CN115926136A - Continuous production process of carbon dioxide-based biodegradable polymer - Google Patents
Continuous production process of carbon dioxide-based biodegradable polymer Download PDFInfo
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Abstract
A continuous production process of a carbon dioxide-based biodegradable polymer belongs to the technical field of degradable plastics. The method is characterized by comprising the following steps: completing carbon dioxide-based multicomponent copolymerization in a reaction kettle (1); continuously mixing the polymer glue solution and the glue solution dissolving agent in a dissolver (3) and then extracting a mixed solution; mixing the mixed solution and the polymer precipitating agent in a precipitator (4) to obtain a solution to be precipitated; when the sedimentation liquid enters the delaminating device (5) for layering, the upper liquid continuously overflows from the upper part of the delaminating device (5), and the material at the bottom continuously discharges from the bottom of the delaminating device (5) and then enters the devolatilization machine (6) for devolatilization. The continuous production process of the carbon dioxide-based biodegradable polymer provided by the invention has the advantages of continuity, operation temperature, good refining effect and low energy consumption, and the content of impurities in the obtained degradable plastic finished product is below 0.5%, so that the process is suitable for industrialization.
Description
Technical Field
A continuous production process of a carbon dioxide-based biodegradable polymer belongs to the technical field of degradable plastics.
Background
The conventional plastic polymer causes a serious white pollution problem with the increase of the amount used due to poor biodegradability. With the increasing awareness of environmental protection, the use of polymer materials with poor degradation properties has been greatly limited. The majority of researchers find that the polymer material is produced by adopting carbon dioxide polymerization, so that the global warming problem caused by carbon dioxide can be relieved, and the biodegradability of the polymer material can be improved.
Polymethyl ethylene carbonate (PPC) is prepared by copolymerization of carbon dioxide and alkylene oxide, is a transparent, completely degradable and environmentally friendly plastic, has excellent biocompatibility, high barrier property and impact toughness, but has a low glass transition temperature (Tg =30-40 ℃), which limits large-scale application. In order to improve the performance of the PPC, a third element is usually introduced into the main chain of the PPC for modification. If phthalic anhydride is introduced into the main chain of PPC, the prepared degradable polymer has high light transmittance, higher glass transition temperature and good foaming performance, and the preparation method and the post-treatment process thereof are reported in patents. However, no relevant patent or literature report exists on the industrial continuous production process from the reaction to the post-treatment until a qualified finished product is obtained.
For example, patent CN 111378101A discloses a composite material prepared from PA, propylene oxide and CO 2 A process for synthesizing carbon dioxide-base polyester-polycarbonate terpolymer includes such steps as proportionally adding phthalic anhydride, epoxy propane and catalyst to high-pressure reactor, charging 1.0MPa CO 2 Reacting at 80 ℃ for 12h, quenching reaction after the reaction is finished, and dissolving, precipitating and drying the product to obtain the product. The purification method of the glue solution prepared by the reaction is only briefly described, and the specific operation for realizing the method is not mentioned.
A biodegradable carbon dioxide-based terpolymer and its preparation method are disclosed in patent CN 114539515A, which is prepared by adding a certain mass of propylene oxide, lactide and catalyst into a reaction kettle, charging 1.0MPa of CO 2 Reacting at 25 ℃ for 36h, dissolving the polymer by acetone after the reaction is finished, washing the polymer by a methanol solution for three times, and drying the washed product in vacuum at 35 ℃ for 24h. The method uses methanol solution to wash for three times to remove the solventAnd a catalyst, and the operation is cumbersome, and a specific operation method is not mentioned.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art, and provides a continuous production process of the carbon dioxide-based biodegradable polymer, which has simple operation, high efficiency and thorough separation.
The technical scheme adopted by the invention for solving the technical problem is as follows: the continuous production process of the carbon dioxide-based biodegradable polymer is characterized by comprising the following steps of:
1) Carbon dioxide and a comonomer are subjected to carbon dioxide-based multicomponent copolymerization in a reaction kettle under the action of a catalyst to obtain a polymer glue solution, and the polymer glue solution obtained after the reaction is finished each time is transferred to a buffer tank for temporary storage;
2) Continuously conveying the polymer glue solution into a dissolver from a buffer tank, and simultaneously keeping conveying a glue solution dissolver into the dissolver to dissolve the glue solution into the glue solution dissolver to obtain a mixed solution; the dissolver keeps continuous feeding and simultaneously continuously extracts;
3) Continuously conveying the mixed solution continuously extracted by the dissolver into the precipitator, and simultaneously maintaining conveying of the polymer precipitant into the precipitator, so that the carbon dioxide-based biodegradable polymer is precipitated from the mixed solution to obtain a solution to be precipitated; the precipitator continuously withdraws while maintaining continuous feeding;
4) The liquid to be settled continuously extracted from the precipitator enters the delayer for layering, the upper layer liquid of the delayer continuously overflows from the upper part of the delayer and then enters the recovery system, the material at the bottom continuously discharges from the bottom of the delayer and then enters the volatile component removed by the devolatilization machine, the volatile component is condensed and then sent to the recovery system, and the discharge of the devolatilization machine is finished products.
The glue solution after the reaction is continuously dissolved in the dissolver, and then is continuously separated out in the separator after being dissolved, so that the dissolving and separating out are continuously carried out, the quality difference among batches during batch discharging in the reaction kettle is avoided, and the production efficiency is improved. The continuous separation of liquid and separated sediments is also realized in the delayer, and the liquid overflows from the upper part of the delayer; the separated sediment is discharged from the bottom of the delaminator in a continuous self-flowing manner, so that the purpose of continuous feeding and continuous separation without external power is achieved, and compared with other separation modes, the production energy consumption is reduced.
Preferably, in the continuous production process of the carbon dioxide-based biodegradable polymer, the comonomer is one or a combination of more of epoxy compounds, anhydride compounds and ester compounds.
Preferably, the epoxy compound is an alkylene oxide. The alkylene oxide is selected from one or a combination of several of ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, epichlorohydrin, cyclopentane oxide and hexane oxide.
The production process can be suitable for the production of most carbon dioxide-based biodegradable polymers by adjusting the types and the use amounts of the glue solution dissolving agent and the polymer precipitating agent.
Aiming at the production of different carbon dioxide-based biodegradable polymers, the type and the dosage of a glue solution dissolving agent need to be adjusted; specifically, in the continuous production process of the carbon dioxide-based biodegradable polymer: the glue solution dissolving agent is one or a combination of more of dichloromethane, 1,2-dichloroethane, 1,2-dichloropropane, acetone, ethyl acetate, carbon tetrachloride, styrene and trichloroethylene; the mass ratio of the polymer glue solution and the glue solution dissolving agent fed into the dissolver within a unit time in the step 2) is 1: (0.1-3). The type and the dosage of the glue solution dissolving agent can meet the continuous production process of various carbon dioxide-based biodegradable polymers, and different choices affect the dissolving time and the dissolving rate, which are not exemplified herein.
Preferably, the glue solution dissolving agent is a mixed solvent of 1,2-dichloroethane and 1,2-dichloropropane; the mass ratio of the polymer glue solution and the glue solution dissolving agent fed into the dissolver within a unit time in the step 2) is 1: (0.1-1). The preferable glue solution dissolving agent is particularly suitable for carbon dioxide-based biodegradable polymers copolymerized by carbon dioxide and epoxy compound monomers, has higher dissolving efficiency on the polymers, and can be dissolved more quickly by using less glue solution dissolving agent. The requirement on the dissolver is low, the time required in the dissolver is shorter, and the production efficiency of the whole production process is improved.
More preferably, the mass ratio of 1,2-dichloroethane and 1,2-dichloropropane in the mixed solvent is 3-7: 1; the mass ratio of the polymer glue solution and the glue solution dissolving agent which are conveyed into the dissolver within a unit time in the step 2) is 1: (0.1-0.3). The more preferable glue solution dissolving agent is particularly suitable for copolymerization of carbon dioxide, alkylene oxide and phthalic anhydride, has faster dissolving efficiency on the polymer, and can complete dissolving more quickly by using less glue solution dissolving agent. The requirement on the retention time and the liquid mixing capacity in the dissolver is low, and the production efficiency of the production process is favorably improved.
Aiming at the production of different carbon dioxide-based biodegradable polymers, the invention needs to adjust the type and the dosage of a polymer precipitating agent; specifically, in the continuous production process of the carbon dioxide-based biodegradable polymer: the polymer precipitation agent is one or a combination of more of alcohols, ethers and alkanes; the mass ratio of the mixed liquid and the polymer precipitating agent which are conveyed into the precipitator in the step 3) per unit time is 1: (0.2-1.5). The types and the dosage of the polymer precipitating agent can meet the continuous production process of various carbon dioxide-based biodegradable polymers, and different choices influence the precipitation time and the precipitation rate of the polymers, which are not exemplified herein.
Preferably, the polymer precipitating agent is absolute ethyl alcohol and n-butyl ether according to a mass ratio of 2-10: 1, compounding a mixed precipitating agent; the mass ratio of the mixed liquid and the polymer precipitating agent which are conveyed into the precipitator in the step 3) per unit time is 1: (0.2-0.4). The preferred polymer precipitation agent is particularly useful for the copolymerization of carbon dioxide, alkylene oxide, and phthalic anhydride, has faster precipitation efficiency for the polymer, and can complete polymer precipitation faster with less polymer precipitation agent. The requirements on the retention time and the liquid mixing capacity in the precipitator are low, and the more preferable liquid glue dissolving agent is matched, so that the production efficiency of the polymer production process is improved.
Specifically, the dissolver and the precipitator are both devices which are provided with 2 feed inlets and have a liquid mixing function. 2 feed inlets of the dissolver respectively feed polymer glue solution and glue solution dissolving agent, and 2 feed inlets of the precipitator respectively feed mixed solution and polymer precipitating agent; the liquid mixing function ensures the full contact of the polymer glue solution and the glue solution dissolving agent or the mixed solution and the polymer precipitating agent.
Specifically, the dissolver is one or a combination of a plurality of pipeline mixers, kettle type stirrers, double-screw extruders, single-screw extruders, mixing pumps and screw pumps; the precipitator is one or a combination of a plurality of pipeline mixers, kettle type stirrers, double-screw extruders, single-screw extruders, mixing pumps and screw pumps. When the kettle type stirrer is used as a dissolver or a precipitator, the kettle type stirrer is combined with a pipeline mixer for use, and the requirements of continuous dissolution and precipitation can also be met.
Specifically, the delayer is of a kettle type, and the length-diameter ratio of the delayer is 2-15: 1. the delayer does not need power such as stirring, rotation and the like, and after the settling liquid enters the delayer, the settling liquid automatically settles under the action of gravity, so that the aim of solid-liquid separation is fulfilled.
The working temperature in the dissolver and the precipitator is 1-100 ℃, and the working temperature in the devolatilization machine in the step 4) is 30-200 ℃. The heating extrusion is carried out in the devolatilization machine, the heating process is favorable for the volatilization separation of the glue solution dissolving agent and the polymer precipitating agent, the recovery can be completed after the condensation, and simultaneously, the purity of the product is improved after the volatilization separation of the glue solution dissolving agent and the polymer precipitating agent.
The invention is applied to the continuous production process of the carbon dioxide-based biodegradable binary and above copolymers.
Compared with the prior art, the continuous production process of the carbon dioxide-based biodegradable polymer has the beneficial effects that:
the invention provides a continuous production process of carbon dioxide-based biodegradable plastic, aiming at the defects in the preparation and purification processes of the existing carbon dioxide-based biodegradable plastic. One of the innovative points of the invention is that the method of solvent dissolution and precipitation of the precipitating agent is adopted to remove the catalyst in the glue solution after the reaction, and a double-screw devolatilization machine is utilized to remove other impurities such as unreacted monomers, solvent molecules, precipitating agent molecules, byproducts and the like. After the bulk polymerization reaction is finished, a catalyst and a large amount of unreacted monomers exist, great difficulty is caused to the next devolatilization refining process, the residual catalyst can deteriorate and denature products after long-term existence, and the process scheme washes away the catalyst and a large amount of unreacted monomers at the same time, so that the devolatilization is easy. The second innovation point is continuous feeding and discharging of dissolution and precipitation, the dissolution and precipitation effects are ensured, meanwhile, the continuity is realized, and proper stirring equipment is selected. The invention adopts a kettle-type delayer with a certain length-diameter ratio and realizes layering by utilizing the density difference of the liquid phase and the solid phase.
In a word, the continuous production process of the carbon dioxide-based biodegradable polymer provided by the invention has the advantages of continuity, operation temperature, good refining effect and low energy consumption, and the content of impurities in the obtained degradable plastic finished product is below 0.5%, so that the process is suitable for industrialization.
Drawings
FIG. 1 is a schematic flow chart of a continuous production process of a carbon dioxide-based biodegradable polymer according to the present invention.
Wherein, the reaction kettle 1, the reaction kettle 2, the buffer tank 3, the dissolver 4, the precipitator 5, the delayer 6, the devolatilization machine 7, the condenser 8 and the solvent receiving tank. 9. Solvent pipeline 10, product output.
Detailed Description
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an", and "the" are intended to include the plural forms as well, and furthermore, the terms "comprises" and "having", and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
The invention is further illustrated by the following specific examples, of which example 1 is the best mode of practice. For comparison of the effects, the polymer glues in examples 1 to 6 were the same batch of glue in the same buffer tank.
Example 1
1) The polymer glue solution after the reaction in the reaction kettle 1 is 2m 3 The flow of the reaction kettle per hour is completely conveyed into the buffer tank 2 at one time, and after the conveying is finished, the reaction kettle 1 can carry out the next batch of reaction feeding.
The polymer glue solution in the buffer tank 2 is continuously conveyed into a dissolver 3 serving as a flow pump with a tee joint at a suction inlet at the flow rate of 200kg/h, and simultaneously, the mixed solvent compounded by 1,2-dichloroethane and 1,2-dichloropropane with the mass ratio of 5:1 is continuously conveyed into the dissolver 3 at the flow rate of 20kg/h, the rotating speed is 60r/min, and the temperature is controlled to be 30 ℃.
The mixed liquid output by the dissolver 3 is continuously conveyed into the precipitator 4 which is a mixing pump with a tee joint at a suction inlet at the flow rate of 220kg/h, and simultaneously, anhydrous ethanol and n-butyl ether are continuously conveyed into the precipitator 4 at the flow rate of 44kg/h according to the mass ratio of 6:1 the mixed precipitant is compounded, the rotating speed is 90r/min, and the temperature is controlled to be 20 ℃.
The liquid to be settled output by the precipitator 4 is continuously conveyed into the delayer 5 at the flow rate of 264kg/h, the length-diameter ratio of the delayer 5 is 8:1, enabling supernatant fluid to continuously overflow from the upper part of a delayer 5 and then enter a solvent receiving tank 8 through a solvent pipeline 9, enabling materials at the bottom to continuously discharge from the bottom of the delayer and then enter a devolatilization machine 6 for devolatilization, enabling the materials entering the devolatilization machine 6 to be devolatilized at the temperature of 150 ℃ and under the vacuum degree of 0.1MPa, and discharging from a product output end 10 of the devolatilization machine 6 to obtain a finished product.
The polymer glue solution is carbon dioxide-based multipolymer, carbon dioxideThe multipolymer is an epoxy propane-phthalic anhydride-carbon dioxide terpolymer with the number average molecular weight of 9.36 multiplied by 10 4 g/mol, solids content 57.65% and viscosity 150880mPa. S at 25 ℃.
The purity of the solid sample after devolatilization is 99.74 percent, and the yield is 99.89 percent. The yield calculation method comprises the following steps: weighing the mass m1 of the obtained solid sample; yield = m (gum solution) × gum solution solid content/m 1 × 100%.
Example 2
1) The polymer glue solution after the reaction in the reaction kettle 1 is 2m 3 The flow of the reaction kettle 1 is conveyed into the buffer tank 2 at one time, and the next batch of reaction feeding can be carried out after the conveying is finished.
The polymer glue solution in the buffer tank 2 is continuously conveyed into a dissolver 3 serving as a mixing pump with a tee joint at a suction inlet at a flow rate of 200kg/h, and simultaneously, 1,2-dichloroethane and 1,2-dichloropropane are continuously conveyed into the dissolver 3 at a flow rate of 40kg/h, wherein the mass ratio of the materials is 3:1 the rotation speed of the mixed solvent is 60r/min, and the temperature is controlled to be 30 ℃.
The mixed liquid output by the dissolver 3 is continuously conveyed into the precipitator 4 which is a mixing pump with a tee joint at a suction inlet at the flow rate of 240kg/h, and simultaneously, anhydrous ethanol and n-butyl ether are continuously conveyed into the precipitator 4 at the flow rate of 72kg/h (1 (0.2-0.4) 1 (0.2-1.5)) according to the mass ratio of 2:1 the mixed precipitant is compounded, the rotating speed is 80-100 r/min, and the temperature is controlled to be 20 ℃.
The liquid to be settled output by the precipitator 4 is continuously conveyed into the delayer 5 at the flow rate of 312kg/h, and the length-diameter ratio of the delayer 5 is 5:1, enabling supernatant fluid to continuously overflow from the upper part of a delayer 5 and then enter a solvent receiving tank 8 through a solvent pipeline 9, enabling materials at the bottom to continuously discharge from the bottom of the delayer and then enter a devolatilization machine 6 for devolatilization, enabling the materials entering the devolatilization machine 6 to be devolatilized at the temperature of 150 ℃ and under the vacuum degree of 0.1MPa, and discharging from a product output end 10 of the devolatilization machine 6 to obtain a finished product.
The polymer glue solution is a carbon dioxide-based multipolymer, the carbon dioxide-based multipolymer is a propylene oxide-phthalic anhydride-carbon dioxide terpolymer, and the number average molecular weight is 9.36 multiplied by 10 4 g/mol, solid content 57.65%And a viscosity at 25 ℃ of 150880mPa.S.
The purity of the solid sample after devolatilization is 99.71 percent, and the yield is 99.89 percent. The yield calculation method comprises the following steps: weighing the mass m1 of the obtained solid sample; yield = m (gum solution) × gum solution solid content/m 1 × 100%.
Example 3
1) The polymer glue solution after the reaction in the reaction kettle 1 is 2m 3 The flow of the reaction kettle 1 is conveyed into the buffer tank 2 at one time, and the next batch of reaction feeding can be carried out after the conveying is finished.
The polymer glue solution in the buffer tank 2 is continuously conveyed into a dissolver 3 serving as a mixing pump with a tee joint at a suction inlet at a flow rate of 200kg/h, and simultaneously, 1,2-dichloroethane and 1,2-dichloropropane are continuously conveyed into the dissolver 3 at a flow rate of 60kg/h, wherein the mass ratio of the materials is 7:1 the rotation speed of the mixed solvent is 60r/min, and the temperature is controlled to be 30 ℃.
The mixed liquid output by the dissolver 3 is continuously conveyed into the precipitator 4 with a three-way mixing pump serving as a suction inlet at a flow rate of 260kg/h, and simultaneously, anhydrous ethanol and n-butyl ether are continuously conveyed into the precipitator 4 at a flow rate of 104kg/h according to a mass ratio of 10:1 the mixed precipitant is compounded, the rotating speed is 80-100 r/min, and the temperature is controlled to be 20 ℃.
The liquid to be settled output by the precipitator 4 is continuously conveyed into the delayer 5 at the flow rate of 364kg/h, and the length-diameter ratio of the delayer 5 is 12:1, continuously overflowing supernatant liquid from the upper part of a delayer 5, then entering a solvent receiving tank 8 through a solvent pipeline 9, continuously discharging bottom materials from the bottom of the delayer, then entering a devolatilization machine 6 for devolatilization, and discharging the materials entering the devolatilization machine 6 at 150 ℃ under the vacuum degree of 0.1MPa, thus obtaining a finished product after discharging from a product output end 10 of the devolatilization machine 6.
The polymer glue solution is a carbon dioxide-based multipolymer, the carbon dioxide-based multipolymer is an epoxy propane-phthalic anhydride-carbon dioxide terpolymer, and the number average molecular weight is 9.36 multiplied by 10 4 g/mol, solids content 57.65% and viscosity 150880mPa. S at 25 ℃.
The purity of the solid sample after devolatilization is 99.70 percent, and the yield is 99.90 percent. The yield calculation method comprises the following steps: weighing the mass m1 of the obtained solid sample; yield = m (gum solution) × gum solution solid content/m 1 × 100%.
Example 4
1) The polymer glue solution after the reaction in the reaction kettle 1 is 2m 3 The flow of the reaction kettle 1 is conveyed into the buffer tank 2 at one time, and the next batch of reaction feeding can be carried out after the conveying is finished.
The polymer glue solution in the buffer tank 2 is continuously conveyed into a dissolver 3 serving as a mixing pump with a tee joint at a suction inlet at the flow rate of 200kg/h, and simultaneously, the mixed solvent compounded by 1,2-dichloroethane and 1,2-dichloropropane with the mass ratio of 1:1 is continuously conveyed into the dissolver 3 at the flow rate of 120kg/h, the rotating speed is 60r/min, and the temperature is controlled to be 25 ℃.
The mixed liquid output by the dissolver 3 is continuously conveyed into the precipitator 4 with a three-way mixing pump serving as a suction inlet at a flow rate of 320kg/h, and simultaneously, anhydrous ethanol and n-butyl ether are continuously conveyed into the precipitator 4 at a flow rate of 256kg/h according to a mass ratio of 0.1:1 the mixed precipitating agent is compounded, the rotating speed is 80-100 r/min, and the temperature is controlled at 25 ℃.
Liquid to be settled output by the precipitator 4 is continuously conveyed into the delayer 5 at the flow rate of 576kg/h, and the length-diameter ratio of the delayer 5 is 2:1, enabling supernatant fluid to continuously overflow from the upper part of a delayer 5 and then enter a solvent receiving tank 8 through a solvent pipeline 9, enabling materials at the bottom to continuously discharge from the bottom of the delayer and then enter a devolatilization machine 6 for devolatilization, enabling the materials entering the devolatilization machine 6 to be devolatilized at the temperature of 150 ℃ and under the vacuum degree of 0.1MPa, and discharging from a product output end 10 of the devolatilization machine 6 to obtain a finished product.
The polymer glue solution is a carbon dioxide-based multipolymer, the carbon dioxide-based multipolymer is a propylene oxide-phthalic anhydride-carbon dioxide terpolymer, and the number average molecular weight is 9.36 multiplied by 10 4 g/mol, solids content 57.65% and viscosity 150880mPa. S at 25 ℃.
The purity of the solid sample after devolatilization is 99.65 percent, and the yield is 99.82 percent. The yield calculation method comprises the following steps: weighing the mass m1 of the obtained solid sample; yield = m (gum solution) × gum solution solid content/m 1 × 100%.
Example 5
1) Reaction in reaction kettle 1The polymer glue solution after finishing is 2m 3 The flow of the reaction kettle 1 is conveyed into the buffer tank 2 at one time, and the next batch of reaction feeding can be carried out after the conveying is finished.
The polymer glue solution in the buffer tank 2 is continuously conveyed into a dissolver 3 serving as a screw pump with a three-way joint at a suction inlet at a flow rate of 200kg/h, and simultaneously the mixed solvent compounded by 1,2-dichloroethane and 1,2-dichloropropane with the mass ratio of 10 is continuously conveyed into the dissolver 3 at a flow rate of 200kg/h, the rotating speed is 60r/min, and the temperature is controlled to be 45 ℃.
The mixed liquid output by the dissolver 3 is continuously conveyed into a precipitator 4 which is a screw pump with a three-way suction inlet and is served as a three-way suction inlet at the flow rate of 400kg/h, and simultaneously, anhydrous ethanol and n-butyl ether are continuously conveyed into the precipitator 4 at the flow rate of 400kg/h according to the mass ratio of 20:1 the mixed precipitant is compounded, the rotating speed is 80-100 r/min, and the temperature is controlled to be 30 ℃.
The liquid to be settled output by the precipitator 4 is continuously conveyed into the delayer 5 at the flow rate of 800kg/h, the length-diameter ratio of the delayer 5 is 15:1, continuously overflowing supernatant liquid from the upper part of a delayer 5, then entering a solvent receiving tank 8 through a solvent pipeline 9, continuously discharging bottom materials from the bottom of the delayer, then entering a devolatilization machine 6 for devolatilization, and discharging the materials entering the devolatilization machine 6 at 150 ℃ under the vacuum degree of 0.1MPa, thus obtaining a finished product after discharging from a product output end 10 of the devolatilization machine 6.
The polymer glue solution is a carbon dioxide-based multipolymer, the carbon dioxide-based multipolymer is a propylene oxide-phthalic anhydride-carbon dioxide terpolymer, and the number average molecular weight is 9.36 multiplied by 10 4 g/mol, solids content 57.65% and viscosity 150880mPa. S at 25 ℃.
The devolatilized solid sample was taken to determine a purity of 99.62% and a yield of 99.85%. The yield calculation method comprises the following steps: weighing the mass m1 of the obtained solid sample; yield = m (gum solution) × gum solution solid content/m 1 × 100%.
Example 6
1) The polymer glue solution after the reaction in the reaction kettle 1 is 2m 3 The flow of the reaction kettle per hour is completely conveyed into the buffer tank 2 at one time, and after the conveying is finished, the reaction kettle 1 can carry out the next batch of reaction feeding.
The polymer glue solution in the buffer tank 2 is continuously conveyed into a dissolver 3 serving as a mixing pump with a tee joint at a suction inlet at the flow rate of 200kg/h, and simultaneously, 1,2-dichloroethane is continuously conveyed into the dissolver 3 at the flow rate of 440kg/h, the rotating speed is 60r/min, and the temperature is controlled to be 30 ℃.
The mixed liquid output by the dissolver 3 is continuously conveyed into the precipitator 4 with a mixing pump with a tee joint at a suction inlet at the flow rate of 640kg/h, and simultaneously, the ether is continuously conveyed into the precipitator 4 at the flow rate of 832kg/h, the rotating speed is 80-100 r/min, and the temperature is controlled to be 20 ℃.
The liquid to be settled output by the precipitator 4 is continuously conveyed into the demixer 5 at a flow rate of 1472kg/h, and the length-diameter ratio of the demixer 5 is 8:1, continuously overflowing supernatant liquid from the upper part of a delayer 5, then entering a solvent receiving tank 8 through a solvent pipeline 9, continuously discharging bottom materials from the bottom of the delayer, then entering a devolatilization machine 6 for devolatilization, and discharging the materials entering the devolatilization machine 6 at 150 ℃ under the vacuum degree of 0.1MPa, thus obtaining a finished product after discharging from a product output end 10 of the devolatilization machine 6.
The polymer glue solution is a carbon dioxide-based multipolymer, the carbon dioxide-based multipolymer is a propylene oxide-phthalic anhydride-carbon dioxide terpolymer, and the number average molecular weight is 9.36 multiplied by 10 4 g/mol, solids content 57.65% and viscosity 150880mPa. S at 25 ℃.
The purity of the devolatilized solid sample was 98.77% and the yield was 99.14%. The yield calculation method comprises the following steps: weighing the mass m1 of the obtained solid sample; yield = m (gum solution) × gum solution solid content/m 1 × 100%.
Example 7
1) The polymer glue solution after the reaction in the reaction kettle 1 is 2m 3 The flow of the reaction kettle 1 is conveyed into the buffer tank 2 at one time, and the next batch of reaction feeding can be carried out after the conveying is finished.
The polymer glue solution in the buffer tank 2 is continuously conveyed into a dissolver 3 serving as a mixing pump with a tee joint at a suction inlet at the flow rate of 200kg/h, and simultaneously, the mixed solvent compounded by 1,2-dichloroethane and 1,2-dichloropropane with the mass ratio of 5:1 is continuously conveyed into the dissolver 3 at the flow rate of 200kg/h, the rotating speed is 60r/min, and the temperature is controlled to be 30 ℃.
The mixed liquid output by the dissolver 3 is continuously conveyed into the precipitator 4 which is a mixing pump with a tee joint at a suction inlet at the flow rate of 400kg/h, and simultaneously, anhydrous ethanol and n-butyl ether are continuously conveyed into the precipitator 4 at the flow rate of 320kg/h according to the mass ratio of 6:1 the mixed precipitant is compounded, the rotating speed is 80-100 r/min, and the temperature is controlled to be 20 ℃.
The liquid to be settled output by the precipitator 4 is continuously conveyed into the delayer 5 at the flow rate of 720kg/h, the length-diameter ratio of the delayer 5 is 8:1, enabling supernatant fluid to continuously overflow from the upper part of a delayer 5 and then enter a solvent receiving tank 8 through a solvent pipeline 9, enabling materials at the bottom to continuously discharge from the bottom of the delayer and then enter a devolatilization machine 6 for devolatilization, enabling the materials entering the devolatilization machine 6 to be devolatilized at the temperature of 150 ℃ and under the vacuum degree of 0.1MPa, and discharging from a product output end 10 of the devolatilization machine 6 to obtain a finished product.
The polymer glue solution is carbon dioxide-based multipolymer, the carbon dioxide-based multipolymer is propylene oxide, lactide-carbon dioxide terpolymer, and the number average molecular weight is 8.79 multiplied by 10 4 g/mol, solids content 55.54%, viscosity 52360mPa.S at 25 ℃.
The devolatilized solid sample was tested for purity of 99.24% and yield of 98.36%. The yield calculation method comprises the following steps: weighing the mass m1 of the obtained solid sample; yield = m (gum solution) × gum solution solid content/m 1 × 100%.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention will still fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. A continuous production process of a carbon dioxide-based biodegradable polymer, characterized by comprising the following steps:
1) Carbon dioxide and a comonomer are subjected to carbon dioxide-based multicomponent copolymerization in the reaction kettle (1) under the action of a catalyst to obtain a polymer glue solution, and the polymer glue solution obtained after each reaction is transferred to a buffer tank (2) for temporary storage;
2) Continuously conveying the polymer glue solution from the buffer tank (2) to a dissolver (3), and simultaneously keeping conveying the glue solution dissolving agent to the dissolver (3) to dissolve the glue solution in the glue solution dissolving agent to obtain a mixed solution; the dissolver (3) keeps continuous feeding and simultaneously continuously extracts;
3) Continuously conveying the mixed solution continuously extracted by the dissolver (3) into the precipitator (4), and simultaneously keeping conveying the polymer precipitating agent into the precipitator (4) to precipitate the carbon dioxide-based biodegradable polymer from the mixed solution to obtain a solution to be precipitated; the separator (4) keeps continuous feeding and simultaneously continuously extracts;
4) The liquid to be settled continuously extracted from the precipitator (4) enters the delayer (5) for layering, the upper layer liquid of the delayer (5) continuously overflows from the upper part of the delayer (5) and then enters the recovery system, the material at the bottom continuously discharges from the bottom of the delayer (5) and then enters the volatile component removed by the devolatilization machine (6), the volatile component is condensed and then sent to the recovery system, and the discharge of the devolatilization machine (6) is finished products.
2. The continuous process for producing a carbon dioxide-based biodegradable polymer according to claim 1, wherein:
the comonomer is one or a combination of more of epoxy compounds, anhydride compounds and ester compounds.
3. The continuous production process of a carbon dioxide-based biodegradable polymer according to claim 1, characterized in that:
the glue solution dissolving agent is one or a combination of more of dichloromethane, 1,2-dichloroethane, 1,2-dichloropropane, acetone, ethyl acetate, carbon tetrachloride, styrene and trichloroethylene; the mass ratio of the polymer glue solution and the glue solution dissolving agent fed into the dissolver (3) in the step 2) per unit time is 1: (0.1-3).
4. The continuous production process of a carbon dioxide-based biodegradable polymer according to claim 1 or 3, characterized in that:
the glue solution dissolving agent is a mixed solvent of 1,2-dichloroethane and 1,2-dichloropropane; the mass ratio of the polymer glue solution and the glue solution dissolving agent fed into the dissolver (3) in the step 2) per unit time is 1: (0.1-1).
5. The continuous production process of a carbon dioxide-based biodegradable polymer according to claim 4, characterized in that:
the mass ratio of 1,2-dichloroethane to 1,2-dichloropropane in the mixed solvent is 3-7: 1; the mass ratio of the polymer glue solution and the glue solution dissolving agent which are conveyed into the dissolver (3) within a unit time in the step 2) is 1: (0.1-0.3).
6. The continuous production process of a carbon dioxide-based biodegradable polymer according to claim 1, characterized in that:
the polymer precipitating agent is one or a combination of more of alcohols, ethers and alkanes; the mass ratio of the mixed liquid and the polymer precipitating agent which are conveyed into the precipitator (4) in the step 3) per unit time is 1: (0.2-1.5).
7. The continuous production process of a carbon dioxide-based biodegradable polymer according to claim 1 or 6, characterized in that:
the polymer precipitating agent is absolute ethyl alcohol and n-butyl ether according to a mass ratio of 2-10: 1, compounding a mixed precipitating agent; the mass ratio of the mixed liquid and the polymer precipitating agent which are conveyed into the precipitator (4) in the step 3) per unit time is 1: (0.2-0.4).
8. The continuous production process of a carbon dioxide-based biodegradable polymer according to claim 1, characterized in that:
the dissolver (3) and the precipitator (4) are both devices with 2 feed inlets and liquid mixing function.
9. The continuous production process of a carbon dioxide-based biodegradable polymer according to claim 1, characterized in that:
the dissolver (3) is one or a combination of a plurality of pipeline mixers, kettle type stirrers, double-screw extruders, single-screw extruders, flow pumps, mixing pumps, rotor pumps and screw pumps;
the separator (4) is one or a combination of a plurality of pipeline mixers, kettle type stirrers, double-screw extruders, single-screw extruders, mixing pumps and screw pumps.
10. The continuous production process of a carbon dioxide-based biodegradable polymer according to claim 1, characterized in that:
the delayer (5) is of a kettle type, and the length-diameter ratio of the delayer (5) is 2-15: 1.
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