WO2024104366A1 - Devolatilization method and devolatilization system - Google Patents

Devolatilization method and devolatilization system Download PDF

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Publication number
WO2024104366A1
WO2024104366A1 PCT/CN2023/131687 CN2023131687W WO2024104366A1 WO 2024104366 A1 WO2024104366 A1 WO 2024104366A1 CN 2023131687 W CN2023131687 W CN 2023131687W WO 2024104366 A1 WO2024104366 A1 WO 2024104366A1
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Prior art keywords
water
discharge port
propylene carbonate
tank
devolatilization
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PCT/CN2023/131687
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French (fr)
Chinese (zh)
Inventor
李洪国
闫怡
傅海
王波
李宜格
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山东联欣环保科技有限公司
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Publication of WO2024104366A1 publication Critical patent/WO2024104366A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
    • B01D3/40—Extractive distillation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/88—Post-polymerisation treatment
    • C08G63/90—Purification; Drying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/32—General preparatory processes using carbon dioxide
    • C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/40—Post-polymerisation treatment

Definitions

  • the invention belongs to the technical field of polymer devolatilization, and in particular relates to a devolatilization method and a devolatilization system.
  • Polymer devolatilization is the process of removing one or more volatile components from a polymer solution. These volatile components mainly include unreacted monomers, solvents, water, and various polymerization by-products.
  • Carbon dioxide-based polyester-polycarbonate terpolymer is a new type of carbon dioxide-based biodegradable plastic. It is a new type of biodegradable plastic obtained by chemically modifying PPC with phthalic anhydride (PA). By introducing PA into the main chain of PPC, the rigidity of the polymer chain is improved, and the mechanical and thermal properties of PPC are significantly improved, which can greatly increase the added value of PPC plastics. In the synthesis process of PPC-P, there will be a lot of unreacted propylene oxide and a certain amount of propylene carbonate by-products. If they are not removed, the purity and performance of PPC-P will be greatly affected.
  • PA phthalic anhydride
  • the Chinese patent with publication number CN111378101A discloses a method for synthesizing PPC-P using PA, propylene oxide and CO 2 as raw materials.
  • a certain mass of PA, PO and catalyst are added to a high-pressure reactor, filled with CO 2 , and reacted at 80°C for 12 hours. After the reaction is completed, the reaction is quenched, and the product is dissolved, precipitated and dried to obtain the product.
  • the product devolatilization method mentioned in the patent only uses solvents for dissolution and precipitation. Since the product is a high molecular polymer with a long molecular chain, propylene oxide and propylene carbonate will still be wrapped between polymer molecules, reducing the purity of the product.
  • the object of the present invention is to provide a devolatilization method and a devolatilization system.
  • the devolatilization method provided by the present invention can improve the purity of a carbon dioxide-based polyester-polycarbonate terpolymer.
  • the present invention provides the following technical solutions:
  • the present invention provides a devolatilization method, comprising the following steps:
  • the crude product glue of the carbon dioxide-based polyester-polycarbonate terpolymer is mixed with water, and propylene oxide and propylene carbonate are removed by separation to obtain the devolatilized carbon dioxide-based polyester-polycarbonate terpolymer;
  • the crude product glue solution includes a carbon dioxide-based polyester-polycarbonate terpolymer, propylene oxide and propylene carbonate;
  • the mixing temperature is 40-95°C.
  • the mass percentage of propylene oxide in the crude product glue is 20-50%;
  • the mass percentage of propylene carbonate in the crude product glue solution is 2-6%.
  • the mass ratio of the crude product glue solution to water is 1:2-8.
  • the water is hot water, and the temperature of the hot water is 40-95°C.
  • the mixing is carried out in a twin-screw extruder
  • the length-to-diameter ratio of the twin-screw extruder is 20-60:1, the rotation speed is 50-600 r/min, and the vacuum degree is -10--90 kPa.
  • the propylene carbonate is removed in the form of an aqueous solution of propylene carbonate
  • the method further comprises extracting the propylene carbonate aqueous solution. obtaining extraction material and water;
  • the water circulation is used to mix with the crude product gum solution.
  • the present invention also provides a devolatilization system, comprising a twin-screw extruder 2, a water storage tank 3, a water receiving tank 4 and a propylene oxide receiving tank 5;
  • the twin-screw extruder 2 is provided with an extruder feed port 16, a propylene oxide discharge port 17, a polymer discharge port 20, a propylene carbonate discharge port 21 and a plurality of extruder water inlets 19;
  • the water receiving tank 4 is arranged directly below the propylene carbonate discharge port 21;
  • the propylene oxide discharge port 17 is connected to the propylene oxide receiving tank 5;
  • the water storage tank 3 is provided with a water storage tank feed port 22 and a water storage tank discharge port 23;
  • the water tank feed port 22 is communicated with the water receiving trough 4 ; the water tank discharge port 23 is communicated with the water inlets 19 of the plurality of extruders.
  • the twin-screw extruder 2 is further provided with a vacuum interface 18 ; the vacuum interface 18 is connected to the vacuum extraction system 6 .
  • it also includes an extraction tank 14 and a propylene carbonate receiving tank 15;
  • the extraction tank 14 is provided with an extraction tank feed port 27, an extraction tank discharge port 26 and an extraction tank liquid outlet 25;
  • the water storage tank 3 is also provided with a water storage tank water inlet 24;
  • the extraction tank feed port 27 is connected to the water storage tank discharge port 23; the extraction tank liquid outlet 25 is connected to the water storage tank water inlet 24; the extraction tank discharge port 26 is connected to the propylene carbonate receiving tank 15.
  • it also includes a pelletizer 7, a dryer 8 and a polymer receiving tank 9;
  • the pelletizer 7 is provided with a pelletizer feed port 28 and a pelletizer discharge port 29;
  • the pelletizer feed port 28 is in communication with the polymer discharge port 20;
  • the dryer 8 is provided with a dryer feed inlet 30 and a dryer discharge outlet 31;
  • the dryer feed port 30 is communicated with the pelletizer discharge port 29 ; the dryer discharge port 31 is communicated with the polymer receiving tank 9 .
  • the present invention provides a devolatilization method, comprising the following steps: mixing a crude product glue liquid of a carbon dioxide-based polyester-polycarbonate terpolymer with water, separating and removing propylene oxide and propylene carbonate, and obtaining a devolatilized carbon dioxide-based polyester-polycarbonate terpolymer; the crude product glue liquid comprises a carbon dioxide-based polyester-polycarbonate terpolymer, propylene oxide and propylene carbonate; and the mixing temperature is 40-95° C.
  • the present invention mixes with water at a limited temperature, and the propylene oxide in the crude product glue liquid is volatilized by heat, thereby achieving removal from the crude product glue liquid; at the same time, by utilizing the property that propylene carbonate can be dissolved in water, while water and copolymers are not miscible, propylene carbonate enters water to form an aqueous solution, and the mixed system is discharged in the form of a propylene carbonate aqueous solution, thereby achieving removal of propylene carbonate from the crude product glue liquid, and finally achieving devolatilization of the carbon dioxide-based polyester-polycarbonate terpolymer, and improving the purity of the carbon dioxide-based polyester-polycarbonate terpolymer.
  • FIG1 is a schematic diagram of the devolatilization system used in Examples 1 to 6;
  • FIG2 is a schematic diagram of the devolatilization system used in Example 7.
  • the present invention provides a devolatilization method, comprising the following steps:
  • the crude product glue of the carbon dioxide-based polyester-polycarbonate terpolymer is mixed with water, and propylene oxide and propylene carbonate are removed by separation to obtain the devolatilized carbon dioxide-based polyester-polycarbonate terpolymer;
  • the crude product glue solution includes a carbon dioxide-based polyester-polycarbonate terpolymer, propylene oxide and propylene carbonate;
  • the mixing temperature is 40-95°C.
  • the crude product glue of the carbon dioxide-based polyester-polycarbonate terpolymer is preferably prepared by polymerization reaction of propylene oxide, phthalic anhydride and carbon dioxide as raw materials.
  • the present invention has no particular limitation on the preparation method, and any method known to those skilled in the art can be used.
  • the mass percentage of propylene oxide in the crude product glue solution is preferably 20-50%; the mass percentage of propylene carbonate in the crude product glue solution is preferably 2-6%.
  • the mass ratio of the crude product gum solution to water is preferably 1:2-8, and more preferably 1:4-6.
  • the water is preferably hot water.
  • the temperature of the water is preferably 40 to 95°C, more preferably 50 to 90°C, and even more preferably 60 to 80°C.
  • the mixing temperature is 40 to 95°C, more preferably 50 to 90°C, and even more preferably 60 to 80°C.
  • mixing is carried out under the above-mentioned temperature conditions, and the propylene oxide in the crude product glue solution is collected after being volatilized by heat, thereby achieving removal from the crude product glue solution; at the same time, propylene carbonate is dissolved in water to obtain a propylene carbonate aqueous solution, and after separation, the propylene carbonate aqueous solution is discharged from the mixed system to form the propylene carbonate aqueous solution, thereby removing propylene carbonate from the crude product glue solution, thereby achieving devolatilization of the carbon dioxide-based polyester-polycarbonate terpolymer; in addition, at the above-mentioned temperature, the carbon dioxide-based polyester-polycarbonate terpolymer can maintain a glue state, thereby preventing the carbon dioxide-based polyester-polycarbonate terpolymer from deteriorating.
  • the mixing is preferably carried out in a twin-screw extruder.
  • the aspect ratio of the twin-screw extruder is preferably 20 to 60:1, more preferably 30 to 50:1, and more preferably 40:1;
  • the rotation speed is preferably 50 to 600 r/min, more preferably 100 to 500 r/min, and more preferably 200 to 400 r/min;
  • the vacuum degree is preferably -10 to -90 kPa, more preferably -20 to -80 kPa, and more preferably -30 to -70 kPa; and the time is preferably 5 to 15 min.
  • the separation is preferably carried out in the twin-screw extruder.
  • the devolatilized carbon dioxide-based polyester-polycarbonate terpolymer can be separated from the glue system by twin-screw extrusion.
  • the present invention preferably further comprises subjecting the propylene carbonate aqueous solution to an extraction treatment to obtain an extraction material and water.
  • the extractant used in the extraction treatment preferably includes one or more of toluene, 1,2-dichloroethane, 1,2-dichloropropane, dichloromethane and acetone.
  • the amount ratio of the propylene carbonate aqueous solution to the extractant is preferably 1:0.2-0.8.
  • the present invention has no special limitation on the extraction treatment process, and the extraction process can be carried out by using the technology in the art. The process that personnel are familiar with can be carried out.
  • the extraction material preferably includes propylene carbonate and an extractant.
  • the present invention also preferably includes recycling the extraction material.
  • the present invention has no particular limitation on the recycling process, and the process well known to those skilled in the art can be used.
  • the water is preferably circulated for mixing with the crude product gum solution.
  • the present invention also preferably includes cooling, pelletizing and drying the separated carbon dioxide-based polyester-polycarbonate terpolymer in sequence.
  • the present invention has no special limitation on the cooling and pelletizing process, and the process well known to those skilled in the art can be used.
  • the drying temperature is preferably 40 to 95° C.
  • the drying time is preferably 6 to 48 hours.
  • the drying is preferably carried out under vacuum conditions.
  • the present invention also provides a devolatilization system, comprising a twin-screw extruder 2, a water storage tank 3, a water receiving tank 4 and a propylene oxide receiving tank 5;
  • the twin-screw extruder 2 is provided with an extruder feed port 16, a propylene oxide discharge port 17, a polymer discharge port 20, a propylene carbonate discharge port 21 and a plurality of extruder water inlets 19;
  • the extruder feed port 16 is connected to the reactor 1;
  • the water receiving tank 4 is arranged directly below the propylene carbonate discharge port 21;
  • the propylene oxide discharge port 17 is connected to the propylene oxide receiving tank 5;
  • the water storage tank 3 is provided with a water storage tank feed port 22 and a water storage tank discharge port 23;
  • the water tank feed port 22 is communicated with the water receiving trough 4 ; the water tank discharge port 23 is communicated with the water inlets 19 of the plurality of extruders.
  • the devolatilization system includes a twin-screw extruder 2, a water storage tank 3, a water receiving tank 4 and a propylene oxide receiving tank 5.
  • the twin-screw extruder is provided with an extruder feed port 16 , a propylene oxide discharge port 17 , a polymer discharge port, a propylene carbonate discharge port 21 , a plurality of extruder water inlets 19 and a vacuum interface 18 .
  • the water receiving tank 4 is arranged directly below the propylene carbonate discharge port 21 .
  • the propylene oxide discharge port 17 is connected to the propylene oxide receiving tank 5 .
  • the water tank 3 is provided with a water tank feed port 22, a water tank discharge port 23 and a water tank water inlet 24; and a heating system is provided in the water tank 3.
  • the water tank feed port 22 is connected to the water receiving tank 4; the water tank discharge port 23 is connected to the water inlets 19 of the plurality of extruders.
  • a water pump 11, a flow meter 12 and a pneumatic valve 13 are sequentially arranged between the water storage tank outlet 23 and the water inlets 19 of the plurality of extruders.
  • the devolatilization system further includes a reaction kettle 1 ; the extruder feed port 16 is connected to the reaction kettle 1 through a melt pump 10 .
  • the devolatilization system further includes an extraction tank 14 and a propylene carbonate receiving tank 15 .
  • the extraction tank 14 is provided with an extraction tank feed port 27 , an extraction tank discharge port 26 and an extraction tank liquid outlet 25 .
  • the extraction tank feed port 27 is connected to the water storage tank discharge port 23; the extraction tank liquid outlet 25 is connected to the water storage tank water inlet 24; the extraction tank discharge port 26 is connected to the propylene carbonate receiving tank 15.
  • a water pump 11 is provided between the extraction tank feed port 27 and the water storage tank discharge port 23 .
  • the twin-screw extruder 2 is further provided with a vacuum interface 18 ; the vacuum interface 18 is connected to the vacuum pumping system 6 .
  • the devolatilization system further includes a pelletizer 7 , a dryer 8 and a polymer receiving tank 9 .
  • the pelletizer 7 is provided with a pelletizer feed port 28 and a pelletizer discharge port 29; the pelletizer feed port 28 is connected to the polymer discharge port 20;
  • the dryer 8 is provided with a dryer feed port 30 and a dryer discharge port 31; the dryer feed port 30 is connected to the pelletizer discharge port 29; the dryer discharge port 31 is connected to the polymer receiving tank 9.
  • the devolatilization system of Figure 1 is used for devolatilization, wherein: 1-reactor, 2-twin screw extruder, 3-water storage tank, 4-water receiving tank, 5-propylene oxide receiving tank, 6-vacuum extraction system, 7-pelletizer, 8-dryer, 9-polymer receiving tank, 10-melt pump, 11-water pump, 12-flow meter, 13-pneumatic valve, 16-extruder feed port, 17-propylene oxide discharge port, 18-vacuum interface, 19-extruder water inlet, 20-polymer discharge port, 21-propylene carbonate discharge port, 22-water storage tank feed port, 23-water storage tank discharge port, 28-pelletizer feed port, 29-pelletizer discharge port, 30-dryer feed port, 31-dryer discharge port;
  • the crude product glue in the reactor (wherein the mass percentage of propylene oxide is 40%; the mass percentage of propylene carbonate is 5%) is continuously pumped into the twin-screw extruder at a flow rate of 150Kg/h by a melt pump; the water in the water storage tank (the temperature is 80° C.) is continuously pumped into the twin-screw extruder through several extruder water inlets by a water pump at a water inlet flow rate of 900Kg/h; the feed liquid to be treated and the water are mixed in the twin-screw extruder (wherein the twin-screw extruder has a length-to-diameter ratio of 40:1, a rotating speed of 100r/min, a vacuum degree of -50KPa, and a time of 7min);
  • propylene oxide is discharged from the propylene oxide discharge port into the propylene oxide receiving tank; the liquid obtained after propylene carbonate is dissolved in water is discharged from the propylene carbonate discharge port into the water receiving tank, and then enters the water storage tank through the water storage tank feed port; the carbon dioxide-based polyester-polycarbonate terpolymer (PPC-P) is discharged from the polymer discharge port, enters the pelletizer through the pelletizer feed port for cooling and pelletizing, and the obtained particles are discharged from the pelletizer discharge port, enter the dryer through the dryer feed port, and after vacuum drying at 60°C for 24 hours, they are discharged from the dryer discharge port into the polymer receiving tank.
  • the propylene carbonate content in the PPC-P obtained by testing is 80ppm, and the propylene oxide content is 0.
  • the devolatilization system shown in Figure 1 is used for devolatilization:
  • the crude product glue liquid in the reaction kettle (wherein the mass percentage of propylene oxide is 30%; the mass percentage of propylene carbonate is 4%) is continuously pumped into the twin-screw extruder by a melt pump at a flow rate of 120Kg/h; the water in the water storage tank (temperature is 80°C) is continuously pumped into the twin-screw extruder through several extruder water inlets by a water pump at a water inlet flow rate of 600Kg/h; the feed liquid to be treated and the water are mixed in the twin-screw extruder (wherein the length-diameter ratio of the twin-screw extruder is 50:1, and the rotation speed is 40000rpm); the reaction mixture is stirred for 2 hours; the mixture is stirred for 3 hours; the mixture is stirred for 4 hours; the mixture is stirred for 5 hours; the mixture is stirred for 1 hour; the mixture is stirred for 2 hours; the mixture is stirred for 3 ... Speed is 120r/min, vacuum degree is
  • propylene oxide is discharged from the propylene oxide discharge port and enters the propylene oxide receiving tank; the liquid obtained after propylene carbonate is dissolved in water is discharged from the propylene carbonate discharge port and enters the water receiving tank, and then enters the water storage tank through the water storage tank feed port; the carbon dioxide-based polyester-polycarbonate terpolymer (PPC-P) is discharged from the polymer discharge port, enters the pelletizer through the pelletizer feed port for cooling and pelletizing, and the obtained particles are discharged from the pelletizer discharge port, enter the dryer through the dryer feed port, and are discharged from the dryer discharge port into the polymer receiving tank after vacuum drying at 70°C for 18 hours.
  • the propylene carbonate content in the PPC-P obtained by detection is 75ppm, and the propylene oxide content is 0.
  • the devolatilization system shown in Figure 1 is used for devolatilization:
  • the crude product glue in the reactor (wherein the mass percentage of propylene oxide is 50%; the mass percentage of propylene carbonate is 3%) is continuously pumped into the twin-screw extruder at a flow rate of 120Kg/h by a melt pump; the water in the water storage tank (the temperature is 80° C.) is continuously pumped into the twin-screw extruder through several extruder water inlets by a water pump at a water inlet flow rate of 840Kg/h; the feed liquid to be treated and water are mixed in the twin-screw extruder (wherein the twin-screw extruder has a length-to-diameter ratio of 50:1, a rotating speed of 80r/min, a vacuum degree of -70KPa, and a time of 9min);
  • propylene oxide is discharged from the propylene oxide discharge port and enters the propylene oxide receiving tank; the liquid obtained after propylene carbonate is dissolved in water is discharged from the propylene carbonate discharge port and enters the water receiving tank, and then enters the water storage tank through the water storage tank feed port; the carbon dioxide-based polyester-polycarbonate terpolymer (PPC-P) is discharged from the polymer discharge port, enters the pelletizer through the pelletizer feed port for cooling and pelletizing, and the obtained particles are discharged from the pelletizer discharge port, enter the dryer through the dryer feed port, and are discharged from the dryer discharge port into the polymer receiving tank after vacuum drying at 50°C for 24 hours.
  • the propylene carbonate content in the PPC-P obtained by testing is 60ppm, and the propylene oxide content is 0.
  • the devolatilization system shown in Figure 1 is used for devolatilization:
  • the crude product glue in the reactor (wherein the mass percentage of propylene oxide is 40%; the mass percentage of propylene carbonate is 4%) is continuously pumped into the twin-screw extruder at a flow rate of 140Kg/h by a melt pump; the water in the water storage tank (the temperature is 80° C.) is continuously pumped into the twin-screw extruder through several extruder water inlets by a water pump at a water inlet flow rate of 700Kg/h; the feed liquid to be treated and the water are mixed in the twin-screw extruder (wherein the twin-screw extruder has a length-to-diameter ratio of 30:1, a rotating speed of 100r/min, a vacuum degree of -80KPa, and a time of 12min);
  • propylene oxide is discharged from the propylene oxide discharge port and enters the propylene oxide receiving tank; the liquid obtained after propylene carbonate is dissolved in water is discharged from the propylene carbonate discharge port and enters the water receiving tank, and then enters the water storage tank through the water storage tank feed port; the carbon dioxide-based polyester-polycarbonate terpolymer (PPC-P) is discharged from the polymer discharge port, enters the pelletizer through the pelletizer feed port for cooling and pelletizing, and the obtained particles are discharged from the pelletizer discharge port, enter the dryer through the dryer feed port, and are discharged from the dryer discharge port into the polymer receiving tank after vacuum drying at 80°C for 20 hours.
  • the propylene carbonate content in the PPC-P obtained by detection is 68ppm, and the propylene oxide content is 0.
  • the devolatilization system shown in Figure 1 is used for devolatilization:
  • the crude product glue liquid in the reaction kettle (wherein the mass percentage of propylene oxide is 20%; the mass percentage of propylene carbonate is 5%) is continuously pumped into the twin-screw extruder at a flow rate of 140Kg/h by a melt pump; the water in the water storage tank (temperature is 80°C) is continuously pumped into the twin-screw extruder through several extruder water inlets by a water pump at a water inlet flow rate of 600Kg/h; the feed liquid to be treated and the water are mixed in the twin-screw extruder (wherein the length-diameter ratio of the twin-screw extruder is 30:1, and the rotation speed is 4000rpm); the reaction mixture is stirred for 2 hours; the mixture is stirred for 3 hours; the mixture is stirred for 4 hours; the mixture is stirred for 5 hours; the mixture is stirred for 1 hour; the mixture is stirred for 2 hours; the mixture is stirred for 3 ... Speed is 50r/min, vacuum degree is
  • propylene oxide is discharged from the propylene oxide discharge port and enters the propylene oxide receiving tank; the liquid obtained after propylene carbonate is dissolved in water is discharged from the propylene carbonate discharge port and enters the water receiving tank, and then enters the water storage tank through the water storage tank feed port; the carbon dioxide-based polyester-polycarbonate terpolymer (PPC-P) is discharged from the polymer discharge port, enters the pelletizer through the pelletizer feed port for cooling and pelletizing, and the obtained particles are discharged from the pelletizer discharge port, enter the dryer through the dryer feed port, and are discharged from the dryer discharge port into the polymer receiving tank after vacuum drying at 60°C for 12 hours.
  • the propylene carbonate content in the PPC-P obtained by testing is 72ppm, and the propylene oxide content is 0.
  • the devolatilization system shown in Figure 1 is used for devolatilization:
  • the crude product glue in the reactor (wherein the mass percentage of propylene oxide is 50%; the mass percentage of propylene carbonate is 4%) is continuously pumped into the twin-screw extruder at a flow rate of 130Kg/h by a melt pump; the water in the water storage tank (the temperature is 80° C.) is continuously pumped into the twin-screw extruder through several extruder water inlets by a water pump at a water inlet flow rate of 780Kg/h; the feed liquid to be treated and water are mixed in the twin-screw extruder (wherein the twin-screw extruder has a length-to-diameter ratio of 40:1, a rotating speed of 65r/min, a vacuum degree of -90KPa, and a time of 15min);
  • propylene oxide is discharged from the propylene oxide discharge port and enters the propylene oxide receiving tank; the liquid obtained after propylene carbonate is dissolved in water is discharged from the propylene carbonate discharge port and enters the water receiving tank, and then enters the water storage tank through the water storage tank feed port; the carbon dioxide-based polyester-polycarbonate terpolymer (PPC-P) is discharged from the polymer discharge port, enters the pelletizer through the pelletizer feed port for cooling and pelletizing, and the obtained particles are discharged from the pelletizer discharge port, enter the dryer through the dryer feed port, and are discharged from the dryer discharge port into the polymer receiving tank after vacuum drying at 70°C for 10 hours.
  • the propylene carbonate content in the PPC-P obtained by detection is 50ppm, and the propylene oxide content is 0.
  • the devolatilization system of Figure 2 is used for devolatilization, wherein 1-reaction kettle, 2-twin screw extruder, 3-water storage tank, 4-water receiving tank, 5-propylene oxide receiving tank, 6-vacuum extraction system, 7-granulator, 8-dryer, 9-polymer receiving tank, 10-melt pump, 11-water pump, 12-flow meter, 13-pneumatic valve, 14-extraction tank, 15-propylene carbonate receiving tank, 16-extruder feed port, 17-propylene oxide Alkane discharge port, 18-vacuum interface, 19-extruder water inlet, 20-polymer discharge port, 21-propylene carbonate discharge port, 22-water tank feed port, 23-water tank discharge port, 24-water tank water inlet, 25-extraction tank liquid outlet, 26-extraction tank discharge port, 27-extraction tank feed port, 28-granulator feed port, 29-granulator discharge port, 30-dryer feed port, 31-dryer discharge port;
  • the crude product glue in the reactor (wherein the mass percentage of propylene oxide is 45%; the mass percentage of propylene carbonate is 3%) is continuously pumped into the twin-screw extruder at a flow rate of 150Kg/h by a melt pump; the water in the water storage tank (the temperature is 80° C.) is continuously pumped into the twin-screw extruder through several extruder water inlets by a water pump at a water inlet flow rate of 900Kg/h; the feed liquid to be treated and water are mixed in the twin-screw extruder (wherein the twin-screw extruder has a length-to-diameter ratio of 40:1, a rotating speed of 100r/min, a vacuum degree of -50KPa, and a time of 10min);
  • propylene oxide is discharged from the propylene oxide discharge port into the propylene oxide receiving tank;
  • the propylene carbonate aqueous solution obtained after propylene carbonate is dissolved in water is discharged from the propylene carbonate discharge port into the water receiving tank, and enters the water storage tank through the water storage tank feed port;
  • the propylene carbonate aqueous solution in the water storage tank is discharged from the water storage tank discharge port, enters the extraction tank through the extraction tank feed port, and is mixed with toluene with a flow rate of 300 kg/h for extraction treatment to obtain extraction material and water, and the obtained extraction material is discharged from the extraction tank discharge port into the propylene carbonate receiving tank for recovery treatment;
  • the obtained water is discharged from the extraction tank liquid outlet, enters the water storage tank through the water storage tank inlet, and is recycled as a raw material;
  • the carbon dioxide-based polyester-polycarbonate terpolymer (PPC-P) is discharged from the polymer discharge port, enters the pelletizer through the pelletizer feed port for cooling and pelletizing, and the obtained particles are discharged from the pelletizer discharge port, enter the dryer through the dryer feed port, and are discharged from the dryer discharge port into the polymer receiving tank after vacuum drying at 60°C for 24 hours.
  • the propylene carbonate content in the PPC-P obtained by testing is 80ppm, and the propylene oxide content is 0.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The present invention relates to the technical field of polymer devolatilization, and in particular to a devolatilization method and a devolatilization system. According to the present invention, a crude product glue of carbon dioxide-based polyester-polycarbonate terpolymer is mixed with water; and separation is performed to remove propylene oxide and propylene carbonate to obtain devolatilized carbon dioxide-based polyester-polycarbonate terpolymer, wherein the crude product glue comprises carbon dioxide-based polyester-polycarbonate terpolymer, propylene oxide, and propylene carbonate, and the temperature of the mixing is 40-95°C. According to the present invention, the mixing with water is performed at a defined temperature, and the propylene oxide in the crude product glue is volatilized due to heating and is thus removed from the crude product glue; in addition, the propylene carbonate is dissolved in water to obtain a propylene carbonate aqueous solution, and is discharged from the mixing system in the form of the propylene carbonate aqueous solution after separation, so that the propylene carbonate is removed from the crude product glue, thereby improving the purity of the carbon dioxide-based polyester-polycarbonate terpolymer.

Description

一种脱挥方法和脱挥系统A devolatilization method and a devolatilization system 技术领域Technical Field
本发明属于聚合物脱挥技术领域，具体涉及一种脱挥方法和脱挥系统。The invention belongs to the technical field of polymer devolatilization, and in particular relates to a devolatilization method and a devolatilization system.
背景技术Background technique
聚合物脱挥是将一种或多种挥发分从聚合物溶液中脱除的过程。这些挥发分主要包括未反应的单体、溶剂、水以及各种聚合副产物。Polymer devolatilization is the process of removing one or more volatile components from a polymer solution. These volatile components mainly include unreacted monomers, solvents, water, and various polymerization by-products.
二氧化碳基聚酯-聚碳酸酯三元共聚物(PPC-P)是一种新型的二氧化碳基生物可降解塑料，是用邻苯二甲酸酐(PA)化学改性PPC得到的新型降解塑料，通过在PPC主链上引入PA，提高了高分子链的刚性，使PPC的力学和热学性能得到显著改善，可大幅提高PPC塑料的附加值。在PPC-P的合成过程中，会存在很多未反应的环氧丙烷以及一定量的碳酸丙烯酯副产物，若不把它们去除，会大大影响PPC-P的纯度和性能。Carbon dioxide-based polyester-polycarbonate terpolymer (PPC-P) is a new type of carbon dioxide-based biodegradable plastic. It is a new type of biodegradable plastic obtained by chemically modifying PPC with phthalic anhydride (PA). By introducing PA into the main chain of PPC, the rigidity of the polymer chain is improved, and the mechanical and thermal properties of PPC are significantly improved, which can greatly increase the added value of PPC plastics. In the synthesis process of PPC-P, there will be a lot of unreacted propylene oxide and a certain amount of propylene carbonate by-products. If they are not removed, the purity and performance of PPC-P will be greatly affected.
公开号为CN111378101A的中国专利公开了一种以PA、环氧丙烷和CO2为原料合成PPC-P的方法，将一定质量的PA、PO、催化剂加入到高压反应釜中，充入CO2，在80℃下反应12h，反应结束后淬火反应，产物经溶解、沉淀、干燥得到产品。但是专利中提到的产品脱挥方法仅用溶剂进行溶解及沉淀，由于产物为高分子聚合物，分子链长，仍然会有环氧丙烷和碳酸丙烯酯被包裹在聚合物分子之间，降低了产品纯度。The Chinese patent with publication number CN111378101A discloses a method for synthesizing PPC-P using PA, propylene oxide and CO 2 as raw materials. A certain mass of PA, PO and catalyst are added to a high-pressure reactor, filled with CO 2 , and reacted at 80°C for 12 hours. After the reaction is completed, the reaction is quenched, and the product is dissolved, precipitated and dried to obtain the product. However, the product devolatilization method mentioned in the patent only uses solvents for dissolution and precipitation. Since the product is a high molecular polymer with a long molecular chain, propylene oxide and propylene carbonate will still be wrapped between polymer molecules, reducing the purity of the product.
发明内容Summary of the invention
本发明的目的在于提供一种脱挥方法和脱挥系统，本发明提供的脱挥方法能够提高二氧化碳基聚酯-聚碳酸酯三元共聚物的纯度。The object of the present invention is to provide a devolatilization method and a devolatilization system. The devolatilization method provided by the present invention can improve the purity of a carbon dioxide-based polyester-polycarbonate terpolymer.
为了实现上述目的，本发明提供如下技术方案：In order to achieve the above object, the present invention provides the following technical solutions:
本发明提供了一种脱挥方法，包括以下步骤：The present invention provides a devolatilization method, comprising the following steps:
将二氧化碳基聚酯-聚碳酸酯三元共聚物的粗产物胶液和水混合，经分离去除环氧丙烷和碳酸丙烯酯，得到脱挥后的二氧化碳基聚酯-聚碳酸酯三元共聚物；The crude product glue of the carbon dioxide-based polyester-polycarbonate terpolymer is mixed with water, and propylene oxide and propylene carbonate are removed by separation to obtain the devolatilized carbon dioxide-based polyester-polycarbonate terpolymer;
所述粗产物胶液中包括二氧化碳基聚酯-聚碳酸酯三元共聚物、环氧丙烷和碳酸丙烯酯；The crude product glue solution includes a carbon dioxide-based polyester-polycarbonate terpolymer, propylene oxide and propylene carbonate;
所述混合的温度为40～95℃。The mixing temperature is 40-95°C.
优选的，所述粗产物胶液中环氧丙烷的质量百分含量为20～50％；Preferably, the mass percentage of propylene oxide in the crude product glue is 20-50%;
所述粗产物胶液中碳酸丙烯酯的质量百分含量为2～6％。The mass percentage of propylene carbonate in the crude product glue solution is 2-6%.
优选的，所述粗产物胶液和水的质量比为1∶2～8。Preferably, the mass ratio of the crude product glue solution to water is 1:2-8.
优选的，所述水为热水，所述热水的温度为40～95℃。Preferably, the water is hot water, and the temperature of the hot water is 40-95°C.
优选的，所述混合在双螺杆挤出机中进行；Preferably, the mixing is carried out in a twin-screw extruder;
所述双螺杆挤出机的长径比为20～60∶1，转速为50～600r/min，真空度为-10～-90kPa。The length-to-diameter ratio of the twin-screw extruder is 20-60:1, the rotation speed is 50-600 r/min, and the vacuum degree is -10--90 kPa.
优选的，所述碳酸丙烯酯以碳酸丙烯酯水溶液的形式去除；Preferably, the propylene carbonate is removed in the form of an aqueous solution of propylene carbonate;
去除得到碳酸丙烯酯水溶液后，还包括对所述碳酸丙烯酯水溶液进行萃取处理， 得到萃取物料和水；After removing the propylene carbonate aqueous solution, the method further comprises extracting the propylene carbonate aqueous solution. obtaining extraction material and water;
所述水循环用于与所述粗产物胶液混合。The water circulation is used to mix with the crude product gum solution.
本发明还提供了一种脱挥系统，包括双螺杆挤出机2、储水罐3、接水槽4和环氧丙烷接收罐5；The present invention also provides a devolatilization system, comprising a twin-screw extruder 2, a water storage tank 3, a water receiving tank 4 and a propylene oxide receiving tank 5;
所述双螺杆挤出机2设置有挤出机进料口16、环氧丙烷出料口17、聚合物出料口20、碳酸丙烯酯出料口21和若干挤出机进水口19；The twin-screw extruder 2 is provided with an extruder feed port 16, a propylene oxide discharge port 17, a polymer discharge port 20, a propylene carbonate discharge port 21 and a plurality of extruder water inlets 19;
所述接水槽4设置于所述碳酸丙烯酯出料口21的正下方；The water receiving tank 4 is arranged directly below the propylene carbonate discharge port 21;
所述环氧丙烷出料口17和所述环氧丙烷接收罐5连通；The propylene oxide discharge port 17 is connected to the propylene oxide receiving tank 5;
所述储水罐3设置有储水罐进料口22和储水罐出料口23；The water storage tank 3 is provided with a water storage tank feed port 22 and a water storage tank discharge port 23;
所述储水罐进料口22和所述接水槽4连通；所述储水罐出料口23和所述若干挤出机进水口19连通。The water tank feed port 22 is communicated with the water receiving trough 4 ; the water tank discharge port 23 is communicated with the water inlets 19 of the plurality of extruders.
优选的，所述双螺杆挤出机2还设置有真空接口18；所述真空接口18和抽真空系统6连通。Preferably, the twin-screw extruder 2 is further provided with a vacuum interface 18 ; the vacuum interface 18 is connected to the vacuum extraction system 6 .
优选的，还包括萃取罐14和碳酸丙烯酯接收罐15；Preferably, it also includes an extraction tank 14 and a propylene carbonate receiving tank 15;
所述萃取罐14设置有萃取罐进料口27、萃取罐出料口26和萃取罐出液口25；The extraction tank 14 is provided with an extraction tank feed port 27, an extraction tank discharge port 26 and an extraction tank liquid outlet 25;
所述储水罐3还设置有储水罐进水口24；The water storage tank 3 is also provided with a water storage tank water inlet 24;
所述萃取罐进料口27和所述储水罐出料口23连通；所述萃取罐出液口25和所述储水罐进水口24连通；所述萃取罐出料口26和碳酸丙烯酯接收罐连通15。The extraction tank feed port 27 is connected to the water storage tank discharge port 23; the extraction tank liquid outlet 25 is connected to the water storage tank water inlet 24; the extraction tank discharge port 26 is connected to the propylene carbonate receiving tank 15.
优选的，还包括切粒机7、干燥机8和聚合物接收罐9；Preferably, it also includes a pelletizer 7, a dryer 8 and a polymer receiving tank 9;
所述切粒机7设置有切粒机进料口28和切粒机出料口29；The pelletizer 7 is provided with a pelletizer feed port 28 and a pelletizer discharge port 29;
所述切粒机进料口28和所述聚合物出料口20连通；The pelletizer feed port 28 is in communication with the polymer discharge port 20;
所述干燥机8设置有干燥机进料口30和干燥机出料口31；The dryer 8 is provided with a dryer feed inlet 30 and a dryer discharge outlet 31;
所述干燥机进料口30和所述切粒机出料口29连通；所述干燥机出料口31和聚合物接收罐9连通。The dryer feed port 30 is communicated with the pelletizer discharge port 29 ; the dryer discharge port 31 is communicated with the polymer receiving tank 9 .
本发明提供了一种脱挥方法，包括以下步骤：将二氧化碳基聚酯-聚碳酸酯三元共聚物的粗产物胶液和水混合，经分离去除环氧丙烷和碳酸丙烯酯，得到脱挥后的二氧化碳基聚酯-聚碳酸酯三元共聚物；所述粗产物胶液中包括二氧化碳基聚酯-聚碳酸酯三元共聚物、环氧丙烷和碳酸丙烯酯；所述混合的温度为40～95℃。本发明在限定的温度下和水混合，所述粗产物胶液中的环氧丙烷受热挥发，实现从所述粗产物胶液中的脱除；同时，利用碳酸丙烯酯能溶于水，而水与共聚物不互溶的性质，碳酸丙烯酯进入水中形成水溶液，以碳酸丙烯酯水溶液的形成排出混合体系，从而实现碳酸丙烯酯从粗产物胶液中脱除，最终实现对二氧化碳基聚酯-聚碳酸酯三元共聚物的脱挥，提高二氧化碳基聚酯-聚碳酸酯三元共聚物的纯度。The present invention provides a devolatilization method, comprising the following steps: mixing a crude product glue liquid of a carbon dioxide-based polyester-polycarbonate terpolymer with water, separating and removing propylene oxide and propylene carbonate, and obtaining a devolatilized carbon dioxide-based polyester-polycarbonate terpolymer; the crude product glue liquid comprises a carbon dioxide-based polyester-polycarbonate terpolymer, propylene oxide and propylene carbonate; and the mixing temperature is 40-95° C. The present invention mixes with water at a limited temperature, and the propylene oxide in the crude product glue liquid is volatilized by heat, thereby achieving removal from the crude product glue liquid; at the same time, by utilizing the property that propylene carbonate can be dissolved in water, while water and copolymers are not miscible, propylene carbonate enters water to form an aqueous solution, and the mixed system is discharged in the form of a propylene carbonate aqueous solution, thereby achieving removal of propylene carbonate from the crude product glue liquid, and finally achieving devolatilization of the carbon dioxide-based polyester-polycarbonate terpolymer, and improving the purity of the carbon dioxide-based polyester-polycarbonate terpolymer.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为实施例1～6采用的脱挥系统的装置示意图；FIG1 is a schematic diagram of the devolatilization system used in Examples 1 to 6;
图2为实施例7采用的脱挥系统的装置示意图；FIG2 is a schematic diagram of the devolatilization system used in Example 7;
其中，1-反应釜，2-双螺杆挤出机，3-储水罐，4-接水槽，5-环氧丙烷接收罐，6-抽真空系统，7-切粒机，8-干燥机，9-聚合物接收罐，10-熔体泵，11-水泵，12-流量计，13-气动 阀，14-萃取罐，15-碳酸丙烯酯接收罐，16-挤出机进料口，17-环氧丙烷出料口，18-真空接口，19-挤出机进水口，20-聚合物出料口，21-碳酸丙烯酯出料口，22-储水罐进料口，23-储水罐出料口，24-储水罐进水口，25-萃取罐出液口，26-萃取罐出料口，27-萃取罐进料口，28-切粒机进料口，29-切粒机出料口，30-干燥机进料口，31-干燥机出料口。Among them, 1-reaction kettle, 2-twin screw extruder, 3-water storage tank, 4-water tank, 5-propylene oxide receiving tank, 6-vacuum system, 7-granulator, 8-dryer, 9-polymer receiving tank, 10-melt pump, 11-water pump, 12-flow meter, 13-pneumatic Valve, 14-extraction tank, 15-propylene carbonate receiving tank, 16-extruder feed port, 17-propylene oxide discharge port, 18-vacuum interface, 19-extruder water inlet, 20-polymer discharge port, 21-propylene carbonate discharge port, 22-water storage tank feed port, 23-water storage tank discharge port, 24-water storage tank water inlet, 25-extraction tank liquid outlet, 26-extraction tank discharge port, 27-extraction tank feed port, 28-granulator feed port, 29-granulator discharge port, 30-dryer feed port, 31-dryer discharge port.
具体实施方式Detailed ways
本发明提供了一种脱挥方法，包括以下步骤：The present invention provides a devolatilization method, comprising the following steps:
将二氧化碳基聚酯-聚碳酸酯三元共聚物的粗产物胶液和水混合，经分离去除环氧丙烷和碳酸丙烯酯，得到脱挥后的二氧化碳基聚酯-聚碳酸酯三元共聚物；The crude product glue of the carbon dioxide-based polyester-polycarbonate terpolymer is mixed with water, and propylene oxide and propylene carbonate are removed by separation to obtain the devolatilized carbon dioxide-based polyester-polycarbonate terpolymer;
所述粗产物胶液中包括二氧化碳基聚酯-聚碳酸酯三元共聚物、环氧丙烷和碳酸丙烯酯；The crude product glue solution includes a carbon dioxide-based polyester-polycarbonate terpolymer, propylene oxide and propylene carbonate;
所述混合的温度为40～95℃。The mixing temperature is 40-95°C.
在本发明中，所述二氧化碳基聚酯-聚碳酸酯三元共聚物的粗产物胶液优选为以环氧丙烷、苯酐和二氧化碳为原料经聚合反应制备得到。本发明对所述制备方法没有特殊的限定，采用本领域技术人员熟知的即可。In the present invention, the crude product glue of the carbon dioxide-based polyester-polycarbonate terpolymer is preferably prepared by polymerization reaction of propylene oxide, phthalic anhydride and carbon dioxide as raw materials. The present invention has no particular limitation on the preparation method, and any method known to those skilled in the art can be used.
在本发明中，所述粗产物胶液中环氧丙烷的质量百分含量优选为20～50％；所述粗产物胶液中碳酸丙烯酯的质量百分含量优选为2～6％。In the present invention, the mass percentage of propylene oxide in the crude product glue solution is preferably 20-50%; the mass percentage of propylene carbonate in the crude product glue solution is preferably 2-6%.
在本发明中，所述粗产物胶液和水的质量比优选为1∶2～8，进一步优选为1∶4～6。In the present invention, the mass ratio of the crude product gum solution to water is preferably 1:2-8, and more preferably 1:4-6.
在本发明中，所述水优选为热水。在本发明中，所述水的温度优选为40～95℃，进一步优选为50～90℃，更优选为60～80℃。In the present invention, the water is preferably hot water. In the present invention, the temperature of the water is preferably 40 to 95°C, more preferably 50 to 90°C, and even more preferably 60 to 80°C.
在本发明中，所述混合的温度为40～95℃，进一步优选为50～90℃，更优选为60～80℃。In the present invention, the mixing temperature is 40 to 95°C, more preferably 50 to 90°C, and even more preferably 60 to 80°C.
在本发明中，在上述温度条件下进行混合，所述粗产物胶液中的环氧丙烷受热挥发后收集，实现从所述粗产物胶液中的脱除；同时，碳酸丙烯酯溶于水中得到碳酸丙烯酯水溶液，经分离后，以碳酸丙烯酯水溶液的形成排出混合体系，进而将碳酸丙烯酯从粗产物胶液中的脱除，实现对二氧化碳基聚酯-聚碳酸酯三元共聚物的脱挥；另外，在上述温度下，二氧化碳基聚酯-聚碳酸酯三元共聚物能够保持胶状态，避免二氧化碳基聚酯-聚碳酸酯三元共聚物发生变质。In the present invention, mixing is carried out under the above-mentioned temperature conditions, and the propylene oxide in the crude product glue solution is collected after being volatilized by heat, thereby achieving removal from the crude product glue solution; at the same time, propylene carbonate is dissolved in water to obtain a propylene carbonate aqueous solution, and after separation, the propylene carbonate aqueous solution is discharged from the mixed system to form the propylene carbonate aqueous solution, thereby removing propylene carbonate from the crude product glue solution, thereby achieving devolatilization of the carbon dioxide-based polyester-polycarbonate terpolymer; in addition, at the above-mentioned temperature, the carbon dioxide-based polyester-polycarbonate terpolymer can maintain a glue state, thereby preventing the carbon dioxide-based polyester-polycarbonate terpolymer from deteriorating.
在本发明中，所述混合优选在双螺杆挤出机中进行。在本发明中，所述双螺杆挤出机的长径比优选为20～60∶1，进一步优选为30～50∶1，更优选为40∶1；转速优选为50～600r/min，进一步优选为100～500r/min，更优选为200～400r/min；真空度优选为-10～-90kPa，进一步优选为-20～-80kPa，更优选为-30～-70kPa；时间优选为5～15min。In the present invention, the mixing is preferably carried out in a twin-screw extruder. In the present invention, the aspect ratio of the twin-screw extruder is preferably 20 to 60:1, more preferably 30 to 50:1, and more preferably 40:1; the rotation speed is preferably 50 to 600 r/min, more preferably 100 to 500 r/min, and more preferably 200 to 400 r/min; the vacuum degree is preferably -10 to -90 kPa, more preferably -20 to -80 kPa, and more preferably -30 to -70 kPa; and the time is preferably 5 to 15 min.
在本发明中，所述分离优选在所述双螺杆挤出机中进行。在本发明中，通过双螺杆挤出能够实现脱挥后的二氧化碳基聚酯-聚碳酸酯三元共聚物从胶液体系中分离。In the present invention, the separation is preferably carried out in the twin-screw extruder. In the present invention, the devolatilized carbon dioxide-based polyester-polycarbonate terpolymer can be separated from the glue system by twin-screw extrusion.
得到所述碳酸丙烯酯水溶液后，本发明还优选包括对所述碳酸丙烯酯水溶液进行萃取处理，得到萃取物料和水。After obtaining the propylene carbonate aqueous solution, the present invention preferably further comprises subjecting the propylene carbonate aqueous solution to an extraction treatment to obtain an extraction material and water.
在本发明中，所述萃取处理采用的萃取剂优选包括甲苯、1，2-二氯乙烷、1，2-二氯丙烷、二氯甲烷和丙酮中的一种或几种。在本发明中，所述碳酸丙烯酯水溶液和萃取剂的用量比优选为1∶0.2～0.8。本发明对所述萃取处理的过程没有特殊的限定，采用本领域技术 人员熟知的过程进行即可。In the present invention, the extractant used in the extraction treatment preferably includes one or more of toluene, 1,2-dichloroethane, 1,2-dichloropropane, dichloromethane and acetone. In the present invention, the amount ratio of the propylene carbonate aqueous solution to the extractant is preferably 1:0.2-0.8. The present invention has no special limitation on the extraction treatment process, and the extraction process can be carried out by using the technology in the art. The process that personnel are familiar with can be carried out.
在本发明中，所述萃取物料优选包括碳酸丙烯酯和萃取剂。本发明还优选包括对所述萃取物料进行回收处理。本发明对所述回收处理的过程没有特殊的限定，采用本领域技术人员熟知的过程进行即可。In the present invention, the extraction material preferably includes propylene carbonate and an extractant. The present invention also preferably includes recycling the extraction material. The present invention has no particular limitation on the recycling process, and the process well known to those skilled in the art can be used.
在本发明中，所述水优选循环用于与所述粗产物胶液混合。In the present invention, the water is preferably circulated for mixing with the crude product gum solution.
所述分离后，本发明还优选包括将所述分离得到的二氧化碳基聚酯-聚碳酸酯三元共聚物依次进行冷却、切粒和干燥。本发明对所述冷却和切粒的过程没有特殊的限定，采用本领域技术人员熟知的过程进行即可。在本发明中，所述干燥的温度优选为40～95℃，时间优选为6～48h。在本发明中，所述干燥优选在真空条件下进行。After the separation, the present invention also preferably includes cooling, pelletizing and drying the separated carbon dioxide-based polyester-polycarbonate terpolymer in sequence. The present invention has no special limitation on the cooling and pelletizing process, and the process well known to those skilled in the art can be used. In the present invention, the drying temperature is preferably 40 to 95° C., and the drying time is preferably 6 to 48 hours. In the present invention, the drying is preferably carried out under vacuum conditions.
本发明还提供了一种脱挥系统，包括双螺杆挤出机2、储水罐3、接水槽4和环氧丙烷接收罐5；The present invention also provides a devolatilization system, comprising a twin-screw extruder 2, a water storage tank 3, a water receiving tank 4 and a propylene oxide receiving tank 5;
所述双螺杆挤出机2设置有挤出机进料口16、环氧丙烷出料口17、聚合物出料口20、碳酸丙烯酯出料口21和若干挤出机进水口19；The twin-screw extruder 2 is provided with an extruder feed port 16, a propylene oxide discharge port 17, a polymer discharge port 20, a propylene carbonate discharge port 21 and a plurality of extruder water inlets 19;
所述挤出机进料口16和所述反应釜1连通；The extruder feed port 16 is connected to the reactor 1;
所述接水槽4设置于所述碳酸丙烯酯出料口21的正下方；The water receiving tank 4 is arranged directly below the propylene carbonate discharge port 21;
所述环氧丙烷出料口17和所述环氧丙烷接收罐5连通；The propylene oxide discharge port 17 is connected to the propylene oxide receiving tank 5;
所述储水罐3设置有储水罐进料口22和储水罐出料口23；The water storage tank 3 is provided with a water storage tank feed port 22 and a water storage tank discharge port 23;
所述储水罐进料口22和所述接水槽4连通；所述储水罐出料口23和所述若干挤出机进水口19连通。The water tank feed port 22 is communicated with the water receiving trough 4 ; the water tank discharge port 23 is communicated with the water inlets 19 of the plurality of extruders.
作为本发明的一个具体实施例，所述脱挥系统包括双螺杆挤出机2、储水罐3、接水槽4和环氧丙烷接收罐5。As a specific embodiment of the present invention, the devolatilization system includes a twin-screw extruder 2, a water storage tank 3, a water receiving tank 4 and a propylene oxide receiving tank 5.
作为本发明的一个具体实施例，所述双螺杆挤出机设置有挤出机进料口16、环氧丙烷出料口17、聚合物出料口、碳酸丙烯酯出料口21、若干挤出机进水口19和真空接口18。As a specific embodiment of the present invention, the twin-screw extruder is provided with an extruder feed port 16 , a propylene oxide discharge port 17 , a polymer discharge port, a propylene carbonate discharge port 21 , a plurality of extruder water inlets 19 and a vacuum interface 18 .
作为本发明的一个具体实施例，所述接水槽4设置于所述碳酸丙烯酯出料口21的正下方。As a specific embodiment of the present invention, the water receiving tank 4 is arranged directly below the propylene carbonate discharge port 21 .
作为本发明的一个具体实施例，所述环氧丙烷出料口17和所述环氧丙烷接收罐5连通。As a specific embodiment of the present invention, the propylene oxide discharge port 17 is connected to the propylene oxide receiving tank 5 .
作为本发明的一个具体实施例，所述储水罐3设置有储水罐进料口22、储水罐出料口23和储水罐进水口24；所述储水罐3中设置有加热系统。As a specific embodiment of the present invention, the water tank 3 is provided with a water tank feed port 22, a water tank discharge port 23 and a water tank water inlet 24; and a heating system is provided in the water tank 3.
作为本发明的一个具体实施例，所述储水罐进料口22和所述接水槽4连通；所述储水罐出料口23和所述若干挤出机进水口19连通。As a specific embodiment of the present invention, the water tank feed port 22 is connected to the water receiving tank 4; the water tank discharge port 23 is connected to the water inlets 19 of the plurality of extruders.
作为本发明的一个具体实施例，所述储水罐出料口23和所述若干挤出机进水口19之间依次设置有水泵11、流量计12和气动阀13。As a specific embodiment of the present invention, a water pump 11, a flow meter 12 and a pneumatic valve 13 are sequentially arranged between the water storage tank outlet 23 and the water inlets 19 of the plurality of extruders.
作为本发明的一个具体实施例，所述脱挥系统还包括反应釜1；所述挤出机进料口16通过熔体泵10和所述反应釜1连通。As a specific embodiment of the present invention, the devolatilization system further includes a reaction kettle 1 ; the extruder feed port 16 is connected to the reaction kettle 1 through a melt pump 10 .
作为本发明的一个具体实施例，所述脱挥系统还包括萃取罐14和碳酸丙烯酯接收罐15。As a specific embodiment of the present invention, the devolatilization system further includes an extraction tank 14 and a propylene carbonate receiving tank 15 .
作为本发明的一个具体实施例，所述萃取罐14设置有萃取罐进料口27、萃取罐出料口26和萃取罐出液口25。 As a specific embodiment of the present invention, the extraction tank 14 is provided with an extraction tank feed port 27 , an extraction tank discharge port 26 and an extraction tank liquid outlet 25 .
作为本发明的一个具体实施例，所述萃取罐进料口27和所述储水罐出料口23连通；所述萃取罐出液口25和所述储水罐进水口24连通；所述萃取罐出料口26和碳酸丙烯酯接收罐15连通。As a specific embodiment of the present invention, the extraction tank feed port 27 is connected to the water storage tank discharge port 23; the extraction tank liquid outlet 25 is connected to the water storage tank water inlet 24; the extraction tank discharge port 26 is connected to the propylene carbonate receiving tank 15.
作为本发明的一个具体实施例，所述萃取罐进料口27和所述储水罐出料口23之间设置有水泵11。As a specific embodiment of the present invention, a water pump 11 is provided between the extraction tank feed port 27 and the water storage tank discharge port 23 .
作为本发明的一个具体实施例，所述双螺杆挤出机2还设置有真空接口18；所述真空接口18和抽真空系统6连通。As a specific embodiment of the present invention, the twin-screw extruder 2 is further provided with a vacuum interface 18 ; the vacuum interface 18 is connected to the vacuum pumping system 6 .
作为本发明的一个具体实施例，所述脱挥系统还包括切粒机7、干燥机8和聚合物接收罐9。As a specific embodiment of the present invention, the devolatilization system further includes a pelletizer 7 , a dryer 8 and a polymer receiving tank 9 .
作为本发明的一个具体实施例，所述切粒机7设置有切粒机进料口28和切粒机出料口29；所述切粒机进料口28和所述聚合物出料口20连通；As a specific embodiment of the present invention, the pelletizer 7 is provided with a pelletizer feed port 28 and a pelletizer discharge port 29; the pelletizer feed port 28 is connected to the polymer discharge port 20;
作为本发明的一个具体实施例，所述干燥机8设置有干燥机进料口30和干燥机出料口31；所述干燥机进料口30和所述切粒机出料口29连通；所述干燥机出料口31和聚合物接收罐9连通。As a specific embodiment of the present invention, the dryer 8 is provided with a dryer feed port 30 and a dryer discharge port 31; the dryer feed port 30 is connected to the pelletizer discharge port 29; the dryer discharge port 31 is connected to the polymer receiving tank 9.
为了进一步说明本发明，下面结合附图和实施例对本发明提供的一种脱挥方法和脱挥系统进行详细地描述，但不能将它们理解为对本发明保护范围的限定。In order to further illustrate the present invention, a devolatilization method and a devolatilization system provided by the present invention are described in detail below in conjunction with the accompanying drawings and embodiments, but they should not be construed as limiting the scope of protection of the present invention.
实施例1Example 1
采用图1的脱挥系统进行脱挥，其中，1-反应釜，2-双螺杆挤出机，3-储水罐，4-接水槽，5-环氧丙烷接收罐，6-抽真空系统，7-切粒机，8-干燥机，9-聚合物接收罐，10-熔体泵，11-水泵，12-流量计，13-气动阀，16-挤出机进料口，17-环氧丙烷出料口，18-真空接口，19-挤出机进水口，20-聚合物出料口，21-碳酸丙烯酯出料口，22-储水罐进料口，23-储水罐出料口，28-切粒机进料口，29-切粒机出料口，30-干燥机进料口，31-干燥机出料口；The devolatilization system of Figure 1 is used for devolatilization, wherein: 1-reactor, 2-twin screw extruder, 3-water storage tank, 4-water receiving tank, 5-propylene oxide receiving tank, 6-vacuum extraction system, 7-pelletizer, 8-dryer, 9-polymer receiving tank, 10-melt pump, 11-water pump, 12-flow meter, 13-pneumatic valve, 16-extruder feed port, 17-propylene oxide discharge port, 18-vacuum interface, 19-extruder water inlet, 20-polymer discharge port, 21-propylene carbonate discharge port, 22-water storage tank feed port, 23-water storage tank discharge port, 28-pelletizer feed port, 29-pelletizer discharge port, 30-dryer feed port, 31-dryer discharge port;
将反应釜中的粗产物胶液(其中环氧丙烷的质量百分含量为40％；碳酸丙烯酯的质量百分含量为5％)利用熔体泵以150Kg/h的流量连续泵入双螺杆挤出机中；将储水罐中的水(温度为80℃)利用水泵以900Kg/h的进水流量通过若干挤出机进水口连续泵入双螺杆挤出机中；将待处理料液和水在双螺杆挤出机中混合(其中双螺杆挤出机长径比为40∶1，转速为100r/min，真空度为-50KPa，时间为7min)；The crude product glue in the reactor (wherein the mass percentage of propylene oxide is 40%; the mass percentage of propylene carbonate is 5%) is continuously pumped into the twin-screw extruder at a flow rate of 150Kg/h by a melt pump; the water in the water storage tank (the temperature is 80° C.) is continuously pumped into the twin-screw extruder through several extruder water inlets by a water pump at a water inlet flow rate of 900Kg/h; the feed liquid to be treated and the water are mixed in the twin-screw extruder (wherein the twin-screw extruder has a length-to-diameter ratio of 40:1, a rotating speed of 100r/min, a vacuum degree of -50KPa, and a time of 7min);
在混合过程中，环氧丙烷从环氧丙烷出料口排出进入环氧丙烷接收罐；碳酸丙烯酯溶于水后得到的料液从碳酸丙烯酯出料口排出进入接水槽，然后经储水罐进料口进入储水罐；二氧化碳基聚酯-聚碳酸酯三元共聚物(PPC-P)从聚合物出料口排出，经切粒机进料口进入切粒机中进行冷却和切粒，得到的颗粒从切粒机出料口排出，经干燥机进料口进入干燥机，在60℃真空烘干24h后，经干燥机出料口排出进入聚合物接收罐，经检测得到的PPC-P中碳酸丙烯酯含量为80ppm，环氧丙烷的含量为0。During the mixing process, propylene oxide is discharged from the propylene oxide discharge port into the propylene oxide receiving tank; the liquid obtained after propylene carbonate is dissolved in water is discharged from the propylene carbonate discharge port into the water receiving tank, and then enters the water storage tank through the water storage tank feed port; the carbon dioxide-based polyester-polycarbonate terpolymer (PPC-P) is discharged from the polymer discharge port, enters the pelletizer through the pelletizer feed port for cooling and pelletizing, and the obtained particles are discharged from the pelletizer discharge port, enter the dryer through the dryer feed port, and after vacuum drying at 60°C for 24 hours, they are discharged from the dryer discharge port into the polymer receiving tank. The propylene carbonate content in the PPC-P obtained by testing is 80ppm, and the propylene oxide content is 0.
实施例2Example 2
采用图1的脱挥系统进行脱挥：The devolatilization system shown in Figure 1 is used for devolatilization:
将反应釜中的粗产物胶液(其中环氧丙烷的质量百分含量为30％；碳酸丙烯酯的质量百分含量为4％)利用熔体泵以120Kg/h的流量连续泵入双螺杆挤出机中；将储水罐中的水(温度为80℃)利用水泵以600Kg/h的进水流量通过若干挤出机进水口连续泵入双螺杆挤出机中；将待处理料液和水在双螺杆挤出机中混合(其中双螺杆挤出机长径比为50∶1，转 速为120r/min，真空度为-50KPa，时间为10min)；The crude product glue liquid in the reaction kettle (wherein the mass percentage of propylene oxide is 30%; the mass percentage of propylene carbonate is 4%) is continuously pumped into the twin-screw extruder by a melt pump at a flow rate of 120Kg/h; the water in the water storage tank (temperature is 80°C) is continuously pumped into the twin-screw extruder through several extruder water inlets by a water pump at a water inlet flow rate of 600Kg/h; the feed liquid to be treated and the water are mixed in the twin-screw extruder (wherein the length-diameter ratio of the twin-screw extruder is 50:1, and the rotation speed is 40000rpm); the reaction mixture is stirred for 2 hours; the mixture is stirred for 3 hours; the mixture is stirred for 4 hours; the mixture is stirred for 5 hours; the mixture is stirred for 1 hour; the mixture is stirred for 2 hours; the mixture is stirred for 3 ... Speed is 120r/min, vacuum degree is -50KPa, time is 10min);
在混合过程中，环氧丙烷从环氧丙烷出料口排出进入环氧丙烷接收罐；碳酸丙烯酯溶于水后得到的料液从碳酸丙烯酯出料口排出进入接水槽，然后经储水罐进料口进入储水罐；二氧化碳基聚酯-聚碳酸酯三元共聚物(PPC-P)从聚合物出料口排出，经切粒机进料口进入切粒机中进行冷却和切粒，得到的颗粒从切粒机出料口排出，经干燥机进料口进入干燥机，在70℃真空烘干18h后经干燥机出料口排出进入聚合物接收罐，经检测得到的PPC-P中碳酸丙烯酯含量为75ppm，环氧丙烷的含量为0。During the mixing process, propylene oxide is discharged from the propylene oxide discharge port and enters the propylene oxide receiving tank; the liquid obtained after propylene carbonate is dissolved in water is discharged from the propylene carbonate discharge port and enters the water receiving tank, and then enters the water storage tank through the water storage tank feed port; the carbon dioxide-based polyester-polycarbonate terpolymer (PPC-P) is discharged from the polymer discharge port, enters the pelletizer through the pelletizer feed port for cooling and pelletizing, and the obtained particles are discharged from the pelletizer discharge port, enter the dryer through the dryer feed port, and are discharged from the dryer discharge port into the polymer receiving tank after vacuum drying at 70°C for 18 hours. The propylene carbonate content in the PPC-P obtained by detection is 75ppm, and the propylene oxide content is 0.
实施例3Example 3
采用图1的脱挥系统进行脱挥：The devolatilization system shown in Figure 1 is used for devolatilization:
将反应釜中的粗产物胶液(其中环氧丙烷的质量百分含量为50％；碳酸丙烯酯的质量百分含量为3％)利用熔体泵以120Kg/h的流量连续泵入双螺杆挤出机中；将储水罐中的水(温度为80℃)利用水泵以840Kg/h的进水流量通过若干挤出机进水口连续泵入双螺杆挤出机中；将待处理料液和水在双螺杆挤出机中混合(其中双螺杆挤出机长径比为50∶1，转速为80r/min，真空度为-70KPa，时间为9min)；The crude product glue in the reactor (wherein the mass percentage of propylene oxide is 50%; the mass percentage of propylene carbonate is 3%) is continuously pumped into the twin-screw extruder at a flow rate of 120Kg/h by a melt pump; the water in the water storage tank (the temperature is 80° C.) is continuously pumped into the twin-screw extruder through several extruder water inlets by a water pump at a water inlet flow rate of 840Kg/h; the feed liquid to be treated and water are mixed in the twin-screw extruder (wherein the twin-screw extruder has a length-to-diameter ratio of 50:1, a rotating speed of 80r/min, a vacuum degree of -70KPa, and a time of 9min);
在混合过程中，环氧丙烷从环氧丙烷出料口排出进入环氧丙烷接收罐；碳酸丙烯酯溶于水后得到的料液从碳酸丙烯酯出料口排出进入接水槽，然后经储水罐进料口进入储水罐；二氧化碳基聚酯-聚碳酸酯三元共聚物(PPC-P)从聚合物出料口排出，经切粒机进料口进入切粒机中进行冷却和切粒，得到的颗粒从切粒机出料口排出，经干燥机进料口进入干燥机，在50℃真空烘干24h后经干燥机出料口排出进入聚合物接收罐，经检测得到的PPC-P中碳酸丙烯酯含量为60ppm，环氧丙烷的含量为0。During the mixing process, propylene oxide is discharged from the propylene oxide discharge port and enters the propylene oxide receiving tank; the liquid obtained after propylene carbonate is dissolved in water is discharged from the propylene carbonate discharge port and enters the water receiving tank, and then enters the water storage tank through the water storage tank feed port; the carbon dioxide-based polyester-polycarbonate terpolymer (PPC-P) is discharged from the polymer discharge port, enters the pelletizer through the pelletizer feed port for cooling and pelletizing, and the obtained particles are discharged from the pelletizer discharge port, enter the dryer through the dryer feed port, and are discharged from the dryer discharge port into the polymer receiving tank after vacuum drying at 50°C for 24 hours. The propylene carbonate content in the PPC-P obtained by testing is 60ppm, and the propylene oxide content is 0.
实施例4Example 4
采用图1的脱挥系统进行脱挥：The devolatilization system shown in Figure 1 is used for devolatilization:
将反应釜中的粗产物胶液(其中环氧丙烷的质量百分含量为40％；碳酸丙烯酯的质量百分含量为4％)利用熔体泵以140Kg/h的流量连续泵入双螺杆挤出机中；将储水罐中的水(温度为80℃)利用水泵以700Kg/h的进水流量通过若干挤出机进水口连续泵入双螺杆挤出机中；将待处理料液和水在双螺杆挤出机中混合(其中双螺杆挤出机长径比为30∶1，转速为100r/min，真空度为-80KPa，时间为12min)；The crude product glue in the reactor (wherein the mass percentage of propylene oxide is 40%; the mass percentage of propylene carbonate is 4%) is continuously pumped into the twin-screw extruder at a flow rate of 140Kg/h by a melt pump; the water in the water storage tank (the temperature is 80° C.) is continuously pumped into the twin-screw extruder through several extruder water inlets by a water pump at a water inlet flow rate of 700Kg/h; the feed liquid to be treated and the water are mixed in the twin-screw extruder (wherein the twin-screw extruder has a length-to-diameter ratio of 30:1, a rotating speed of 100r/min, a vacuum degree of -80KPa, and a time of 12min);
在混合过程中，环氧丙烷从环氧丙烷出料口排出进入环氧丙烷接收罐；碳酸丙烯酯溶于水后得到的料液从碳酸丙烯酯出料口排出进入接水槽，然后经储水罐进料口进入储水罐；二氧化碳基聚酯-聚碳酸酯三元共聚物(PPC-P)从聚合物出料口排出，经切粒机进料口进入切粒机中进行冷却和切粒，得到的颗粒从切粒机出料口排出，经干燥机进料口进入干燥机，在80℃真空烘干20h后经干燥机出料口排出进入聚合物接收罐，经检测得到的PPC-P中碳酸丙烯酯含量为68ppm，环氧丙烷的含量为0。During the mixing process, propylene oxide is discharged from the propylene oxide discharge port and enters the propylene oxide receiving tank; the liquid obtained after propylene carbonate is dissolved in water is discharged from the propylene carbonate discharge port and enters the water receiving tank, and then enters the water storage tank through the water storage tank feed port; the carbon dioxide-based polyester-polycarbonate terpolymer (PPC-P) is discharged from the polymer discharge port, enters the pelletizer through the pelletizer feed port for cooling and pelletizing, and the obtained particles are discharged from the pelletizer discharge port, enter the dryer through the dryer feed port, and are discharged from the dryer discharge port into the polymer receiving tank after vacuum drying at 80°C for 20 hours. The propylene carbonate content in the PPC-P obtained by detection is 68ppm, and the propylene oxide content is 0.
实施例5Example 5
采用图1的脱挥系统进行脱挥：The devolatilization system shown in Figure 1 is used for devolatilization:
将反应釜中的粗产物胶液(其中环氧丙烷的质量百分含量为20％；碳酸丙烯酯的质量百分含量为5％)利用熔体泵以140Kg/h的流量连续泵入双螺杆挤出机中；将储水罐中的水(温度为80℃)利用水泵以600Kg/h的进水流量通过若干挤出机进水口连续泵入双螺杆挤出机中；将待处理料液和水在双螺杆挤出机中混合(其中双螺杆挤出机长径比为30∶1，转 速为50r/min，真空度为-30KPa，时间为6min)；The crude product glue liquid in the reaction kettle (wherein the mass percentage of propylene oxide is 20%; the mass percentage of propylene carbonate is 5%) is continuously pumped into the twin-screw extruder at a flow rate of 140Kg/h by a melt pump; the water in the water storage tank (temperature is 80°C) is continuously pumped into the twin-screw extruder through several extruder water inlets by a water pump at a water inlet flow rate of 600Kg/h; the feed liquid to be treated and the water are mixed in the twin-screw extruder (wherein the length-diameter ratio of the twin-screw extruder is 30:1, and the rotation speed is 4000rpm); the reaction mixture is stirred for 2 hours; the mixture is stirred for 3 hours; the mixture is stirred for 4 hours; the mixture is stirred for 5 hours; the mixture is stirred for 1 hour; the mixture is stirred for 2 hours; the mixture is stirred for 3 ... Speed is 50r/min, vacuum degree is -30KPa, time is 6min);
在混合过程中，环氧丙烷从环氧丙烷出料口排出进入环氧丙烷接收罐；碳酸丙烯酯溶于水后得到的料液从碳酸丙烯酯出料口排出进入接水槽，然后经储水罐进料口进入储水罐；二氧化碳基聚酯-聚碳酸酯三元共聚物(PPC-P)从聚合物出料口排出，经切粒机进料口进入切粒机中进行冷却和切粒，得到的颗粒从切粒机出料口排出，经干燥机进料口进入干燥机，在60℃真空烘干12h后经干燥机出料口排出进入聚合物接收罐，经检测得到的PPC-P中碳酸丙烯酯含量为72ppm，环氧丙烷的含量为0。During the mixing process, propylene oxide is discharged from the propylene oxide discharge port and enters the propylene oxide receiving tank; the liquid obtained after propylene carbonate is dissolved in water is discharged from the propylene carbonate discharge port and enters the water receiving tank, and then enters the water storage tank through the water storage tank feed port; the carbon dioxide-based polyester-polycarbonate terpolymer (PPC-P) is discharged from the polymer discharge port, enters the pelletizer through the pelletizer feed port for cooling and pelletizing, and the obtained particles are discharged from the pelletizer discharge port, enter the dryer through the dryer feed port, and are discharged from the dryer discharge port into the polymer receiving tank after vacuum drying at 60°C for 12 hours. The propylene carbonate content in the PPC-P obtained by testing is 72ppm, and the propylene oxide content is 0.
实施例6Example 6
采用图1的脱挥系统进行脱挥：The devolatilization system shown in Figure 1 is used for devolatilization:
将反应釜中的粗产物胶液(其中环氧丙烷的质量百分含量为50％；碳酸丙烯酯的质量百分含量为4％)利用熔体泵以130Kg/h的流量连续泵入双螺杆挤出机中；将储水罐中的水(温度为80℃)利用水泵以780Kg/h的进水流量通过若干挤出机进水口连续泵入双螺杆挤出机中；将待处理料液和水在双螺杆挤出机中混合(其中双螺杆挤出机长径比为40∶1，转速为65r/min，真空度为-90KPa，时间为15min)；The crude product glue in the reactor (wherein the mass percentage of propylene oxide is 50%; the mass percentage of propylene carbonate is 4%) is continuously pumped into the twin-screw extruder at a flow rate of 130Kg/h by a melt pump; the water in the water storage tank (the temperature is 80° C.) is continuously pumped into the twin-screw extruder through several extruder water inlets by a water pump at a water inlet flow rate of 780Kg/h; the feed liquid to be treated and water are mixed in the twin-screw extruder (wherein the twin-screw extruder has a length-to-diameter ratio of 40:1, a rotating speed of 65r/min, a vacuum degree of -90KPa, and a time of 15min);
在混合过程中，环氧丙烷从环氧丙烷出料口排出进入环氧丙烷接收罐；碳酸丙烯酯溶于水后得到的料液从碳酸丙烯酯出料口排出进入接水槽，然后经储水罐进料口进入储水罐；二氧化碳基聚酯-聚碳酸酯三元共聚物(PPC-P)从聚合物出料口排出，经切粒机进料口进入切粒机中进行冷却和切粒，得到的颗粒从切粒机出料口排出，经干燥机进料口进入干燥机，在70℃真空烘干10h后经干燥机出料口排出进入聚合物接收罐，经检测得到的PPC-P中碳酸丙烯酯含量为50ppm，环氧丙烷的含量为0。During the mixing process, propylene oxide is discharged from the propylene oxide discharge port and enters the propylene oxide receiving tank; the liquid obtained after propylene carbonate is dissolved in water is discharged from the propylene carbonate discharge port and enters the water receiving tank, and then enters the water storage tank through the water storage tank feed port; the carbon dioxide-based polyester-polycarbonate terpolymer (PPC-P) is discharged from the polymer discharge port, enters the pelletizer through the pelletizer feed port for cooling and pelletizing, and the obtained particles are discharged from the pelletizer discharge port, enter the dryer through the dryer feed port, and are discharged from the dryer discharge port into the polymer receiving tank after vacuum drying at 70°C for 10 hours. The propylene carbonate content in the PPC-P obtained by detection is 50ppm, and the propylene oxide content is 0.
实施例7Example 7
采用图2的脱挥系统进行脱挥，其中，1-反应釜，2-双螺杆挤出机，3-储水罐，4-接水槽，5-环氧丙烷接收罐，6-抽真空系统，7-切粒机，8-干燥机，9-聚合物接收罐，10-熔体泵，11-水泵，12-流量计，13-气动阀，14-萃取罐，15-碳酸丙烯酯接收罐，16-挤出机进料口，17-环氧丙烷出料口，18-真空接口，19-挤出机进水口，20-聚合物出料口，21-碳酸丙烯酯出料口，22-储水罐进料口，23-储水罐出料口，24-储水罐进水口，25-萃取罐出液口，26-萃取罐出料口，27-萃取罐进料口，28-切粒机进料口，29-切粒机出料口，30-干燥机进料口，31-干燥机出料口；The devolatilization system of Figure 2 is used for devolatilization, wherein 1-reaction kettle, 2-twin screw extruder, 3-water storage tank, 4-water receiving tank, 5-propylene oxide receiving tank, 6-vacuum extraction system, 7-granulator, 8-dryer, 9-polymer receiving tank, 10-melt pump, 11-water pump, 12-flow meter, 13-pneumatic valve, 14-extraction tank, 15-propylene carbonate receiving tank, 16-extruder feed port, 17-propylene oxide Alkane discharge port, 18-vacuum interface, 19-extruder water inlet, 20-polymer discharge port, 21-propylene carbonate discharge port, 22-water tank feed port, 23-water tank discharge port, 24-water tank water inlet, 25-extraction tank liquid outlet, 26-extraction tank discharge port, 27-extraction tank feed port, 28-granulator feed port, 29-granulator discharge port, 30-dryer feed port, 31-dryer discharge port;
将反应釜中的粗产物胶液(其中环氧丙烷的质量百分含量为45％；碳酸丙烯酯的质量百分含量为3％)利用熔体泵以150Kg/h的流量连续泵入双螺杆挤出机中；将储水罐中的水(温度为80℃)利用水泵以900Kg/h的进水流量通过若干挤出机进水口连续泵入双螺杆挤出机中；将待处理料液和水在双螺杆挤出机中混合(其中双螺杆挤出机长径比为40∶1，转速为100r/min，真空度为-50KPa，时间为10min)；The crude product glue in the reactor (wherein the mass percentage of propylene oxide is 45%; the mass percentage of propylene carbonate is 3%) is continuously pumped into the twin-screw extruder at a flow rate of 150Kg/h by a melt pump; the water in the water storage tank (the temperature is 80° C.) is continuously pumped into the twin-screw extruder through several extruder water inlets by a water pump at a water inlet flow rate of 900Kg/h; the feed liquid to be treated and water are mixed in the twin-screw extruder (wherein the twin-screw extruder has a length-to-diameter ratio of 40:1, a rotating speed of 100r/min, a vacuum degree of -50KPa, and a time of 10min);
在混合过程中，环氧丙烷从环氧丙烷出料口排出进入环氧丙烷接收罐；碳酸丙烯酯溶于水后得到的碳酸丙烯酯水溶液从碳酸丙烯酯出料口排出进入接水槽，经储水罐进料口进入储水罐；储水罐中的碳酸丙烯酯水溶液从储水罐出料口排出，经萃取罐进料口进入萃取罐，和流量为300Kg/h的甲苯混合进行萃取处理，得到萃取物料和水，得到的萃取物料经萃取罐出料口排出进入碳酸丙烯酯接收罐进行回收处理；得到的水经萃取罐出液口排出，经储水罐进水口进行储水罐，作为原料进行循环利用； During the mixing process, propylene oxide is discharged from the propylene oxide discharge port into the propylene oxide receiving tank; the propylene carbonate aqueous solution obtained after propylene carbonate is dissolved in water is discharged from the propylene carbonate discharge port into the water receiving tank, and enters the water storage tank through the water storage tank feed port; the propylene carbonate aqueous solution in the water storage tank is discharged from the water storage tank discharge port, enters the extraction tank through the extraction tank feed port, and is mixed with toluene with a flow rate of 300 kg/h for extraction treatment to obtain extraction material and water, and the obtained extraction material is discharged from the extraction tank discharge port into the propylene carbonate receiving tank for recovery treatment; the obtained water is discharged from the extraction tank liquid outlet, enters the water storage tank through the water storage tank inlet, and is recycled as a raw material;
二氧化碳基聚酯-聚碳酸酯三元共聚物(PPC-P)从聚合物出料口排出，经切粒机进料口进入切粒机中进行冷却和切粒，得到的颗粒从切粒机出料口排出，经干燥机进料口进入干燥机，在60℃真空烘干24h后经干燥机出料口排出进入聚合物接收罐，经检测得到的PPC-P中碳酸丙烯酯含量为80ppm，环氧丙烷的含量为0。The carbon dioxide-based polyester-polycarbonate terpolymer (PPC-P) is discharged from the polymer discharge port, enters the pelletizer through the pelletizer feed port for cooling and pelletizing, and the obtained particles are discharged from the pelletizer discharge port, enter the dryer through the dryer feed port, and are discharged from the dryer discharge port into the polymer receiving tank after vacuum drying at 60°C for 24 hours. The propylene carbonate content in the PPC-P obtained by testing is 80ppm, and the propylene oxide content is 0.
尽管上述实施例对本发明做出了详尽的描述，但它仅仅是本发明一部分实施例，而不是全部实施例，还可以根据本实施例在不经创造性前提下获得其他实施例，这些实施例都属于本发明保护范围。 Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims (10)

  1. 一种脱挥方法，其特征在于，包括以下步骤：A devolatilization method, characterized in that it comprises the following steps:
    将二氧化碳基聚酯-聚碳酸酯三元共聚物的粗产物胶液和水混合，经分离去除环氧丙烷和碳酸丙烯酯，得到脱挥后的二氧化碳基聚酯-聚碳酸酯三元共聚物；The crude product glue of the carbon dioxide-based polyester-polycarbonate terpolymer is mixed with water, and propylene oxide and propylene carbonate are removed by separation to obtain the devolatilized carbon dioxide-based polyester-polycarbonate terpolymer;
    所述粗产物胶液中包括二氧化碳基聚酯-聚碳酸酯三元共聚物、环氧丙烷和碳酸丙烯酯；The crude product glue solution includes a carbon dioxide-based polyester-polycarbonate terpolymer, propylene oxide and propylene carbonate;
    所述混合的温度为40～95℃。The mixing temperature is 40-95°C.
  2. 根据权利要求1所述的脱挥方法，其特征在于，所述粗产物胶液中环氧丙烷的质量百分含量为20～50％；The devolatilization method according to claim 1, characterized in that the mass percentage of propylene oxide in the crude product glue is 20-50%;
    所述粗产物胶液中碳酸丙烯酯的质量百分含量为2～6％。The mass percentage of propylene carbonate in the crude product glue solution is 2-6%.
  3. 根据权利要求2所述的脱挥方法，其特征在于，所述粗产物胶液和水的质量比为1∶2～8。The devolatilization method according to claim 2 is characterized in that the mass ratio of the crude product glue solution to water is 1:2-8.
  4. 根据权利要求1或3所述的脱挥方法，其特征在于，所述水为热水，所述热水的温度为40～95℃。The devolatilization method according to claim 1 or 3 is characterized in that the water is hot water, and the temperature of the hot water is 40 to 95°C.
  5. 根据权利要求1所述的脱挥方法，其特征在于，所述混合在双螺杆挤出机中进行；The devolatilization method according to claim 1, characterized in that the mixing is carried out in a twin-screw extruder;
    所述双螺杆挤出机的长径比为20～60∶1，转速为50～600r/min，真空度为-10～-90kPa。The length-to-diameter ratio of the twin-screw extruder is 20-60:1, the rotation speed is 50-600 r/min, and the vacuum degree is -10--90 kPa.
  6. 根据权利要求1所述的脱挥方法，其特征在于，所述碳酸丙烯酯以碳酸丙烯酯水溶液的形式去除；The devolatilization method according to claim 1, characterized in that the propylene carbonate is removed in the form of a propylene carbonate aqueous solution;
    去除得到碳酸丙烯酯水溶液后，还包括对所述碳酸丙烯酯水溶液进行萃取处理，得到萃取物料和水；After removing the propylene carbonate aqueous solution, the method further includes extracting the propylene carbonate aqueous solution to obtain an extraction material and water;
    所述水循环用于与所述粗产物胶液混合。The water circulation is used to mix with the crude product gum solution.
  7. 一种脱挥系统，其特征在于，包括双螺杆挤出机(2)、储水罐(3)、接水槽(4)和环氧丙烷接收罐(5)；A devolatilization system, characterized in that it comprises a twin-screw extruder (2), a water storage tank (3), a water receiving tank (4) and a propylene oxide receiving tank (5);
    所述双螺杆挤出机(2)设置有挤出机进料口(16)、环氧丙烷出料口(17)、聚合物出料口(20)、碳酸丙烯酯出料口(21)和若干挤出机进水口(19)；The twin-screw extruder (2) is provided with an extruder feed port (16), a propylene oxide discharge port (17), a polymer discharge port (20), a propylene carbonate discharge port (21) and a plurality of extruder water inlets (19);
    所述接水槽(4)设置于所述碳酸丙烯酯出料口(21)的正下方；The water receiving tank (4) is arranged directly below the propylene carbonate discharge port (21);
    所述环氧丙烷出料口(17)和所述环氧丙烷接收罐(5)连通；The propylene oxide discharge port (17) is in communication with the propylene oxide receiving tank (5);
    所述储水罐(3)设置有储水罐进料口(22)和储水罐出料口(23)；The water storage tank (3) is provided with a water storage tank feed port (22) and a water storage tank discharge port (23);
    所述储水罐进料口(22)和所述接水槽(4)连通；所述储水罐出料口(23)和所述若干挤出机进水口(19)连通。The water storage tank feed port (22) is connected to the water receiving trough (4); the water storage tank discharge port (23) is connected to the water inlets (19) of the plurality of extruders.
  8. 根据权利要求7所述的脱挥系统，其特征在于，所述双螺杆挤出机(2)还设置有真空接口(18)；所述真空接口(18)和抽真空系统(6)连通。The devolatilization system according to claim 7 is characterized in that the twin-screw extruder (2) is also provided with a vacuum interface (18); the vacuum interface (18) is connected to the vacuum extraction system (6).
  9. 根据权利要求7所述的脱挥系统，其特征在于，还包括萃取罐(14)和碳酸丙烯酯接收罐(15)；The devolatilization system according to claim 7, characterized in that it also includes an extraction tank (14) and a propylene carbonate receiving tank (15);
    所述萃取罐(14)设置有萃取罐进料口(27)、萃取罐出料口(26)和萃取罐出液口(25)；The extraction tank (14) is provided with an extraction tank feed port (27), an extraction tank discharge port (26) and an extraction tank liquid outlet (25);
    所述储水罐(3)还设置有储水罐进水口(24)；The water storage tank (3) is also provided with a water storage tank water inlet (24);
    所述萃取罐进料口(27)和所述储水罐出料口(23)连通；所述萃取罐出液口(25)和所述储水罐进水口(24)连通；所述萃取罐出料口(26)和碳酸丙烯酯接收罐连通(15)。The extraction tank feed port (27) is connected to the water storage tank discharge port (23); the extraction tank liquid outlet (25) is connected to the water storage tank water inlet (24); and the extraction tank discharge port (26) is connected to the propylene carbonate receiving tank (15).
  10. 根据权利要求7～9任一项所述的脱挥系统，其特征在于，还包括切粒机(7)、干燥机 (8)和聚合物接收罐(9)；The devolatilization system according to any one of claims 7 to 9, characterized in that it also includes a pelletizer (7), a dryer (8) and a polymer receiving tank (9);
    所述切粒机(7)设置有切粒机进料口(28)和切粒机出料口(29)；The pelletizer (7) is provided with a pelletizer feed port (28) and a pelletizer discharge port (29);
    所述切粒机进料口(28)和所述聚合物出料口(20)连通；The pelletizer feed port (28) is in communication with the polymer discharge port (20);
    所述干燥机(8)设置有干燥机进料口(30)和干燥机出料口(31)；The dryer (8) is provided with a dryer feed port (30) and a dryer discharge port (31);
    所述干燥机进料口(30)和所述切粒机出料口(29)连通；所述干燥机出料口(31)和聚合物接收罐(9)连通。 The dryer feed port (30) is in communication with the pelletizer discharge port (29); the dryer discharge port (31) is in communication with the polymer receiving tank (9).
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