CN114941184A - Preparation method of spinning solution, spinning solution and filtering membrane - Google Patents
Preparation method of spinning solution, spinning solution and filtering membrane Download PDFInfo
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- CN114941184A CN114941184A CN202210747619.3A CN202210747619A CN114941184A CN 114941184 A CN114941184 A CN 114941184A CN 202210747619 A CN202210747619 A CN 202210747619A CN 114941184 A CN114941184 A CN 114941184A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
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- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
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- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
Abstract
The invention provides a preparation method of spinning solution, which at least comprises the following steps: firstly, mixing and reacting a bisphenol compound, a double halogenated aromatic compound in molar excess relative to the bisphenol compound and a first combined alkali salt; then adding a second combined alkali salt into the reactant, and reacting to obtain an intermediate polymerization solution; then treating the intermediate polymerization solution to obtain an intermediate polymer; finally, the intermediate polymer and the spinning assistant are dissolved in a spinning solvent together to obtain a spinning solution. In the preparation method of the spinning solution, the combined alkali salt is adopted, and the reaction degree of the polycondensation reaction is improved by adding the first combined alkali salt and the second combined alkali salt in batches. Experimental results show that the spinning solution prepared by the method is uniform and limpid, the content of insoluble substances is lower than 0.1%, the spinning solution is stable in long-time storage, and the spinning solution has the advantages of stable spinning process, little or no phenomena of hole blockage and yarn breakage, convenience and safety in use and high economy.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of a spinning solution, the spinning solution and a filtering membrane.
Background
The sulfone polymer is an important variety in special engineering plastics, and has high temperature resistance (the glass transition temperature is above 185 ℃), excellent thermal stability, excellent model performance, excellent chemical resistance and the like. Based on the good comprehensive performance of the sulfone polymer, polysulfone series products are widely applied to high-end fields of medical instruments, aerospace, electronics and the like. And the filtering membrane prepared by the sulfone polymer not only has excellent temperature resistance, solvent resistance and higher mechanical strength, but also has excellent permeability, so the filtering membrane is widely applied to the aspects of ultrafiltration, microfiltration, reverse osmosis, gas separation, alcohol/water separation, olefin/alkane separation, immobilized carriers, hemodialysis and the like.
The filtering membrane is usually prepared by preparing a spinning solution from a sulfone polymer, an additive and a solvent, then feeding the spinning solution into a spinning nozzle through a filter screen and a metering pump under the pressure of nitrogen, then extruding the spinning solution from spinning holes of the spinning nozzle, and finally preparing and forming the filtering membrane through processes of conversion, rinsing, soaking, airing and the like.
But the existing sulfone polymer has poor solubility in the process of preparing spinning solution, and the phenomena of turbid and uneven solution and the like occur; and the processing performance and the application performance of the spinning membrane are low, so that the spinning orifices are easily blocked in the process of extruding from the spinning orifices of the spinning nozzle, the spinning efficiency and the stability are greatly influenced, the regularity of membrane product materials is damaged, the strength of the spinning membrane is reduced, the processing difficulty of spinning is increased, and the economical efficiency of products is reduced.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a spinning solution, which effectively increases the solubility of sulfone polymers, enables the spinning solution to be uniform and clear and to be stably stored for a long time, enables the spinning to be smooth and stable in the spinning process, and has few or no phenomena of hole plugging and filament breakage, greatly improves the production efficiency of products, and simultaneously improves the regularity and strength of materials, and has higher economical efficiency.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of spinning solution at least comprises the following steps:
1) mixing a bisphenol compound, a bis-halogenated aromatic compound in molar excess relative to the bisphenol compound, and a first combined base salt for reaction;
2) after reacting under certain conditions, adding a second combined alkali salt into the reactant, and reacting to obtain an intermediate polymerization solution;
3) treating the intermediate polymerization solution to obtain an intermediate polymer;
4) and dissolving the intermediate polymer and the spinning auxiliary agent in a spinning solvent to obtain the spinning solution.
Preferably, the first and second combined base salts are both mixtures of alkali metal carbonates and metal hydroxides;
the molar ratio of the alkali metal carbonate to the metal hydroxide in the first combined alkali salt is 1-0.9: 0-0.1;
the molar ratio of the alkali metal carbonate to the metal hydroxide in the second alkali salt composition is 0-0.1: 1-0.9.
Preferably, the molar ratio between the sum of the bisphenol compound, the bis-halogenated aromatic compound, the first combined base salt, and the second combined base salt is 1: 1-1.05: 1 to 1.2.
Preferably, in step 2), when the degree of reaction of the bisphenol compound reaches at least 65%, the second salt of the combination alkali is added to the above reactant.
Preferably, in the step 2), after the reaction time is 4-8 hours, the second combined alkali salt is added into the reactants.
Preferably, in step 2), the second alkali salt is dissolved in an organic solvent to prepare a homogeneous suspension, and then the homogeneous suspension is added to the above reactant.
Preferably, the particle size of the second combination base salt dissolved in the organic solvent is 10-200 microns.
Preferably, the concentration of the second combined base salt in the homogeneous suspension is 20-70%.
Preferably, the halogenated aromatic compound is one or more of 4,4 '-dichlorodiphenyl sulfone, 4' -difluorodiphenyl sulfone, 4 '-dibromodiphenyl sulfone and 4, 4' -diiododiphenyl sulfone;
the bisphenol compound is one or more of 4,4 '-bisphenol, bisphenol A, 4' -dihydroxy-diphenyl sulfone, hydroquinone, 4 '-dihydroxy-diphenyl ether, alpha' -bis- (4-hydroxyphenyl) -p-diisopropylbenzene and 1, 4-bis (4-hydroxyphenoxy) benzene.
The invention also provides a spinning solution, and the mass content of insoluble substances in the spinning solution is not higher than 0.1% by adopting the preparation method.
The invention also provides a filter membrane which is prepared from the spinning solution and is used for water purification, air purification and hemodialysis.
Compared with the prior art, the invention has the advantages and positive effects that:
in the preparation method of the spinning solution, the deprotonation and polycondensation reaction of reactants are promoted by adopting the combined alkali salt, the deprotonation and polycondensation reaction effects of different alkalies between the first combined alkali salt and the second combined alkali salt are fully utilized by adopting a batch adding mode, and a hydrolysis side reaction caused by accumulation of excessive alkali salt due to one-time addition is avoided, so that the whole reaction degree is accelerated, the reaction time is shortened, the reaction efficiency is improved, and the existence of small molecular compounds or insoluble substances generated by the side reaction in an intermediate polymer is greatly reduced.
Experimental results show that when the preparation method provided by the invention is adopted to prepare the spinning solution, the intermediate polymer has better solubility, the content of insoluble substances filtered in the spinning solution is not higher than 0.1%, and the spinning solution is uniform, clear and stable to store for a long time. The spinning solution provided by the invention has the advantages of smooth and stable spinning in the spinning process, no or few phenomena of hole blockage and yarn breakage, greatly improved production efficiency of products, improved regularity and strength of materials, and higher economy.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in purity, and the present invention preferably employs industrial purity or purity which is conventional in the field of polymer polymerization.
All the noun expressions and acronyms of the invention belong to the conventional noun expressions and acronyms in the field, each noun expression and acronym is clearly and definitely clear in the relevant application field, and a person skilled in the art can clearly, exactly and uniquely understand the noun expressions and acronyms.
The invention provides a preparation method of spinning solution, which at least comprises the following steps:
1) mixing and reacting a bisphenol compound, a molar excess of a bishaloaromatic compound relative to the bisphenol compound, and a first combination base salt;
2) after reacting under certain conditions, adding a second combined alkali salt into the reactant, and reacting to obtain an intermediate polymerization solution;
3) treating the intermediate polymerization solution to obtain an intermediate polymer;
4) and dissolving the intermediate polymer and a spinning auxiliary agent in a spinning solvent to obtain the spinning solution.
The halogenated aromatic compound is an aromatic compound containing two halogenated groups in a molecule, and can be selected from one or more of 4,4 '-dichlorodiphenyl sulfone, 4' -difluorodiphenyl sulfone, 4 '-dibromodiphenyl sulfone and 4, 4' -diiododiphenyl sulfone.
The bisphenol compound is an aromatic compound having two phenolic hydroxyl groups in the molecule, and may be one or more selected from 4,4 '-bisphenol, bisphenol a, 4' -dihydroxy-diphenylsulfone, hydroquinone, 4 '-dihydroxy-diphenylether, α' -bis- (4-hydroxyphenyl) -p-diisopropylbenzene, and 1, 4-bis (4-hydroxyphenoxy) benzene.
In the present invention, the first combined base salt is preferably a mixture of an alkali metal carbonate and a metal hydroxide. Wherein the molar ratio of the alkali metal carbonate to the metal hydroxide in the first alkali salt composition is 1-0.9: 0-0.1.
More preferably, the molar ratio of the alkali metal carbonate to the metal hydroxide in the first combined base salt is 1-0.95: 0-0.05, i.e. when the first combined base salt is mainly alkali metal carbonate and only a small amount or trace amount of metal hydroxide.
In the present invention, the second combined base salt is preferably a mixture of an alkali metal carbonate and a metal hydroxide, similar to the first combined base salt. Wherein the molar ratio of the alkali metal carbonate to the metal hydroxide in the second alkali salt composition is 0-0.1: 1-0.9.
More preferably, the molar ratio of the alkali metal carbonate to the metal hydroxide in the second alkali base salt is 0-0.05: 1-0.95, and the content ratio of each component in the second alkali base salt is opposite to that of each component in the first alkali base salt, i.e. most of the components are metal hydroxide, and a small amount of the components are alkali metal carbonate.
In the present invention, the molar ratio of the bisphenol compound, the halogenated aromatic compound and the combined alkali salt participating in the reaction is 1: 1-1.05: 1 to 1.2, wherein the combined base salt is the sum of the first combined base salt and the second combined base salt. Preferably, the first combined alkali salt is added in an amount of 60% to 100% (excluding 100%) of the total, and the second combined alkali salt is added in an amount of 0% to 40% (excluding 0%) of the total
In step 2), the second alkali salt composition is dissolved in an organic solvent to prepare a homogeneous suspension, and then the prepared homogeneous suspension is added into a mixed reaction system of a halogenated aromatic compound and a bisphenol compound.
The organic solvent is selected from high-polarity solvent, such as dimethyl sulfoxide, dimethyl sulfone, diphenyl sulfone, diethyl sulfoxide, diethyl sulfone, diisopropyl sulfone, tetrahydrothiophene-1, 1-dioxide (commonly called tetramethylene sulfone or sulfolane), tetrahydrothiophene-1-monoxide and their mixture; or nitrogen-containing polar aprotic solvents such as dimethylacetamide, dimethylformamide and N-methylpyrrolidone have been disclosed in the prior art. In the present invention, sulfolane or N-methylpyrrolidone is preferably used.
In the preparation of the homogeneous suspension, the second alkali salt is ground into powder particles, preferably, the particle size of the second alkali salt dissolved in the organic solvent is 10 to 200 micrometers, more preferably 50 to 100 micrometers.
In preparing a homogeneous suspension, the concentration of the second alkali salt composition in the homogeneous suspension is preferably controlled to be 20-70%. More preferably 40 to 60%.
In the present invention, when the halogenated aromatic compound is reacted with the bisphenol compound, it is preferable that the homogeneous suspension containing the second alkali salt or the second alkali salt is added to the reaction system in step 2) when the degree of reaction of the bisphenol compound reaches at least 65%.
In the present invention, when the halogenated aromatic compound and the bisphenol compound are reacted, in the step 2), the prepared homogeneous suspension containing the second alkali salt or the second alkali salt may be added to the reaction system after the reaction time is 4 to 8 hours.
The invention also provides a spinning solution, and the mass content of insoluble substances in the spinning solution prepared by the preparation method is not higher than 0.1%.
The invention also provides a filter membrane which is prepared from the spinning solution and is used for water purification, air purification and hemodialysis.
Specifically, under the catalytic action of the first alkali salt, the double-halogen aromatic compound and the bisphenol compound are subjected to polycondensation reaction, and the second alkali salt is added during the stage or at the end of the reaction to further catalyze the reactants to perform polycondensation. After the polycondensation reaction is finished, the intermediate polymer is obtained through the steps of precipitation, desalination, washing, drying and the like.
Weighing a certain amount of the intermediate polymer and the spinning auxiliary agent, adding the intermediate polymer and the spinning auxiliary agent into a spinning solvent, stirring and dissolving at room temperature under the protection of nitrogen, standing, and removing the blister to obtain the spinning solution. The spinning auxiliary agent adopts hydrophilic high molecular compound, such as polyvinylpyrrolidone or polyethylene glycol or their mixture derivatives, etc., and the spinning solvent adopts organic solvent, such as NMP or DMF, etc.
And taking the spinning solution as shell solution, extruding at a constant speed by spinning equipment under the control of a metering pump, performing phase conversion in a coagulating bath to form a membrane product, then leading the membrane product out to winding equipment, and then performing processes of cutting, soaking, airing and the like to obtain the filtering membrane.
In the above process, the first alkali salt composition is first catalytically polymerized, and the second alkali salt composition is added during or at the end of the reaction to further catalyze the condensation polymerization of the reactants. From the whole course of the reaction, the first combination base salt is less basic and the reaction is relatively mild, allowing relatively more time and space for the reactants to deprotonate. The second alkali salt composition has relatively strong alkalinity and relatively strong catalytic effect compared with the first alkali salt composition, further accelerates the reaction process on the basis of the catalytic effect of the first alkali salt composition, improves the reaction rate of polycondensation, avoids the formation of small molecular compounds by the cyclization reaction of oligomers, enhances the polymerization effect of polymers, enables the molecular weight distribution of the polymers to be relatively concentrated and narrow, and effectively improves the regularity of products generated in intermediate polymers.
Therefore, in the preparation method of the spinning solution, the combined alkali salt mode is adopted to improve the reaction process of the polycondensation reaction, the batch adding mode is adopted to fully utilize the effect of different alkalis between the first combined alkali salt and the second combined alkali salt on the reaction polycondensation, and the hydrolysis side reaction caused by accumulation of excessive alkali salt due to one-time addition is avoided, so that the whole reaction process is accelerated, the reaction time is shortened, the production efficiency is improved, and the existence of micromolecule compounds or insoluble substances generated by the side reaction in the intermediate polymer is greatly reduced.
Experimental results show that the spinning solution prepared by the method has good dissolubility, the content of insoluble substances filtered in the spinning solution is not higher than 0.1%, and the spinning solution is uniform, clear and stable to store for a long time.
The spinning solution provided by the invention has smooth and stable spinning in the spinning process, has no or few phenomena of hole blockage and yarn breakage, greatly improves the production efficiency of products, improves the regularity and strength of materials, and has higher economical efficiency.
For further illustration of the present invention, the following will describe in detail a method for preparing a spinning solution provided by the present invention with reference to the following examples, but it should be understood that these examples are carried out on the premise of the technical scheme of the present invention, and the detailed embodiments and specific procedures are given only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
Dichlorodiphenyl sulfone (20.68g), bisphenol A (15.29g), anhydrous potassium carbonate (average particle diameter 20 μm) (9.95g), and NMP (45g) were charged into a 250ml 4-necked flask. The 4-neck flask was equipped with an overhead mechanical stirrer, nitrogen dip tube, thermocouple, and a Dean-Stark trap with condenser (Dean-Stark trap). The reaction mixture was stirred and the temperature was raised to 150-170 ℃ and held for 3-4.5 h. Collecting water in the water separator to test the water content; after the content of the drained water reaches 1.3g, the temperature is raised to 180 ℃ and 200 ℃, the reaction is carried out for 2h, 10mL of sodium hydroxide suspension with the solid content of 40 percent is added, and the temperature is maintained for reaction for 3-6 h. Diluting the reaction mixture by NMP, carrying out end-capping treatment by using chloromethane at the temperature of 140 ℃ for 30min, and centrifuging to remove salts; the centrifuged polymerization solution was coagulated into rapidly stirred water. The coagulum was reslurried with hot water, filtered, and dried in a vacuum oven at 140 ℃ for 4 hours to give a polysulfone product.
Weighing a certain amount of polysulfone (15g) in a weight ratio, putting the polysulfone into a dissolving tank, weighing additives of polyvinylpyrrolidone (10g), water (0.2g) and polyethylene glycol (4g), adding the additives into the dissolving tank in the same way, and then adding an organic solvent of DMAc (75 g). Stirring and dissolving for 6h at 60 ℃, and then standing for 8h to remove bubbles in the feed liquid to form the spinning solution.
Example 2
Dichlorodiphenyl sulfone (20.68g), bisphenol A (15.29g), anhydrous potassium carbonate (average particle size 20 μm) (9.95g), sodium hydroxide (1g) and NMP (45g) were charged to a 250ml 4-neck flask equipped with an overhead mechanical stirrer, nitrogen dip tube, thermocouple and a Dean-Stark trap with condenser (Dean-Stark trap). The reaction mixture was stirred and the temperature was raised to 150-170 ℃ and held for 3-4.5 h. Collecting water in the water separator to test the water content; when the water content reaches 1.3g, the temperature is raised to 180 ℃ and 200 ℃, the reaction is carried out for 3h, then 8mL of potassium hydroxide suspension with the solid content of 40 percent is added, and the temperature is maintained for reaction for 3-6 h. Diluting the reaction mixture by NMP, carrying out end-capping treatment by using chloromethane at the temperature of 140 ℃ for 30min, and centrifuging to remove salts; the centrifuged polymerization solution was coagulated into rapidly stirred water. The coagulum was reslurried with hot water, filtered, and dried in a vacuum oven at 140 ℃ for 4 hours to give a polysulfone product.
Weighing a certain amount of polysulfone (15g) in a weight ratio, putting the polysulfone into a dissolving tank, weighing additives of polyvinylpyrrolidone (10g), water (0.2g) and polyethylene glycol (4g), adding the additives into the dissolving tank in the same way, and then adding an organic solvent of DMAc (75 g). Stirring and dissolving for 6h at 60 ℃, and then standing for 8h to remove bubbles in the feed liquid to form the spinning solution.
Example 3
Dichlorodiphenyl sulfone (20.68g), bisphenol S (17.67g), anhydrous potassium carbonate (average particle size 20 μm) (9.95g), and NMP (45g) were charged to a 250ml 4-neck flask equipped with an overhead mechanical stirrer, nitrogen dip tube, thermocouple, and a Dean-Stark trap (Dean-Stark trap) with a condenser. The reaction mixture was stirred and the temperature was raised to 150-170 ℃ and held for 3-4.5 h. Collecting water in the water separator to test the water content; when the water content reaches 1.3g, the temperature is raised to 180 ℃ and 200 ℃, then the reaction is carried out for 2h, 8mL of potassium hydroxide suspension with the solid content of 40 percent is added, and the temperature is maintained for reaction for 3-6 h. Diluting the reaction mixture by NMP, carrying out end-capping treatment by using chloromethane at the temperature of 140 ℃ for 30min, and centrifuging to remove salts; the centrifuged polymer solution was coagulated into rapidly stirred water. The coagulum was reslurried with hot water, filtered, and dried in a vacuum oven at 140 ℃ for 4 hours to give the polyethersulfone product.
Weighing a certain amount of polysulfone (15g) in a weight ratio, putting the polysulfone into a dissolving tank, weighing additives of polyvinylpyrrolidone (10g), water (0.2g) and polyethylene glycol (4g), adding the additives into the dissolving tank in the same way, and then adding an organic solvent of DMAc (75 g). Stirring and dissolving for 6h at 60 ℃, and then standing for 8h to remove bubbles in the feed liquid to form the spinning solution.
Example 4
Dichlorodiphenyl sulfone (20.68g), bisphenol S (17.47g), anhydrous potassium carbonate (average particle size 20 μm) (9.95g), potassium hydroxide (1g) and NMP (45g) were charged to a 250ml 4-neck flask equipped with an overhead mechanical stirrer, nitrogen dip tube, thermocouple and a Dean-Stark trap with condenser (Dean-Stark trap). The reaction mixture was stirred and the temperature was raised to 150-170 ℃ and held for 3-4.5 h. Collecting water in the water separator to test the water content; when the water content reaches 1.3g, the temperature is raised to 180 ℃ and 200 ℃, then 8mL of potassium hydroxide suspension with the solid content of 40 percent is added for reaction for 2h, and the temperature is maintained for reaction for 3-6 h. Diluting the reaction mixture by NMP, carrying out end-capping treatment by using chloromethane at the temperature of 140 ℃ for 30min, and centrifuging to remove salts; the centrifuged polymerization solution was coagulated into rapidly stirred water. The coagulum was reslurried with hot water, filtered, and dried in a vacuum oven at 140 ℃ for 4 hours to give the polyethersulfone product.
Weighing a certain amount of polysulfone (15g) into a dissolving tank according to the weight ratio, weighing additives of polyvinylpyrrolidone (10g), water (0.2g) and polyethylene glycol (4g), adding the additives into the dissolving tank in the same way, and then adding an organic solvent DMAc (75 g). Stirring and dissolving for 6h at 60 ℃, and then standing for 8h to remove bubbles in the feed liquid to form the spinning solution.
Example 5
Dichlorodiphenyl sulfone (20.68g), biphenol (13.27g), anhydrous potassium carbonate (average particle size 20 μm) (10.95g), and NMP (45g) were charged to a 250ml 4-neck flask equipped with an overhead mechanical stirrer, nitrogen dip tube, thermocouple, and a Dean-Stark trap (Dean-Stark trap) with a condenser. The reaction mixture was stirred and the temperature was raised to 150-170 ℃ and held for 3-4.5 h. Collecting water in the water separator to test the water content; when the water content reaches 1.3g, the temperature is raised to 180-200 ℃, 8mL of potassium hydroxide suspension with the solid content of 40% is added, and the temperature is maintained for reaction for 3-6 h. Diluting the reaction mixture by NMP, carrying out end-capping treatment by using chloromethane at the temperature of 140 ℃ for 30min, and centrifuging to remove salts; the centrifuged polymerization solution was coagulated into rapidly stirred water. The coagulum was reslurried with hot water, filtered, and dried in a vacuum oven at 140 ℃ for 4h to give polyphenylsulfone product.
Weighing a certain amount of polysulfone (15g) into a dissolving tank according to the weight ratio, weighing additives of polyvinylpyrrolidone (10g), water (0.2g) and polyethylene glycol (4g), adding the additives into the dissolving tank in the same way, and then adding an organic solvent DMAc (75 g). Stirring and dissolving for 6h at 60 ℃, and then standing for 8h to remove bubbles in the feed liquid to form the spinning solution.
Comparative example 1
Dichlorodiphenyl sulfone (20.68g), bisphenol A (15.29g), anhydrous potassium carbonate (average particle size 20 μm) (9.95g), and NMP (45g) were charged to a 250ml 4-neck flask equipped with an overhead mechanical stirrer, nitrogen dip tube, thermocouple, and a Dean-Stark trap (Dean-Stark trap) with a condenser. The reaction mixture was stirred and the temperature was raised to 150-170 ℃ and held for 3-4.5 h. Collecting water in the water separator to test the water content; when the content of the drained water reaches 1.3g, the temperature is raised to 200 ℃ of 180 ℃, and then the temperature is kept for reaction for 3-6 h. Diluting the reaction mixture by NMP, carrying out end-capping treatment by using chloromethane at the temperature of 140 ℃ for 30min, and centrifuging to remove salts; the centrifuged polymerization solution was coagulated into rapidly stirred water. The coagulum was reslurried with hot water, filtered, and dried in a vacuum oven at 140 ℃ for 4 hours to give a polysulfone product.
Weighing a certain amount of polysulfone (15g) in a weight ratio, putting the polysulfone into a dissolving tank, weighing additives of polyvinylpyrrolidone (10g), water (0.2g) and polyethylene glycol (4g), adding the additives into the dissolving tank in the same way, and then adding an organic solvent of DMAc (75 g). Stirring and dissolving for 6h at 60 ℃, and then standing for 8h to remove bubbles in the feed liquid to form the spinning solution.
Comparative example 2
Dichlorodiphenyl sulfone (20.68g), bisphenol S (17.47g), anhydrous potassium carbonate (average particle size 20 μm) (10.3g), and NMP (45g) were charged to a 250ml 4-neck flask equipped with an overhead mechanical stirrer, nitrogen dip tube, thermocouple, and a Dean-Stark trap (Dean-Stark trap) with a condenser. The reaction mixture was stirred and the temperature was raised to 150-170 ℃ and held for 3-4.5 h. Collecting water in the water separator to test the water content; when the content of the drained water reaches 1.3g, the temperature is raised to 180-200 ℃, and then the temperature is kept for reaction for 3-6 h. Diluting the reaction mixture by NMP, carrying out end-capping treatment by using chloromethane at the temperature of 140 ℃ for 30min, and centrifuging to remove salts; the centrifuged polymerization solution was coagulated into rapidly stirred water. The coagulum was reslurried with hot water, filtered, and dried in a vacuum oven at 140 ℃ for 4 hours to give the polyethersulfone product.
Weighing a certain amount of polysulfone (15g) into a dissolving tank according to the weight ratio, weighing additives of polyvinylpyrrolidone (10g), water (0.2g) and polyethylene glycol (4g), adding the additives into the dissolving tank in the same way, and then adding an organic solvent DMAc (75 g). Stirring and dissolving for 6h at 60 ℃, and then standing for 8h to remove bubbles in the feed liquid to form the spinning solution.
Taking 1000g of each spinning solution in the examples and the comparative examples, filtering by using a metal screen with 1000 meshes (the aperture is 13 microns), and after the spinning solution completely passes through, washing the metal screen for 4 times (the dosage is 250g each time) by using 1000g of organic solvent DMAc to ensure that all polymers in the screen completely pass through; then drying the filtered screen mesh in a vacuum drying oven at 200 ℃ for 30 min; accurately weighing the weight of the metal screen and calculating the difference value of the metal screen, thereby obtaining the mass of the filtered insoluble substances, wherein the specific data are as follows:
TABLE 1 content of insoluble matter in dope obtained in examples of the present invention and comparative examples
The above detailed description of the method for preparing a spinning dope according to the present invention, and the principle and embodiments of the present invention are explained herein using specific examples, which are provided only to help understanding the method of the present invention and the core idea thereof, including the best mode, and also to enable any person skilled in the art to practice the present invention, including making and using any devices or systems and performing any combined methods.
It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be included within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A preparation method of spinning solution is characterized by at least comprising the following steps:
1) mixing a bisphenol compound, a bis-halogenated aromatic compound in molar excess relative to the bisphenol compound, and a first combined base salt for reaction;
2) after reacting under certain conditions, adding a second combined alkali salt into the reactant, and reacting to obtain an intermediate polymerization solution;
3) treating the intermediate polymerization solution to obtain an intermediate polymer;
4) and dissolving the intermediate polymer and the spinning auxiliary agent in a spinning solvent to obtain the spinning solution.
2. The process for producing a spinning dope according to claim 1, wherein the first combined base salt and the second combined base salt are each a mixture of an alkali metal carbonate and a metal hydroxide;
the molar ratio of the alkali metal carbonate to the metal hydroxide in the first combined alkali salt is 1-0.9: 0-0.1;
the molar ratio of the alkali metal carbonate to the metal hydroxide in the second alkali salt composition is 0-0.1: 1-0.9.
3. The method according to claim 2, wherein a molar ratio of the sum of the bisphenol compound, the dihaloaromatic compound, and the first combined alkali salt to the second combined alkali salt is 1: 1-1.05: 1 to 1.2.
4. The method of claim 2, wherein in step 2), when the reaction degree of the bisphenol compound reaches at least 65%, the second combined alkali salt is added to the reactant.
5. The method of preparing the spinning dope according to claim 2, wherein the second combined alkali salt is added to the reactants after the reaction time is 4 to 8 hours in the step 2).
6. The process of claim 1, wherein in step 2), the second alkali salt is dissolved in an organic solvent to prepare a homogeneous suspension, and the homogeneous suspension is added to the reaction mixture.
7. The method of producing the spinning dope according to claim 6, wherein the particle size of the second combined alkali salt dissolved in the organic solvent is 10 to 200 μm.
8. The method according to claim 6, wherein the concentration of the second combined alkali salt in the homogeneous suspension is 20 to 70%.
9. A spinning dope characterized in that the mass content of insolubles in the spinning dope is not higher than 0.1% by the production method according to any one of claims 1 to 8.
10. A filtration membrane, characterized by being produced using the spinning dope containing the spinning dope of claim 9, and used for water purification, air purification, hemodialysis.
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| CN105555819A (en) * | 2013-08-13 | 2016-05-04 | 费森尤斯医疗保健集团 | Process for making polyarylethers and use in membrane preparation |
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