CN111234058A - Method for treating polymer solution - Google Patents
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- CN111234058A CN111234058A CN202010188436.3A CN202010188436A CN111234058A CN 111234058 A CN111234058 A CN 111234058A CN 202010188436 A CN202010188436 A CN 202010188436A CN 111234058 A CN111234058 A CN 111234058A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/06—Treatment of polymer solutions
- C08F6/12—Separation of polymers from solutions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C2/00—Treatment of rubber solutions
- C08C2/06—Wining of rubber from solutions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/08—Butenes
- C08F10/10—Isobutene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/06—Treatment of polymer solutions
- C08F6/10—Removal of volatile materials, e.g. solvents
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Abstract
The invention discloses a method for treating polymer solution. Before the polymer is separated by water precipitation and coagulation, the polymer solution is concentrated and evaporated to obtain a polymer solution with improved concentration. And (3) contacting the polymer solution with the increased concentration with hot water and water vapor, precipitating the polymer in a solid form, and discharging mixed vapor formed by the organic solvent and the water for recovery. According to the invention, before the polymer is separated by the water precipitation coagulation, the polymer solution is concentrated to evaporate part of the solvent, so that the amount of water vapor directly contacted with the polymer solution in the water precipitation coagulation process is reduced, the energy consumption is reduced, and meanwhile, the amount of water vapor condensate entering the coagulation kettle is reduced due to the reduction of the water vapor consumption, and the sewage discharge is reduced.
Description
Technical Field
The invention belongs to the field of polymer preparation, and particularly relates to a method for treating a polymer solution.
Background
Solution polymerization generally employs a method of aqueous precipitation coagulation to separate the polymer and solvent and recover unreacted monomers. The reaction solution containing a large amount of solvent and a small amount of reaction monomer is sprayed into hot water of a condensation kettle, the solvent is vaporized by steam and carried out of the kettle, the polymer in the polymer solution is gradually concentrated along with vaporization of a large amount of solvent so as to form solid particles, and simultaneously the solvent contained in the polymer solution is gradually diffused to the surface, and finally porous small particles containing less solvent and more water are formed. The polymer solution elutriation and condensation device concentrates 80% of the loss amount of the solvent and 50% of energy consumption, is the equipment with the largest energy consumption and material consumption in the polymer production process, and is one of the fields of energy conservation and consumption reduction key issues in the polymer production process by the solution method.
The function of the water vapor in the process of the water precipitation and condensation mainly comprises the following steps: (1) sensible heat required for heating the glue solution and the condensation hot water to the condensation temperature is provided; (2) providing latent heat of vaporization of the hydrocarbon solvent in the glue solution; (3) carrying out the gaseous hydrocarbons in the condensation kettle. Based on this, in the prior art, measures such as increasing the monomer concentration, increasing the gel content of the polymer solution, reducing the water-gel ratio during coagulation, and preserving the heat of the polymer solution and the circulating hot water system are mainly taken, so as to reduce the steam consumption during coagulation to achieve the purpose of energy saving and consumption reduction.
Disclosure of Invention
The invention provides a method for treating polymer solution, which comprises the following steps: before the polymer is separated by water precipitation and coagulation, the polymer solution is concentrated and evaporated to obtain a polymer solution with improved concentration.
According to the invention, the water-out coagulation is a process in which a polymer solution is brought into contact with water vapor and/or hot water, and the water causes the polymer to precipitate in solid form, while obtaining a mixed vapor of an organic solvent and water.
According to the invention, the method for treating the polymer solution comprises the following steps:
(1) concentrating and evaporating the polymer solution to obtain a polymer solution with improved concentration;
(2) and (3) contacting the polymer solution with the increased concentration with hot water and water vapor, precipitating the polymer in a solid form, and discharging mixed vapor formed by the organic solvent and the water for recovery.
According to the invention, the polymer solution is a polymer solution prepared by solution polymerization.
According to the present invention, the polymer is a polymer dissolved in a hydrocarbon solvent, such as at least one of cis-Butadiene Rubber (BR), solution-polymerized styrene-butadiene rubber (SSBR), styrene-butadiene-styrene block copolymer (SBS) or a hydrogenated product thereof, styrene-isoprene-styrene block copolymer or a hydrogenated product thereof, hydrogenated nitrile rubber, halogenated butyl rubber, polyisoprene rubber, acrylonitrile-butadiene-styrene (ABS), and the like; preferably halogenated butyl rubber; brominated butyl rubber or chlorinated butyl rubber is exemplified. Wherein the hydrocarbon solvent has the meaning as described below.
According to the invention, in step (1), the polymer solution contains the same organic solvent as the organic solvent discharged in the elutriation and coagulation stage. For example, the organic solvent is a hydrocarbon solvent, such as a C5-C7 hydrocarbon, e.g., at least one of pentane, hexane, cyclohexane, heptane, preferably n-hexane or cyclohexane.
According to the invention, the polymer solution is brought into contact with a reaction terminator before the concentration and evaporation, the terminator being a compound which is capable of terminating the chemical reaction for the synthesis of polymers by the solution process. The addition of a suitable terminator can be selected by those skilled in the art according to the monomers.
According to the invention, the mass concentration of the polymer in the polymer solution is 10 to 25 wt.%, for example 13 to 22 wt.%, exemplary 17 wt.%.
According to the present invention, the concentration-increased polymer solution refers to a polymer solution in which the mass concentration of the polymer is increased by 5 to 15 wt% as compared to that before concentration, for example, by 7 to 13 wt%, illustratively by 5 wt%, 7 wt%, 9 wt%, 10 wt%, 11 wt%, 13 wt%, 15 wt%, and the like. Since the viscosity of the polymer solution increases with the increase in concentration, it is not preferable to exceed 32 wt%, and the increase in solution viscosity makes it difficult to transport the polymer solution and disperse the polymer solution in hot water.
According to the invention, the concentration and evaporation process is carried out in an evaporator.
According to the present invention, in the step (1), part of the organic solvent is distilled off during the concentration evaporation. Wherein the distilled organic solvent can be recovered.
According to the present invention, the concentration and evaporation may be performed by steam heating, and the polymer solution is heated to raise the temperature thereof so that a part of the organic solvent is distilled off. For example, 0.2 to 2.0MPa (preferably 0.4 to 1.0MPa, illustratively 0.2MPa, 0.3MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 1.0MPa) of water vapor may be added to the evaporator, and the temperature of the polymer solution may be raised by heating to distill off part of the organic solvent. Further, in order to obtain the polymer solution having an increased concentration, it is necessary to control the discharge flow rate of the gas phase from which the organic solvent is distilled off, for example, 4000-.
According to the invention, in step (2), the polymer solution of increased concentration is contacted with hot water and water vapor in a coagulation reactor. Wherein the temperature in the coagulation vessel is controlled to be 70 to 120 deg.C, for example, 90 to 110 deg.C, and exemplified by 70 deg.C, 80 deg.C, 90 deg.C, 95 deg.C, 100 deg.C, 105 deg.C, 110 deg.C, 115 deg.C, 120 deg.C, etc. Preferably, the temperature in the coagulum kettle is higher than the temperature of the polymer solution of increased concentration.
According to the invention, in step (2), the hot water has a temperature of 80-120 ℃, such as 85-115 ℃, exemplary 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃.
According to the invention, in step (2), the water vapor may be a vapor of 0.2 to 2.0MPa (preferably 0.4 to 1.0MPa, illustratively 0.2MPa, 0.3MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 1.0 MPa).
According to the invention, in the step (2), the mixed steam is separated to obtain the organic solvent and water, the organic solvent is recovered, and the water is discharged as sewage.
According to the invention, in step (2), the precipitated polymer and water form a polymer solids/water mixture which is separated to obtain the crumb and water. Wherein, part of water is returned to the condensation kettle and the other part of water is discharged as sewage. Further, the resulting crumb was dried and used to prepare the finished polymer.
The invention has the beneficial effects that:
research shows that in the water precipitation condensation process of the solution polymerization process, under the conditions that the volume ratio of water to colloid is fixed and the mass ratio of solvent to dry glue is not changed, sensible heat and latent heat in the water precipitation condensation process can be regarded as a certain value, and the key of condensation energy saving is to reduce the consumption of steam carrying out gas phase solvent from a condensation kettle. The invention provides a method for treating polymer solution in a solution polymerization method, which is characterized in that before a polymer is separated by elutriation and condensation, the polymer solution is concentrated to evaporate part of organic solvent, the amount of water vapor which is directly contacted with the polymer solution in the elutriation and condensation process is reduced, the energy consumption is reduced, and meanwhile, the amount of water vapor entering a condensation kettle is reduced and the sewage discharge is reduced due to the reduction of the amount of the water vapor.
Drawings
FIG. 1 is a flow chart of the polymer solution treatment provided in example 1.
Reference numerals; 1. polymer solution, 2, an evaporator, 3, organic solvent steam, 4, polymer solution with improved concentration, 5, water steam, 6, hot water, 7, a coagulation kettle, 8, gas phase at the top of the coagulation kettle, 9 and colloidal particle water.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
As shown in FIG. 1, a polymer solution 1 is formed after adding a terminating agent to a polymer reaction solution, the polymer solution 1 enters an evaporator 2, and is heated by a heating medium to obtain an organic solvent vapor 3, wherein the organic solvent is recovered and is evaporated and concentrated to obtain a polymer solution 4 with improved concentration. The polymer solution 4 with improved concentration enters a condensation kettle 7 and contacts with hot water 6 and water vapor 5 entering the condensation kettle 7, the organic solvent and the polymer solid in the polymer solution 4 with improved concentration are separated, mixed vapor formed by the organic solvent and the water is taken as a gas phase 8 at the top of the condensation kettle and is discharged from the top of the condensation kettle, the organic solvent is separated and recovered, polymer particle mixed water phase and colloidal particle water 9 separated out from the condensation kettle are discharged from the condensation kettle, the polymer is separated to obtain the polymer, and the separated water is partially returned to the condensation kettle and is partially discharged as sewage.
The treatment method can be applied to polymer solution obtained by solution polymerization, and the polymer can be selected from Butadiene Rubber (BR), solution polymerized styrene-butadiene rubber (SSBR), styrene-butadiene-styrene block copolymer (SBS) or hydrogenated product thereof, styrene-isoprene-styrene block copolymer or hydrogenated product thereof, hydrogenated nitrile rubber, brominated butyl rubber, chlorinated butyl rubber, polyisoprene rubber, acrylonitrile-butadiene-styrene (ABS) and the like.
Specifically, the brominated butyl rubber cement was treated using the process flow shown in FIG. 1. And (3) carrying out contact reaction on the n-hexane solution of the butyl rubber and bromine to obtain a brominated butyl rubber reaction solution, and adding a reaction terminator sodium hydroxide solution to obtain a brominated butyl rubber glue solution.
The concentration of rubber in the brominated butyl rubber glue solution is 17 wt%, the temperature is 55 ℃, the flow rate is 25000kg/h, the brominated butyl rubber glue solution enters an evaporator, the brominated butyl rubber glue solution is heated by 0.7MPa water vapor, the temperature of the glue solution is increased to 80-85 ℃, the gas phase flow rate of a solvent at the top of the evaporator is controlled to be 9300kg/h, and the brominated butyl rubber glue solution with the mass concentration of about 27 wt% is obtained after concentration and evaporation.
And (3) feeding the 27 wt% brominated butyl rubber glue solution into a condensation kettle, contacting with hot water at 95 ℃ and water vapor at 0.7MPa, controlling the temperature of the condensation kettle at 95 ℃, separating out the polymer in a solid form, and forming colloidal particle water with water. And ejecting mixed steam formed by the normal hexane and the water from the condensation kettle, wherein the temperature of the mixed steam is 95 ℃, the mixed steam contains 75 wt% of the normal hexane and 25 wt% of the water, separating and recovering the normal hexane, and discharging the separated water phase as sewage. The colloidal particle water at the bottom of the coagulation kettle is filtered to separate colloidal particles and water, the separated colloidal particles are further dried to prepare a finished product of the brominated butyl rubber, and part of the separated water returns to the coagulation kettle and is discharged as sewage.
The consumption of 0.7MPa water vapor in the whole treatment process is 7.5 t/h. The sewage discharge amount is 4.9 t/h.
Example 2
And (3) carrying out contact reaction on the normal hexane solution of the butyl rubber and bromine to obtain a brominated butyl rubber reaction solution, and adding a reaction terminator sodium hydroxide solution into the reaction solution to obtain a brominated butyl rubber glue solution. The concentration of the brominated butyl rubber glue solution is 17 wt%, the temperature is 55 ℃, the flow rate is 25000kg/h, the brominated butyl rubber glue solution enters an evaporator, the brominated butyl rubber glue solution is heated by 0.7MPa water vapor, the temperature of the glue solution is increased to 80-85 ℃, the gas phase flow rate of a solvent at the top of the evaporator is controlled to be 5700kg/h, and the brominated butyl rubber glue solution is concentrated and evaporated to obtain the glue solution with the mass concentration of 22 wt%.
And (2) allowing 22 wt% of brominated butyl rubber glue solution to enter a condensation kettle, contacting with hot water at 95 ℃ and steam at 0.7MPa, controlling the temperature of the condensation kettle at 95 ℃, separating out the polymer in a solid form, and forming colloidal particle water with water. And ejecting mixed steam formed by the normal hexane and the water from the condensation kettle, wherein the temperature of the mixed steam is 95 ℃, the mixed steam contains 75 wt% of the normal hexane and 25 wt% of the water, separating and recovering the normal hexane, and discharging the separated water phase as sewage. The colloidal particle water at the bottom of the coagulation kettle is filtered to separate colloidal particles and water, the separated colloidal particles are further dried to prepare a finished product of the brominated butyl rubber, and part of the separated water returns to the coagulation kettle and is discharged as sewage.
The consumption of 0.7MPa steam in the whole treatment process is 8.3 t/h. The sewage discharge amount is 6 t/h.
Example 3
And (3) carrying out contact reaction on the normal hexane solution of the butyl rubber and bromine to obtain a brominated butyl rubber reaction solution, and adding a reaction terminator sodium hydroxide solution into the reaction solution to obtain a brominated butyl rubber glue solution. The concentration of the brominated butyl rubber glue solution is 17 wt%, the temperature is 55 ℃, the flow rate is 25000kg/h, the brominated butyl rubber glue solution enters an evaporator, the brominated butyl rubber glue solution is heated by 0.7MPa water vapor, the temperature of the glue solution is increased to 80-85 ℃, the gas phase flow rate of a solvent at the top of the evaporator is controlled to 11800kg/h, and the brominated butyl rubber glue solution is concentrated and evaporated to obtain the glue solution with the mass concentration of about 32 wt%.
And (2) allowing 32 wt% of brominated butyl rubber glue solution to enter a condensation kettle, contacting with hot water at 95 ℃ and steam at 0.7MPa, controlling the temperature of the condensation kettle at 95 ℃, separating out the polymer in a solid form, and forming colloidal particle water with water. And ejecting mixed steam formed by the normal hexane and the water from the condensation kettle, wherein the temperature of the mixed steam is 95 ℃, the mixed steam contains 75 wt% of the normal hexane and 25 wt% of the water, separating and recovering the normal hexane, and discharging the separated water phase as sewage. The colloidal particle water at the bottom of the coagulation kettle is filtered to separate colloidal particles and water, the separated colloidal particles are further dried to prepare a finished product of the brominated butyl rubber, and part of the separated water returns to the coagulation kettle and is discharged as sewage.
The consumption of 0.7MPa steam in the whole treatment process is 7.0 t/h. The sewage discharge amount is 4.0 t/h.
Comparative example 1
The normal hexane solution of butyl rubber is in contact reaction with bromine to obtain a brominated butyl rubber reaction solution, a reaction terminator sodium hydroxide solution is added into the reaction solution to obtain a brominated butyl rubber glue solution, the concentration of the glue solution is 17 wt%, the temperature is 55 ℃, the flow rate is 25000kg/h, the brominated butyl rubber glue solution enters a condensation kettle and is in contact with hot water at 95 ℃ and water vapor at 0.7MPa, the temperature of the condensation kettle is controlled at 95 ℃, a polymer is separated out in a solid form, and the polymer and the water form colloidal particle water. And ejecting mixed steam formed by the normal hexane and the water out of the condensation kettle, wherein the temperature of the mixed steam is 95 ℃, the mixed steam contains 75 wt% of the normal hexane and 25 wt% of the water, and separating and recovering the normal hexane. The colloidal particle water in the tower kettle is filtered to separate colloidal particles and water, the separated colloidal particles are further dried to prepare a finished product of the brominated butyl rubber, and part of the separated water returns to the condensation kettle and is discharged as sewage.
The consumption of 0.7MPa water vapor in the whole treatment process is 9.6 t/h. The sewage discharge amount is 8.8 t/h.
It can be seen through the comparison that before the polymer solution enters the water precipitation condensation kettle, the steam dosage can be reduced and the sewage discharge amount can be reduced through concentration and temperature increase, and the energy conservation is more remarkable as the concentration increase range is larger. The treatment method can effectively reduce the water vapor consumption in the process of water precipitation and coagulation, reduce the sewage discharge and save energy.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method of treating a polymer solution, the method comprising the steps of: before the polymer is separated by water precipitation and coagulation, the polymer solution is concentrated and evaporated to obtain a polymer solution with improved concentration.
2. The process according to claim 1, characterized in that it comprises the following steps:
(1) concentrating and evaporating the polymer solution to obtain a polymer solution with improved concentration;
(2) and (3) contacting the polymer solution with the increased concentration with hot water and water vapor, precipitating the polymer in a solid form, and discharging mixed vapor formed by the organic solvent and the water for recovery.
3. The process according to claim 1, wherein the water-out coagulation is a process of bringing the polymer solution into contact with steam and/or hot water, and the water causes the polymer to be precipitated in a solid form while obtaining a mixed steam of the organic solvent and water.
4. The treatment method according to any one of claims 1 to 3, wherein the polymer solution is a polymer solution prepared by solution polymerization;
preferably, the polymer is a polymer dissolved in a hydrocarbon solvent, and is preferably at least one of butadiene rubber, solution-polymerized styrene-butadiene rubber, a styrene-butadiene-styrene block copolymer or a hydrogenated product thereof, a styrene-isoprene-styrene block copolymer or a hydrogenated product thereof, hydrogenated nitrile rubber, halogenated butyl rubber, polyisoprene rubber, acrylonitrile-butadiene-styrene.
Preferably, the polymer solution contains an organic solvent, and the organic solvent is the same as the organic solvent discharged in the water precipitation coagulation stage;
preferably, the organic solvent is a hydrocarbon solvent, such as a C5-C7 hydrocarbon.
5. The process according to any one of claims 1 to 4, wherein the mass concentration of the polymer in the polymer solution is from 10 to 25 wt%;
preferably, the concentration-increased polymer solution refers to a polymer solution in which the mass concentration of the polymer is increased by 5 to 15 wt% as compared to that before concentration.
6. The process according to any one of claims 1 to 5, wherein the concentration and evaporation are carried out in an evaporator.
7. The process according to any one of claims 2 to 6, wherein in the step (1), part of the organic solvent is distilled off during the concentration and evaporation;
preferably, the concentration and evaporation mode is a steam heating mode, and the heating raises the temperature of the polymer solution so as to evaporate part of the organic solvent.
8. The process according to any one of claims 2 to 7, wherein in step (2), the polymer solution having an increased concentration is contacted with hot water and water vapor in a coagulation reactor;
preferably, the temperature in the condensation kettle is controlled to be 70-120 ℃;
preferably, the temperature in the coagulum kettle is higher than the temperature of the polymer solution of increased concentration.
9. The process according to any one of claims 2 to 8, wherein in the step (2), the temperature of the hot water is 80 to 120 ℃;
preferably, the water vapor is 0.2 to 2.0MPa of steam.
10. The process according to any one of claims 2 to 9, wherein in the step (2), the mixed steam is separated to obtain an organic solvent and water, the organic solvent is recovered, and the water is discharged as sewage;
preferably, the precipitated polymer and water form a polymer solids/water mixture that is separated to obtain a crumb and water.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111718436A (en) * | 2020-07-27 | 2020-09-29 | 山东京博中聚新材料有限公司 | Production process of brominated butyl rubber |
| CN114316095A (en) * | 2020-09-29 | 2022-04-12 | 北京诺维新材科技有限公司 | Polymer coagulation method |
| CN114316090A (en) * | 2020-09-29 | 2022-04-12 | 北京诺维新材科技有限公司 | Low-solvent-residue polymer and preparation method thereof |
| CN114430748A (en) * | 2020-07-22 | 2022-05-03 | 株式会社Lg化学 | Method for recovering solvent and solvent recovery apparatus |
| CN114432721A (en) * | 2020-11-03 | 2022-05-06 | 北京诺维新材科技有限公司 | Method for concentrating polymer solution and application thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114430748A (en) * | 2020-07-22 | 2022-05-03 | 株式会社Lg化学 | Method for recovering solvent and solvent recovery apparatus |
| US11970558B2 (en) | 2020-07-22 | 2024-04-30 | Lg Chem, Ltd. | Method of recovering solvent and solvent recovery apparatus |
| CN114430748B (en) * | 2020-07-22 | 2024-05-10 | 株式会社Lg化学 | Method for recovering solvent and solvent recovery apparatus |
| CN111718436A (en) * | 2020-07-27 | 2020-09-29 | 山东京博中聚新材料有限公司 | Production process of brominated butyl rubber |
| CN111718436B (en) * | 2020-07-27 | 2023-01-31 | 山东京博中聚新材料有限公司 | Production process of brominated butyl rubber |
| CN114316095A (en) * | 2020-09-29 | 2022-04-12 | 北京诺维新材科技有限公司 | Polymer coagulation method |
| CN114316090A (en) * | 2020-09-29 | 2022-04-12 | 北京诺维新材科技有限公司 | Low-solvent-residue polymer and preparation method thereof |
| CN114316090B (en) * | 2020-09-29 | 2023-06-30 | 北京诺维新材科技有限公司 | Polymer with low solvent residue and preparation method thereof |
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| CN114432721A (en) * | 2020-11-03 | 2022-05-06 | 北京诺维新材科技有限公司 | Method for concentrating polymer solution and application thereof |
| CN114432721B (en) * | 2020-11-03 | 2023-09-15 | 北京诺维新材科技有限公司 | Polymer solution concentration method and application thereof |
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