[0085] (6) Extrusion granulation: The material flow leaving the cleaning device 26 is transported from the inlet S22 to the TSD extrusion granulation device 30 for granulation through the melt metering pump 27. Here, the process variables temperature is controlled to be 120°C and the pressure is 0.001 MPa. The obtained granular product is sent out from the outlet S23 through the granular product flow 31.

[0086] After the system stabilized, samples were taken every 3 hours. A total of three samples were taken to determine the molecular weight of the copolymer and the content of carbonate chain segments. The results are as follows:

[0087] Mn = 79.8, 81.1, 80.6 kDa, mean 80.5 ± 0.7 kDa;

[0088] PDI = 2.5, 2.6, 2.5, with an average of 2.5 ± 0.1;

[0089] The carbonate chain contents are 15.2%, 14.9%, 15.8%, and the average value is (15.3±0.5)%.

[0090] The catalyst contents were 0.51 ppm, 0.64 ppm, and 0.48 ppm, with an average value of (0.54±0.09) ppm.

[0091] Example 2 A continuous polymerization production method for carbon dioxide-based polycarbonate

[0092] This embodiment uses Figure 1 The continuous polymerization production device of carbon dioxide-based polycarbonate shown in the figure, the method for continuously polymerizing and producing carbon dioxide-based polycarbonate comprises the following steps:

[0093] (1) Aromatic ring block synthesis: Phthalic anhydride 1, epoxy compound 2 (propylene oxide) and catalyst 3 (a tetrahydrofuran solution containing 20 wt% triethylboron and bis(triphenylphosphine)ammonium chloride in a molar ratio of 2:1) are continuously transported to an aromatic ring block polymerization reactor 7 with a volume of 120 L through inlets S1-S3 using metering pumps 4-6 at flow rates of 15 kg / h, 74.5 kg / h and 0.6 kg / h, respectively, for anionic copolymerization to generate aromatic ring-containing blocks. The feed liquid temperature is controlled at 50° C. and the average residence time is 0.8 h. The reacted materials leave through outlet S4.

[0094] (2) Introduction of carbonate block: The material leaving the aromatic ring block polymerization reactor 7 is transported to a carbonate block reactor 9 with a volume of 320 L by a metering pump 8 through an inlet S5 for polymerization reaction. The process temperature is controlled to be 80° C., the pressure is 1.2 MPa (the pressure is controlled by passing carbon dioxide 10 into an inlet S7), and the average residence time is 3 h. The block containing aromatic rings is copolymerized with carbon dioxide to embed carbonate blocks between the blocks containing aromatic rings to form copolymer block segments. The material after the reaction is completed leaves through an outlet S6.

[0095] (3) Molecular structure adjustment: The logistics leaving the carbonate block reactor 9 is transported to a molecular structure adjustment reactor 16 with a volume of 210 L by a metering pump 11 through an inlet S8, and is redistributed with a regulator 12 (10 wt% of phthalic anhydride, 50 wt% of cyclohexene oxide, 5 wt% of 3,3′,4,4′-dibenzophenonetetracarboxylic dianhydride, and 35 wt% of propylene oxide) and a catalyst 13 (a tetrahydrofuran solution of 20 wt% triethylboron and bis(triphenylphosphine)ammonium chloride in a molar ratio of 2:1) input through inlets S10 and S11 at 1 kg / h and 0.005 kg / h respectively through metering pumps 14 and 15. The temperature is controlled at 80°C, the pressure is 1.2 MPa, and the average residence time is 2 h for structure adjustment. The logistics after the reaction leaves through an outlet S9.

[0096] (4) Polymerization termination: The material leaving the molecular structure setting reactor 16 is transported to the polymerization termination reactor 21 with a volume of 60 L through the inlet S13 by the metering pump 18, and the terminator 19 (water) is input through the inlet S14 by the metering pump 20 at a flow rate of 5 kg / h to terminate the polymerization reaction (the mass ratio of the terminator 19 to the material entering the polymerization termination reactor is 0.058). The temperature is controlled at 75°C and the average residence time is 0.3h. After the reaction is completed, the material leaves through the outlet S15.

[0097] (5) Cleaning: The material leaving the polymerization termination reactor 21 is transported to the SCP cleaning device 26 through the inlet S16 by the metering pump 22, and interacts with the steam 23 (the mass ratio of steam to the material from the polymerization termination reactor is 0.6) input through the inlet S17 at a flow rate of 6.0 kg / h and the cleaning liquid 24 (the cleaning liquid is water with a pH of 6 to 8, and the mass ratio of the cleaning liquid to the material from the polymerization termination reactor is 2.6) input through the metering pump 25 through the inlet S18 at a flow rate of 260 kg / h. The process variables are controlled to have a temperature of 80° C., a pressure of 0.02 MPa and an average residence time of 1 h, so that the catalyst and by-products in the material enter the water phase and are discharged through the outlet S20 by the metering pump 28; the residual propylene oxide becomes a gas phase and is discharged from the pressure regulating pipeline 29 through the outlet S19; the polymer product becomes a solid phase and leaves through the outlet S21, wherein the solid phase polymer enters the granulation device 30.

[0098] (6) Extrusion granulation: The material flow leaving the cleaning device 26 is transported from the inlet S22 to the TSD extrusion granulation device 30 for granulation through the melt metering pump 27. Here, the process variables temperature is controlled to be 120°C and the pressure is 0.004 MPa. The obtained granular product is sent out from the outlet S23 through the granular product flow 31.

[0099] After the system stabilized, samples were taken every 3 hours. A total of three samples were taken to determine the molecular weight of the copolymer and the content of carbonate chain segments. The results are as follows:

[0100] Mn = 94.8, 96.1, 95.3 kDa, average 95.4 ± 0.7 kDa;

[0101] PDI = 2.9, 3.2, 3.0, mean 3.0 ± 0.2;

[0102] The carbonate chain contents are 12.5%, 12.8%, and 12.1%, with an average value of (12.5±0.4)%.

[0103] The catalyst contents were 0.22 ppm, 0.18 ppm, and 0.25 ppm, with an average value of (0.22±0.04) ppm.

[0104] Example 3 A continuous polymerization production method for carbon dioxide-based polycarbonate

[0105] This embodiment uses Figure 1 The continuous polymerization production device of carbon dioxide-based polycarbonate shown in the figure, the method for continuously polymerizing and producing carbon dioxide-based polycarbonate comprises the following steps:

[0106] (1) Aromatic ring block synthesis: Phthalic anhydride 1, epoxy compound 2 (propylene oxide) and catalyst 3 (a tetrahydrofuran solution containing 20 wt% triethylboron and bis(triphenylphosphine)ammonium chloride in a molar ratio of 2:1) are continuously transported to an aromatic ring block polymerization reactor 7 with a volume of 120 L through inlets S1-S3 by metering pumps 4-6 at flow rates of 30 kg / h, 59.5 kg / h and 0.5 kg / h, respectively, for anionic copolymerization to generate aromatic ring-containing blocks. The feed liquid temperature is controlled to 70°C and the average residence time is 1.2 h. The reacted materials leave through outlet S4.

[0107] (2) Introducing carbonate blocks: The material leaving the aromatic ring block polymerization reactor 7 is transported to the carbonate block reactor 9 through the inlet S5 by the metering pump 8 for polymerization reaction. The process temperature is controlled to be 70° C., the pressure is 1.2 MPa (the pressure is controlled by passing carbon dioxide 10 into the inlet S7) and the average residence time is 3 h. The blocks containing aromatic rings are copolymerized with carbon dioxide to embed carbonate blocks between the blocks containing aromatic rings to form copolymer block segments. The materials after the reaction are completed leave through the outlet S6.

[0108] (3) Molecular structure adjustment: The logistics leaving the carbonate block reactor 9 is transported to the molecular structure adjustment reactor 16 through the inlet S8 by the metering pump 11, and is redistributed with the regulator 12 (15 wt% of phthalic anhydride, 45 wt% of cyclohexene oxide, 5 wt% of 3,3′,4,4′-dibenzophenonetetracarboxylic dianhydride, and 35 wt% of propylene oxide) and the catalyst 13 (a tetrahydrofuran solution of 30 wt% triethylboron and bis(triphenylphosphine)ammonium chloride in a molar ratio of 2:1) introduced through the inlets S10 and S11 through the metering pumps 14 and 15 at 80 kg / h and 0.024 kg / h, respectively. The temperature is controlled at 65°C, the pressure is 1.3 MPa (the pressure is controlled by passing carbon dioxide 17 into the inlet S12), and the average residence time is 2 h for structural adjustment. The logistics after the reaction leave through the outlet S9.

[0109] (4) Polymerization termination: The material leaving the molecular structure setting reactor 16 is transported to the polymerization termination reactor 21 through the inlet S13 by the metering pump 18, and the terminator 19 (water) is input through the inlet S14 by the metering pump 20 at a flow rate of 1.4 kg / h to terminate the polymerization reaction (the mass ratio of the terminator 19 to the material entering the polymerization termination reactor is 0.008). The temperature is controlled at 70°C and the average residence time is 0.3h. After the reaction is completed, the material leaves through the outlet S15.

[0110] (5) Cleaning: The material leaving the polymerization termination reactor 21 is transported to the cleaning device 26 through the inlet S16 by the metering pump 22, and interacts with the steam 23 input at a flow rate of 18 kg / h through the inlet S17 (the mass ratio of steam to material from the polymerization termination reactor is 0.1), and the cleaning liquid 24 (the cleaning liquid is water with a pH of 6 to 8, and the mass ratio of the cleaning liquid to material from the polymerization termination reactor is 3.7) input at a flow rate of 360 kg / h through the metering pump 25 through the inlet S18, and the process variables are controlled to have a temperature of 90°C, a pressure of 0.05 MPa and an average residence time of 1 hour, so that the catalyst and by-products in the material enter the water phase and are discharged through the outlet S20 by the metering pump 28; the residual propylene oxide becomes a gas phase and is discharged from the pressure regulating pipeline 29 through the outlet S19; the polymer product becomes a solid phase and leaves through the outlet S21, wherein the solid phase polymer enters the granulation device 30.

[0111] (6) Extrusion granulation: The material flow leaving the cleaning device 26 is transported to the extrusion granulation device 30 through the inlet S22 by the melt metering pump 27 for granulation. Here, the process variables temperature is controlled to be 120°C and the pressure is 0.007 MPa. The obtained granular product is sent out through the outlet S23 through the granular product flow 31.

[0112] After the system stabilized, samples were taken every 3 hours. A total of three samples were taken to determine the molecular weight of the copolymer and the content of carbonate chain segments. The results are as follows:

[0113] Mn = 106.4 ± 0.4 kDa, PDI = 2.7 ± 0.2, carbonate chain content 9.1 ± 0.2%;

[0114] Mn = 106.1, 104.8, 105.6 kDa, average 105.5 ± 0.7 kDa;

[0115] PDI = 2.6, 2.7, 2.6, mean 2.6 ± 0.1;

[0116] The carbonate chain contents are 9.5%, 8.8%, 9.3% and the average value is (9.2±0.4)%.

[0117] The catalyst content was 0.1ppm, 0.12ppm, and 0.14ppm, with an average value of (0.12±0.02)ppm.

[0118] Comparative Example 1

[0119] In a 120L polymerization kettle, 10kg of phthalic anhydride, 79.5kg of propylene oxide, 0.5kg of a catalyst (a tetrahydrofuran solution containing 20wt% triethyl boron and bis(triphenylphosphine) ammonium chloride in a molar ratio of 2:1), 1.5kg of a molecular weight regulator (20wt% phthalic anhydride, 30wt% cyclohexane oxide, 1wt% pyromellitic dianhydride, 49wt% propylene oxide) and 0.01kg of a catalyst (a tetrahydrofuran solution containing 10wt% triethyl boron and bis(triphenylphosphine) ammonium chloride in a molar ratio of 2:1) were added in an intermittent operation; the reactor was heated to 60°C, carbon dioxide gas was introduced to make the pressure in the reactor 0.9MPa, and the polymerization reaction was carried out for 3.5h; the reaction pressure was increased to 1.5MPa, and the reaction was continued for 2h; 1.8kg of a terminator (water) was added to the reactor, and the mixture was stirred for 0.3h; the mixture was discharged to an SCP cleaning device, and the subsequent operations were the same as steps (5) and (6) in Example 1.

[0120] The above experiment was repeated for 3 batches, and the molecular weight and carbonate chain content of the copolymer were determined as follows:

[0121] Mn = 100.5 kDa, 120.4 kDa, 90.8 kDa, mean = 103.9 ± 15 kDa;

[0122] PDI = 2.1, 4.0, 2.9, mean 3.0 ± 0.9;

[0123] The carbonate chain content is 14%, 11%, and 20%, with an average value of (15.0±4.5)%.

[0124] The catalyst content was 2.5ppm, 0.8ppm, and 1.3ppm, with an average value of (1.5±0.9)ppm.

Claims

1. A continuous polymerization production method for carbon dioxide-based polycarbonate, comprising the following steps: (1) Aromatic ring block synthesis: Phthalic anhydride, epoxy compound and catalyst are continuously transported to the aromatic ring block polymerization reactor through the inlet, respectively, so that the phthalic anhydride and the epoxy compound undergo anionic copolymerization to generate a block containing an aromatic ring. After the reaction is completed, the material enters the inlet of the carbonate block reactor through the outlet of the aromatic ring block polymerization reactor; (2) Introducing carbonate blocks: in a carbonate block reactor, the blocks containing aromatic rings in the material from the aromatic ring block polymerization reactor are copolymerized with carbon dioxide to embed carbonate blocks between the blocks containing aromatic rings to form copolymerized block segments. After the reaction is completed, the materials enter the inlet of the molecular structure setting reactor through the outlet of the carbonate block reactor; the reaction pressure is controlled by the introduction of carbon dioxide; (3) Molecular structure adjustment: In the molecular structure adjustment reactor, the copolymer block segments in the material from the carbonate block reactor are subjected to a redistribution reaction with the input regulator and catalyst to adjust the structure. After the reaction is completed, the material enters the inlet of the polymerization termination reactor through the outlet of the molecular structure adjustment reactor; the reaction pressure is controlled by the introduction of carbon dioxide; (4) Polymerization termination: In the polymerization termination reactor, the material from the molecular structure adjustment reactor is subjected to a termination reaction with the input terminator. After the reaction is completed, the material flow enters the inlet of the cleaning equipment through the outlet of the polymerization termination reactor.

2. The production method according to claim 1, characterized in that In step (1): In the aromatic ring block polymerization reactor, the conversion rate of phthalic anhydride is 70-100%; and / or The epoxy compound is selected from one or more of propylene oxide, cyclohexene oxide and epichlorohydrin; and / or The phthalic anhydride accounts for 0.5 to 60 wt % of the total feed, preferably 10 to 40 wt %; and / or The catalyst is a metal catalyst or a non-metal catalyst; wherein the metal catalyst is selected from one or more combinations of salen-type cobalt-based catalysts, piperazine-bridged bimetallic cobalt complex catalysts, and hexacyanometallic zinc catalysts, preferably a salen-type cobalt-based catalyst; the non-metal catalyst is selected from one or more combination catalysts of triethyl boron, triphenyl boron, bis(triphenylphosphine) ammonium chloride, and tri(pentafluorophenyl) boron, preferably a triethyl boron type, or a combination of triethyl boron and bis(triphenylphosphine) ammonium chloride in a molar ratio of 2:1; the catalyst is fed in the form of a solution, and its solvent is selected from one or more combinations of tetrahydrofuran, dimethyl ether, and petroleum ether, preferably tetrahydrofuran; in the catalyst solution, the catalyst concentration is 10 to 40 wt%; and / or The catalyst accounts for 0.005-0.5wt% of the total feed, preferably 0.01-0.15wt%; and / or The reaction temperature is 20 to 90° C., preferably 50 to 70° C.; and / or The average residence time of the material in the aromatic ring block polymerization reactor is 0.5 to 3 hours, preferably 0.5 to 2 hours.

3. The production method according to claim 1, characterized in that: In step (2): The reaction temperature is 30 to 95° C., preferably 60 to 80° C.; and / or The reaction pressure is 0.1-2.1 MPa, preferably 0.9-1.2 MPa; and / or The average residence time of the material in the carbonate block reactor is 0.5 to 10 hours, preferably 1 to 5 hours.

4. The production method according to claim 1, characterized in that: In step (3): The regulator is a propylene oxide solution of one or more of phthalic anhydride, cyclohexene oxide, and tetracarboxylic anhydride, wherein the tetracarboxylic anhydride is a combination of one or more of 3,3',4,4'-benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride, and cyclohexanetetracarboxylic dianhydride; and / or In the regulator, phthalic anhydride accounts for 1-50wt% of the total amount of the regulator, cyclohexene oxide accounts for 1-70wt% of the total amount of the regulator, and tetracarboxylic anhydride accounts for 0.1-10wt% of the total amount of the regulator; and / or The catalyst is a metal catalyst or a non-metal catalyst; wherein the metal catalyst is selected from one or more combinations of salen-type cobalt-based catalysts, piperazine-bridged bimetallic cobalt complex catalysts, and hexacyanometallic zinc catalysts, preferably a salen-type cobalt-based catalyst; the non-metal catalyst is selected from one or more combination catalysts of triethyl boron, triphenyl boron, bis(triphenylphosphine) ammonium chloride, and tri(pentafluorophenyl) boron, preferably a triethyl boron type, or a combination of triethyl boron and bis(triphenylphosphine) ammonium chloride in a molar ratio of 2:1; the catalyst is fed in the form of a solution, and its solvent is selected from one or more combinations of tetrahydrofuran, dimethyl ether and petroleum ether, preferably tetrahydrofuran; in the catalyst solution, the catalyst concentration is 10 to 40 wt%; and / or The catalyst accounts for 0.005-0.5 wt% of the mass of the regulator, and the regulator accounts for 1-100 wt% of the mass of the material from the carbonate block reactor entering the molecular structure adjustment reactor; and / or The reaction temperature is 30 to 95° C., preferably 65 to 80° C.; and / or The reaction pressure is 0.1-2 MPa, preferably 1.2-1.5 MPa; and / or The average residence time of the material in the molecular structure setting reactor is 0.5 to 10 hours, preferably 1 to 3 hours.

5. The production method according to claim 1, characterized in that: In step (4): The terminator is one or more of water, methanol and ethanol; and / or The mass ratio of the terminator to the material entering the polymerization termination reactor is 0.001 to 0.1; and / or The reaction temperature is 30-90°C, preferably 65-75°C; and / or The average residence time of the material in the polymerization termination reactor is 0.1 to 1 h.

6. The production method according to claim 1, characterized in that: The continuous polymerization production method further comprises the following steps: (5) Cleaning: In the cleaning device, the material from the polymerization termination reactor interacts with the input steam and cleaning liquid, so that the catalyst and by-products in the material enter the water phase and are discharged, the residual epoxy compound becomes the gas phase and is discharged, and the solid phase polymer is transported to the extrusion granulation unit; (6) Extrusion granulation: The solid polymer from the cleaning equipment is pelletized in the extrusion equipment.

7. The production method according to claim 6, characterized in that: In step (5): The cleaning solution is water with a pH of 6 to 8; and / or The mass ratio of the cleaning liquid to the material from the polymerization termination reactor is 0.1 to 5, preferably 1 to 2.5; and / or The mass ratio of the steam to the material from the polymerization termination reactor is 0.01 to 1.5, preferably 0.1 to 0.5; and / or In the cleaning device, the temperature at which the materials interact is 35 to 120°C, preferably 80 to 90°C; and / or The pressure is 0.02-0.05 MPa; and / or The average residence time of materials in the cleaning equipment is 0.5 to 3 hours.

8. The production method according to claim 6, characterized in that: In step (6): The temperature of the extrusion equipment is 60-210°C, preferably 100-140°C; and / or The pressure is 0 to 0.1 MPa, preferably 0.001 to 0.007 MPa.

9. A continuous polymerization production device for carbon dioxide-based polycarbonate, characterized in that: The production device includes 4 reactors, namely an aromatic ring block polymerization reactor, a carbonate block reactor, a molecular structure adjustment reactor, and a polymerization termination reactor; The aromatic ring block polymerization reactor has material mixing function and external heat exchange function, including a monomer inlet, a catalyst inlet, a material outlet and an instrument port; The carbonate block reactor has material mixing function and external heat exchange function, including material inlet, carbon dioxide gas inlet, material outlet and instrument port, and preferably adopts a horizontal and radial mixing axial non-back mixing reactor; The molecular structure adjustment reactor has material mixing function and external heat exchange function, including material inlet, regulator inlet, catalyst inlet, material outlet and instrument port; The polymerization termination reactor has a material mixing function, including a material inlet, a terminator inlet, a material outlet and an instrument port; The material outlet and the material inlet of the reactor are connected in sequence through a connecting pipeline; The pressures of the carbonate block reactor and the molecular structure setting reactor are controlled by the introduction of carbon dioxide, and there is a gas-liquid interface in the reactor.

10. The continuous polymerization production device according to claim 9, characterized in that: The continuous polymerization production device also includes a cleaning device and an extrusion device; Wherein, the cleaning equipment is a device for realizing solid-liquid-gas three-phase separation, having a material inlet, a cleaning liquid inlet, a solid material outlet, a liquid material outlet, a gas outlet and an instrument port, and having pressure and temperature control functions, and is preferably a double-axis washing self-cleaning device; The extrusion equipment is a screw extruder with the function of adjusting pressure and temperature; The material inlet and the solid material outlet of the cleaning device are respectively connected to the material outlet of the polymerization termination reactor and the extrusion device through connecting pipelines.

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