CN114653215A - Method for preparing hydrophilic ultrafiltration membrane containing carboxyl polysulfate from phenolphthalein copolymerization type sulfate - Google Patents
Method for preparing hydrophilic ultrafiltration membrane containing carboxyl polysulfate from phenolphthalein copolymerization type sulfate Download PDFInfo
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- CN114653215A CN114653215A CN202210347052.0A CN202210347052A CN114653215A CN 114653215 A CN114653215 A CN 114653215A CN 202210347052 A CN202210347052 A CN 202210347052A CN 114653215 A CN114653215 A CN 114653215A
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Abstract
The invention relates to a method for preparing a carboxyl-containing polysulfate hydrophilic ultrafiltration membrane from phenolphthalein copolymer sulfate, which comprises the following steps: s1, dissolving phenolphthalein copolymerization type sulfuric ester in an organic solvent, adding an alkali solution for hydrolysis, and adding a metal reducing agent into a system for reduction after the hydrolysis is finished; s2, filtering the reaction liquid obtained in the step S1 to obtain phenolphthalein copolymerization type sulfuric ester solution; s3, adding the phenolphthalein copolymerization type sulfuric ester solution obtained in the step S3 into an acidic aqueous solution, precipitating a solid polymer, washing with water, and drying to obtain carboxyl-containing copolymerization sulfuric ester; s4, dissolving the co-sulfated obtained in the step S3 in an organic solvent, adding a pore-forming additive, stirring, filtering and standing to obtain a membrane casting solution; and S5, preparing the ultrafiltration membrane by using the membrane casting solution. A structural monomer with high rigidity is introduced into a high molecular polymer by using a click chemistry method, and a high molecular weight polysulfate material is successfully prepared.
Description
Technical Field
The invention belongs to the technical field of ultrafiltration membrane separation, and particularly relates to a method for preparing a carboxyl-containing polysulfate hydrophilic ultrafiltration membrane from phenolphthalein copolymerization type sulfuric ester.
Background
As a novel separation technology, the membrane separation technology has the advantages of simple operation, high equipment filling density, mild working conditions, energy conservation, no secondary pollution and the like, is an important technology for solving the problems of resource type water shortage and water quality type water shortage, and is also considered as a key technology of the chemical industry in the 21 st century. The membrane technology can be divided into microfiltration, ultrafiltration, nanofiltration, reverse osmosis, pervaporation, gas separation and the like according to different separation processes. The ultrafiltration technology usually adopts a porous membrane with the pore diameter of 2-100nm and the skin thickness of 0.1-10 μm as a separation membrane, operates under the operation pressure of 0.1-0.4MPa, utilizes micropores on the surface of the membrane to sieve, can meet the separation and purification requirements of substances with different molecular weights, effectively intercepts particles, colloids, bacteria, various organic matters and the like, and is widely applied to industrial wastewater treatment, municipal sewage treatment, food, pharmaceutical industry and the like. In practical applications, the membrane separation technology still leaves many problems to be solved, and the operation cost is high. The operation cost of the ultrafiltration membrane is high mainly because the ultrafiltration membrane is easy to generate membrane pollution and block membrane pores in the use process, so that the membrane flux is reduced, and the service life of the membrane is shortened. Therefore, enhancing the hydrophilicity and the anti-pollution performance of the ultrafiltration membrane are one of the keys of prolonging the service life of the membrane and reducing the cost of the membrane.
The polysulfate material as a new engineering plastic has strong solvent resistance, acid and alkali corrosion resistance, chemical corrosion resistance, high glass transition temperature and excellent mechanical strength. And the polysulfate material has excellent hydrophilicity, high water flux and excellent pollution resistance on the water treatment membrane. Phenolphthalein is used as a cheap chemical raw material, the raw material is easy to obtain, and a large-group monomer is difficult to form a high molecular weight due to strong rigidity of the molecule in the polymerization process. The polysulfate material is polymerized by a click chemistry mode, so that the phenolphthalein monomer is easy to form a high molecular material with high molecular weight and narrow molecular weight distribution in the process of synthesizing phenolphthalein copolymerization type sulfuric ester. And the lactone structure of phenolphthalein is a good active group, which is very helpful for modifying the side chain of the polymer.
Disclosure of Invention
The invention aims to provide a method for preparing a carboxyl-containing polysulfate hydrophilic ultrafiltration membrane from phenolphthalein copolymerization type sulfuric acid ester, so as to solve the problems of high running cost and short service life of the ultrafiltration membrane in the prior art.
In order to achieve the aim, the invention provides a method for preparing a carboxyl-containing polysulfate hydrophilic ultrafiltration membrane from phenolphthalein copolymer type sulfuric ester, which comprises the following steps:
s1, dissolving phenolphthalein copolymerization type sulfuric ester in an organic solvent, adding an alkali solution for hydrolysis, and adding a metal reducing agent into a system for reduction after the hydrolysis is finished;
s2, filtering the reaction liquid obtained in the step S1 to obtain phenolphthalein copolymerization type sulfuric ester solution;
s3, adding the phenolphthalein copolymerization type sulfuric ester solution obtained in the step S3 into an acidic aqueous solution, precipitating a solid polymer, washing with water, and drying to obtain carboxyl-containing copolymerization sulfuric ester;
s4, dissolving the co-sulfated obtained in the step S3 in an organic solvent, adding a pore-forming additive, stirring, filtering and standing to obtain a membrane casting solution;
and S5, preparing the ultrafiltration membrane by using the membrane casting solution.
The invention relates to a method for preparing a carboxyl-containing polysulfate hydrophilic ultrafiltration membrane by using phenolphthalein copolymerization type sulfuric ester, wherein the phenolphthalein copolymerization type sulfuric ester has the following structure:
wherein m is a positive integer, n is an integer greater than or equal to 0, and Ar is one or more of the following groups:
wherein denotes a connecting position of a sulfate ester bond on an aromatic ring.
The method for preparing the hydrophilic ultrafiltration membrane containing the carboxyl polysulfate from the phenolphthalein copolymerization type sulfuric ester has the number average molecular weight of 10000-80000.
According to the method for preparing the hydrophilic ultrafiltration membrane containing the carboxyl polysulfate from the phenolphthalein copolymerization type sulfuric ester, the organic solvent in the steps S1 and S4 is one or more of sulfolane, dimethyl sulfoxide, N-dimethylacetamide, N-dimethylformamide and N-methylpyrrolidone.
In the method for preparing the hydrophilic ultrafiltration membrane containing the carboxyl polysulfate from the phenolphthalein copolymerization type sulfuric ester, in the step S1, the alkali solution is one or more of a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, a sodium carbonate aqueous solution, a potassium carbonate aqueous solution, an ethanol solution of sodium ethoxide, a methanol solution of sodium methoxide, an ethanol solution of triethylamine and an aqueous solution of triethylamine.
The method for preparing the hydrophilic ultrafiltration membrane containing the carboxyl polysulfate from the phenolphthalein copolymerization type sulfuric ester has the advantages that the mass fraction of the organic alkali solution is 10-30 percent, and the concentration of the inorganic alkali solution is 1-5 mol/L.
The method for preparing the hydrophilic ultrafiltration membrane containing the carboxyl polysulfate from the phenolphthalein copolymerization type sulfate has the advantages that in the step S1, the dissolving temperature is 120-130 ℃, the hydrolysis temperature is 70-90 ℃, the hydrolysis time is 5-12h, the reduction temperature is 70-100 ℃, and the reduction time is 6-15 h.
The method for preparing the hydrophilic ultrafiltration membrane containing the carboxyl polysulfate from the phenolphthalein copolymerization type sulfuric ester comprises the step S1, wherein the metal reducing agent is one or more of a complex of palladium and phosphate, zinc powder, iron powder and copper powder.
The invention relates to a method for preparing a hydrophilic ultrafiltration membrane containing carboxyl polysulfate from phenolphthalein copolymer sulfate, wherein in step S3, an acidic aqueous solution is a hydrochloric acid aqueous solution and/or a sulfuric acid aqueous solution, and the concentration of the hydrochloric acid aqueous solution is 0.1-10 mol/L.
The invention relates to a method for preparing a hydrophilic ultrafiltration membrane containing carboxyl polysulfate from phenolphthalein copolymerization type sulfate, which comprises the steps of S3, wherein the washing temperature is 90-170 ℃, the washing pressure is 0-1.5 Mpa, the washing time is 5-12 hours, and the drying mode is drying for 10-20 hours in a vacuum oven at 110-130 ℃.
The method for preparing the hydrophilic ultrafiltration membrane containing the carboxyl polysulfate from the phenolphthalein copolymerization type sulfuric ester comprises the step S3 of washing water until the salinity of the water is less than 50ppm, and finishing the washing.
The method for preparing the hydrophilic ultrafiltration membrane containing the carboxyl polysulfate from the phenolphthalein copolymerization type sulfuric ester has the advantage that the mass fraction of a polymer solution obtained by dissolving the copolymerization sulfuric ester in an organic solvent in the step S4 is 15-30%.
The invention relates to a method for preparing a hydrophilic ultrafiltration membrane containing carboxyl polysulfate by phenolphthalein copolymerization type sulfate, wherein a pore-forming additive is one or more of polyethylene glycol, polyvinylpyrrolidone, methanol, ethanol, isopropanol, glycerol, acetone, ethylene glycol, pluronic, tween, sodium dodecyl benzene sulfonate, deionized water, lithium chloride, lithium nitrate and organic acid, and the organic acid is one or more of formic acid, acetic acid and propionic acid.
The method for preparing the hydrophilic ultrafiltration membrane containing the carboxyl polysulfate from the phenolphthalein copolymerization type sulfuric ester comprises the step S4 of stirring for 3 to 5 hours at the temperature of 120 to 130 ℃, and standing and defoaming for 15 to 24 hours at the temperature of 20 to 30 ℃ under the vacuum condition.
The invention relates to a method for preparing a hydrophilic ultrafiltration membrane containing carboxyl polysulfate from phenolphthalein copolymerization type sulfuric ester, which comprises the steps of uniformly coating a defoamed membrane casting solution on a glass plate through a membrane scraping machine, then immersing the glass plate into deionized water to form a solid membrane at room temperature, and continuously immersing the solid membrane in the water for 20-30 hours to obtain a modified flat plate membrane ultrafiltration membrane containing carboxylic acid copolymerization sulfuric ester; or pouring the membrane casting solution after standing and defoaming into a spinning solution tank, extruding the spinning solution into an annular space of a spinneret plate through a metering pump under the pressure of 0.5-2 MPa, simultaneously quantitatively feeding an internal coagulating solution into an insertion pipe of the spinneret plate through the pump, and feeding nascent fibers into an external coagulating tank of deionized water for coagulation after the nascent fibers pass through 20-40cm in air to obtain the modified carboxyl-containing co-sulfated hollow fiber ultrafiltration membrane.
In the method for preparing the hydrophilic ultrafiltration membrane containing the carboxyl polysulfate from the phenolphthalein copolymerization type sulfuric ester, the carboxyl-containing copolymerization sulfuric ester obtained in the step S3 has the following structure:
wherein m is a positive integer, n is an integer greater than or equal to 0, and Ar is one or more of the following groups:
wherein denotes a connecting position of a sulfate ester bond on an aromatic ring.
The beneficial effects of the invention are:
a structural monomer with high rigidity is introduced into a high molecular polymer by using a click chemistry method, a high molecular weight polysulfate material is successfully prepared, the mechanical property and the temperature resistance of the polysulfate material are improved by taking cheap and easily-obtained phenolphthalein as a monomer, the solubility of the material is increased, the high-performance phenolphthalein type polysulfate film material is prepared, and finally, the carboxyl-containing copolymerization type polysulfate hydrophilic ultrafiltration film is successfully prepared in a hydrolysis mode. It has good hydrophilicity, high pure water flux, pollution resistance, easy cleaning and low production cost.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a pure bisphenol A-type polysulfate polymer prepared in example 1;
FIG. 2 is a nuclear magnetic hydrogen spectrum of a phenolphthalein-type polysulfate polymer after hydrolysis reduction in example 2;
FIG. 3 is a nuclear magnetic hydrogen spectrum of a phenolphthalein-type polysulfate polymer after hydrolysis reduction in example 3;
FIG. 4 is a nuclear magnetic hydrogen spectrum of a phenolphthalein-type polysulfate polymer after hydrolysis reduction in example 4;
FIG. 5 is a nuclear magnetic hydrogen spectrum of a phenolphthalein-type polysulfate polymer after hydrolysis reduction in example 5;
FIG. 6 is a nuclear magnetic hydrogen spectrum of a phenolphthalein-type polysulfate polymer after hydrolysis reduction in example 6;
FIG. 7 is a scanning electron micrograph of film 1;
FIG. 8 is a scanning electron micrograph of film 2;
FIG. 9 is a scanning electron micrograph of film 3;
FIG. 10 is a scanning electron micrograph of film 4;
FIG. 11 is a scanning electron micrograph of film 5;
fig. 12 is a scanning electron micrograph of the film 6.
Detailed Description
The present invention will be specifically described below by way of examples. It should be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as many insubstantial modifications and variations of the invention may be made by those skilled in the art in light of the above teachings.
Comparative example 1: preparation of pure bisphenol A type polysulfate ultrafiltration membrane without phenolphthalein structure
3kg of bisphenol A and 30L of dichloromethane are added into a 50L high-pressure reaction kettle, nitrogen is used for protection, 2.1kg of sulfuryl fluoride gas is added, stirring is carried out, and reaction is carried out for 8 hours. And washing the reaction liquid for three times by using a hydrochloric acid aqueous solution, a sodium bicarbonate aqueous solution and a sodium chloride aqueous solution, recovering the solvent, adding ethanol for recrystallization, filtering the system, and drying to obtain the bisphenol A fluorosulfonate with the yield of 92% and the liquid phase purity of 99.8%.
Sequentially adding 1.3kg of bisphenol A, 1.7kg of bisphenol A fluorosulfonate, 0.94kg of sodium carbonate and 5.8 kg of sulfolane into a 10L reaction kettle, reacting at 250 ℃ under the protection of argon gas for 6 hours, cooling to room temperature, adding the reaction solution into ethanol, and crushing after the polymer is completely separated out. The polymer was boiled three times with ethanol in a high pressure reactor at 90 ℃ to wash off excess monomer, the polymer was boiled five times with deionized water at 120 ℃ to remove inorganic salts from the polymer, and the polymer was dried at 120 ℃ with a yield of 98%.
The structure of the pure bisphenol A type polysulfate is as follows:
where n is equal to 258.
Taking 10g of the high polymer, adding 52.6g of N, N-dimethylacetamide and 2g of polyethylene glycol, magnetically stirring at 120 ℃ until the high polymer is completely dissolved, cooling to room temperature, standing in a constant-temperature water bath kettle at 25 ℃ for 24 hours, blade-coating on a prepared clean glass plate, immediately soaking in deionized water, forming a film by first transferring to obtain a solid phenolphthalein type co-sulfated ultrafiltration membrane containing carboxyl, maintaining the water bath temperature at 20 ℃, standing, replacing the deionized water every 6 hours, and finally storing the ultrafiltration membrane in the deionized water to obtain the unmodified bisphenol A type polysulfate flat ultrafiltration membrane (membrane 1).
Example 2: a carboxyl-containing hydrophilic ultrafiltration membrane is prepared by hydrolyzing/reducing bisphenol A type polysulfate with a phenolphthalein structure, wherein the cyclic ester bond accounts for 25 percent, and the method comprises the following steps:
the structure of phenolphthalein type fluorosulfonate is as follows:
the reaction route of the phenolphthalein fluorosulfonate is as follows:
the preparation method comprises the following steps:
adding 3kg of phenolphthalein and 30L of dichloromethane into a 50L high-pressure reaction kettle, adding 2.1kg of sulfuryl fluoride gas under the protection of nitrogen, stirring, and reacting for 8 hours. Washing the reaction solution with hydrochloric acid water solution, sodium bicarbonate water solution and sodium chloride water solution for three times, recovering the solvent, adding ethanol for recrystallization, filtering the system, drying, wherein the yield is 92% and the liquid phase purity is 99.8%.
1.16kg of bisphenol A, 1kg of bisphenol A fluorosulfonate (same as comparative example 1), 1.05kg of phenolphthalein fluorosulfonate, 1.2kg of sodium carbonate and 7L of sulfolane are sequentially added into a 10L reaction kettle, and the mixture is reacted at 250 ℃ under the protection of argon gas for 6 hours, cooled to room temperature, added into ethanol, and crushed after the polymer is completely separated out. And (3) boiling and washing the polymer for three times at 90 ℃ by using ethanol in a high-pressure reaction kettle, washing off redundant monomers for 6 hours each time, boiling and washing the polymer for five times at 120 ℃ by using deionized water and 1.2MPa for 5 hours each time, removing inorganic salt in the polymer, and drying the polymer at 120 ℃ to obtain the yield of 98%.
Step (1): weighing 50g of the phenolphthalein type polysulfate (50% of bisphenol A fluorosulfonate is replaced by phenolphthalein fluorosulfonate, and Mn is 70000g/mol), adding into 200g of N, N-dimethylacetamide, magnetically stirring at 120 ℃ until the mixture is completely dissolved, cooling to 90 ℃, adding 40g of ethanol solution of sodium ethoxide, protecting with nitrogen, and stirring at 90 ℃ for 6 hours. And after the reaction is finished, 5g of zinc powder is added into the system, and the stirring is continued for 6 hours.
Step (2): and after the reduction is finished, filtering the system while the system is hot, and filtering out metals.
And (3): the filtrate was precipitated into an aqueous hydrochloric acid solution (c 2mol/L), rapidly stirred, and filtered to obtain a white filamentous polymer. Pulverizing the polymer, boiling at 150 deg.C under 1.2Mpa for 8 hr, and boiling for three times. Drying the purified high polymer at 120 ℃ for 10 h.
And (4): and taking 10g of the high polymer, adding 52.6g of N, N-dimethylacetamide and 2g of polyethylene glycol, magnetically stirring at 120 ℃ until the high polymer is completely dissolved, cooling to room temperature, and standing in a constant-temperature water bath kettle at 25 ℃ for 24 hours to obtain a casting solution.
And (5): and (3) blade-coating the membrane casting solution on a prepared clean glass plate, immediately immersing the clean glass plate into deionized water, forming a membrane by transferring to obtain a solid phenolphthalein type co-sulfated ultrafiltration membrane containing carboxyl, maintaining the water bath temperature at 20 ℃, standing, replacing the deionized water every 6 hours, and finally storing the ultrafiltration membrane in the deionized water to obtain the modified flat ultrafiltration membrane (membrane 2).
The structure of the above embodiment is:
example 3: a carboxyl-containing hydrophilic ultrafiltration membrane is prepared by hydrolyzing/reducing bisphenol A type polysulfate with a phenolphthalein structure (cyclic ester bond accounts for 50 percent) and comprises the following steps:
1.16kg of bisphenol A, 2.1kg of phenolphthalein fluorosulfonate (same as example 2), 1.2kg of sodium carbonate and 7L of sulfolane are sequentially added into a 10L reaction kettle, and the mixture is reacted at 250 ℃ under the protection of argon gas for 6 hours, cooled to room temperature, added into ethanol, and crushed after the polymer is completely precipitated. And (3) boiling and washing the polymer for three times at 90 ℃ by using ethanol in a high-pressure reaction kettle, washing off redundant monomers for 6 hours each time, boiling and washing the polymer for five times at 120 ℃ by using deionized water and 1.2MPa for 5 hours each time, removing inorganic salt in the polymer, and drying the polymer at 120 ℃ to obtain the yield of 98%.
Step (1): weighing 50g of the phenolphthalein type polysulfate (bisphenol A fluorosulfonate is replaced by phenolphthalein fluorosulfonate for 100 percent, and Mn is 75000g/mol), adding into 200g of N, N-dimethylacetamide, magnetically stirring at 120 ℃ until completely dissolved, cooling to 90 ℃, adding 40g of ethanol solution of sodium ethoxide, protecting with nitrogen, and stirring at 90 ℃ for 6 hours. And after the reaction is finished, 5g of zinc powder is added into the system, and the stirring is continued for 6 hours.
Step (2): and after the reduction is finished, filtering the system while the system is hot, and filtering out metals.
And (3): the filtrate was precipitated into an aqueous hydrochloric acid solution (c 2mol/L), rapidly stirred, and filtered to obtain a white filamentous polymer. Pulverizing the polymer, boiling at 150 deg.C under 1.2Mpa for 8 hr, and boiling for three times. Drying the purified high polymer at 120 ℃ for 10 h.
And (4): and taking 10g of the high polymer, adding 52.6g of N, N-dimethylacetamide and 2g of polyethylene glycol, magnetically stirring at 120 ℃ until the high polymer is completely dissolved, cooling to room temperature, and standing in a constant-temperature water bath kettle at 25 ℃ for 24 hours to obtain a casting solution.
And (5): and (3) blade-coating the membrane casting solution on a prepared clean glass plate, immediately immersing the clean glass plate into deionized water, forming a membrane by transferring to obtain a solid phenolphthalein type co-sulfated ultrafiltration membrane containing carboxyl, maintaining the water bath temperature at 20 ℃, standing, replacing the deionized water every 6 hours, and finally storing the ultrafiltration membrane in the deionized water to obtain the modified flat ultrafiltration membrane (membrane 3).
The structure of the embodiment is as follows:
example 4: a carboxyl-containing hydrophilic ultrafiltration membrane is prepared by hydrolyzing/reducing bisphenol A type polysulfate with a phenolphthalein structure (cyclic ester bond accounts for 75 percent) and comprises the following steps:
0.56kg of bisphenol A, 0.64g of phenolphthalein, 2.1kg of phenolphthalein fluorosulfonate (same as example 2), 1kg of sodium carbonate and 6L of sulfolane are sequentially added into a 10L reaction kettle, and the mixture is reacted at 250 ℃ under the protection of argon gas for 6 hours, cooled to room temperature, added into ethanol, and crushed after the polymer is completely separated out. And (3) boiling and washing the polymer for three times at 90 ℃ by using ethanol in a high-pressure reaction kettle, washing off redundant monomers for 6 hours each time, boiling and washing the polymer for five times at 120 ℃ by using deionized water and 1.2MPa for 5 hours each time, removing inorganic salt in the polymer, and drying the polymer at 120 ℃ to obtain the yield of 98%.
Step (1): weighing 50g of the phenolphthalein type polysulfate (bisphenol A fluorosulfonate is replaced by phenolphthalein fluorosulfonate by 100 percent, and Mn is 80000g/mol), adding the weighed 50g of the phenolphthalein type polysulfate into 200g of N, N-dimethylacetamide, magnetically stirring the mixture at 120 ℃ until the mixture is completely dissolved, cooling the mixture to 90 ℃, adding 40g of an ethanol solution of sodium ethoxide, protecting the mixture with nitrogen, and stirring the mixture for 6 hours at 90 ℃. And after the reaction is finished, 5g of zinc powder is added into the system, and the stirring is continued for 6 hours.
Step (2): and after the reduction is finished, filtering the system while the system is hot, and filtering out metals.
And (3): the filtrate was precipitated into an aqueous hydrochloric acid solution (c 2mol/L), rapidly stirred, and filtered to obtain a white filamentous polymer. Pulverizing the polymer, boiling at 150 deg.C under 1.2Mpa for 8 hr, and boiling for three times. Drying the purified high polymer at 120 ℃ for 10 h.
And (4): taking 10g of the high polymer, adding 52.6g of N, N-dimethylacetamide and 2g of polyethylene glycol, magnetically stirring at 120 ℃ until the high polymer is completely dissolved, cooling to room temperature, and standing in a constant-temperature water bath kettle at 25 ℃ for 24 hours.
And (5): and (3) blade-coating the membrane casting solution on a prepared clean glass plate, immediately immersing the clean glass plate into deionized water, forming a membrane by transferring to obtain a solid phenolphthalein type co-sulfated ultrafiltration membrane containing carboxyl, maintaining the water bath temperature at 20 ℃, standing, replacing the deionized water every 6 hours, and finally storing the ultrafiltration membrane in the deionized water to obtain a modified flat ultrafiltration membrane (membrane 4).
The structure of the embodiment is as follows:
example 5: a carboxyl-containing hydrophilic ultrafiltration membrane is prepared by hydrolyzing/reducing bisphenol A type polysulfate with a phenolphthalein structure (cyclic ester bond accounts for 100 percent) and comprises the following steps:
1.3g of phenolphthalein, 2.1kg of phenolphthalein fluorosulfonate (same as in example 2), 1kg of sodium carbonate and 6L of sulfolane are sequentially added into a 10L reaction kettle, and the mixture is reacted at 250 ℃ for 6 hours under the protection of argon gas, cooled to room temperature, added into ethanol, and crushed after the polymer is completely separated out. And (3) boiling and washing the polymer for three times at 90 ℃ by using ethanol in a high-pressure reaction kettle, washing off redundant monomers for 6 hours each time, boiling and washing the polymer for five times at 120 ℃ by using deionized water and 1.2MPa for 5 hours each time, removing inorganic salt in the polymer, and drying the polymer at 120 ℃ to obtain the yield of 98%.
Step (1): weighing 50g of the phenolphthalein type polysulfate (bisphenol A fluorosulfonate is replaced by phenolphthalein fluorosulfonate by 100 percent, and Mn is 80000g/mol), adding the weighed 50g of the phenolphthalein type polysulfate into 200g of N, N-dimethylacetamide, magnetically stirring the mixture at 120 ℃ until the mixture is completely dissolved, cooling the mixture to 90 ℃, adding 40g of an ethanol solution of sodium ethoxide, protecting the mixture with nitrogen, and stirring the mixture for 6 hours at 90 ℃. And after the reaction is finished, 5g of zinc powder is added into the system, and the stirring is continued for 6 hours.
Step (2): and after the reduction is finished, filtering the system while the system is hot, and filtering out metals.
And (3): the filtrate was precipitated into an aqueous hydrochloric acid solution (c 2mol/L), rapidly stirred, and filtered to obtain a white filamentous polymer. Pulverizing the polymer, boiling at 150 deg.C under 1.2Mpa for 8 hr, and boiling for three times. Drying the purified high polymer at 120 ℃ for 10 h.
And (4): taking 10g of the high polymer, adding 52.6g of N, N-dimethylacetamide and 2g of polyethylene glycol, magnetically stirring at 120 ℃ until the high polymer is completely dissolved, cooling to room temperature, and standing in a constant-temperature water bath kettle at 25 ℃ for 24 hours.
And (5): and (3) blade-coating the membrane casting solution on a prepared clean glass plate, immediately immersing the clean glass plate into deionized water, forming a membrane by transferring to obtain a solid phenolphthalein type co-sulfated ultrafiltration membrane containing carboxyl, maintaining the water bath temperature at 20 ℃, standing, replacing the deionized water every 6 hours, and finally storing the ultrafiltration membrane in the deionized water to obtain a modified flat ultrafiltration membrane (membrane 5).
Example 6: a carboxyl-containing hydrophilic ultrafiltration membrane is prepared by hydrolyzing/reducing diphenyl ether type poly-sulfate with a phenolphthalein structure (the proportion of cyclic ester bonds is 50 percent) and comprises the following steps:
1.01g of dihydroxy diphenyl ether, 2.1kg of phenolphthalein fluorosulfonate (same as example 2), 1kg of sodium carbonate and 5.5L of sulfolane are sequentially added into a 10L reaction kettle, and the mixture is reacted at 250 ℃ for 6 hours under the protection of argon, cooled to room temperature, added into ethanol, and crushed after the polymer is completely precipitated. The polymer was boiled and washed three times with ethanol at 90 ℃ for 6 hours each time in a high pressure reactor to wash off excess monomer, the polymer was boiled and washed five times with deionized water at 120 ℃ and 1.2MPa for 5 hours each time to remove inorganic salts in the polymer, and the polymer was dried at 120 ℃ to obtain a yield of 98%.
Step (1): weighing 50g of the phenolphthalein type polysulfate (bisphenol A fluorosulfonate is replaced by phenolphthalein fluorosulfonate for 100 percent, and Mn is 60000g/mol), adding 200g of sulfolane, performing magnetic stirring at 110 ℃ until the mixture is completely dissolved, cooling to 90 ℃, adding 40g of ethanol solution of sodium ethoxide, performing nitrogen protection, and stirring at 90 ℃ for 6 hours. And after the reaction is finished, 5g of zinc powder is added into the system, and the stirring is continued for 6 hours.
Step (2): and after the reduction is finished, filtering the system while the system is hot, and filtering out metals.
And (3): the filtrate was precipitated into an aqueous hydrochloric acid solution (c 3mol/L), rapidly stirred, and filtered to obtain a white filamentous polymer. Pulverizing the polymer, boiling at 150 deg.C under 1.2Mpa for 8 hr, and boiling for three times. Drying the purified high polymer at 120 ℃ for 10 h.
And (4): taking 10g of the high polymer, adding 52.6g of sulfolane and 2g of polyethylene glycol, magnetically stirring at 120 ℃ until the high polymer is completely dissolved, cooling to room temperature, and standing in a constant-temperature water bath kettle at 45 ℃ for 24 hours.
And (5): and (3) blade-coating the membrane casting solution on a prepared clean glass plate, immediately immersing the clean glass plate into deionized water, forming a membrane by transfer to obtain a solid phenolphthalein type co-sulfated ultrafiltration membrane containing carboxyl, maintaining the water bath temperature at 20 ℃, standing, replacing the deionized water every 6 hours, and finally storing the ultrafiltration membrane in the deionized water to obtain a modified flat ultrafiltration membrane (membrane 6).
The structure of the embodiment is as follows:
table 1: examples 1-6 product Property data
Note: the membrane dimensions (50mm by 10mm, thickness 100 μm) were tested under the following conditions: 25 ℃, 225psi operating pressure, protein solution concentration of 1.0g/L, BAS (0.1M PBS buffer).
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (16)
1. A method for preparing a carboxyl-containing polysulfate hydrophilic ultrafiltration membrane from phenolphthalein copolymer sulfate is characterized by comprising the following steps of:
s1, dissolving phenolphthalein copolymerization type sulfuric ester in an organic solvent, adding an alkali solution for hydrolysis, and adding a metal reducing agent into a system for reduction after the hydrolysis is finished;
s2, filtering the reaction liquid obtained in the step S1 to obtain phenolphthalein copolymerization type sulfuric ester solution;
s3, adding the phenolphthalein copolymerization type sulfuric ester solution obtained in the step S3 into an acidic aqueous solution, precipitating a solid polymer, washing with water, and drying to obtain carboxyl-containing copolymerization sulfuric ester;
s4, dissolving the co-sulfated obtained in the step S3 in an organic solvent, adding a pore-forming additive, stirring, filtering and standing to obtain a membrane casting solution;
and S5, preparing the ultrafiltration membrane by using the membrane casting solution.
2. The method of claim 1, wherein the phenolphthalein copolymer sulfate is of the following structure:
wherein m is a positive integer, n is an integer greater than or equal to 0, and Ar is one or more of the following groups:
wherein denotes a connecting position of a sulfate ester bond on an aromatic ring.
3. The method for preparing the hydrophilic ultrafiltration membrane containing the carboxyl polysulfate from the phenolphthalein copolymerization type sulfuric ester as claimed in claim 2, wherein the number average molecular weight of the phenolphthalein copolymerization type sulfuric ester is 10000-80000.
4. The method for preparing hydrophilic ultrafiltration membrane containing carboxyl polysulfate from phenolphthalein copolymer sulfate as claimed in claim 1, wherein the organic solvent in steps S1 and S4 is one or more selected from sulfolane, dimethyl sulfoxide, N-dimethylacetamide, N-dimethylformamide and N-methylpyrrolidone.
5. The method for preparing a hydrophilic ultrafiltration membrane containing polythioate by phenolphthalein copolymerization type sulfate as claimed in claim 1, wherein the alkali solution in step S1 is one or more of aqueous sodium hydroxide solution, aqueous potassium hydroxide solution, aqueous sodium carbonate solution, aqueous potassium carbonate solution, ethanol solution of sodium ethoxide, methanol solution of sodium methoxide, ethanol solution of triethylamine and aqueous solution of triethylamine.
6. The method for preparing the hydrophilic ultrafiltration membrane containing the carboxyl polysulfate from the phenolphthalein copolymerization type sulfate according to claim 5, wherein the mass fraction of the organic alkali solution is 10-30%, and the concentration of the inorganic alkali solution is 1-5 mol/L.
7. The method for preparing the hydrophilic ultrafiltration membrane containing the carboxyl polysulfate from the phenolphthalein copolymerization type sulfate according to claim 1, wherein the dissolving temperature in the step S1 is 120-130 ℃, the hydrolysis temperature is 70-90 ℃, the hydrolysis time is 5-12h, the reduction temperature is 70-100 ℃, and the reduction time is 6-15 h.
8. The method for preparing the hydrophilic ultrafiltration membrane containing the carboxyl polysulfate from the phenolphthalein copolymerization type sulfuric ester as claimed in claim 1, wherein the metal reducing agent in the step S1 is one or more of a complex of palladium and phosphate, zinc powder, iron powder and copper powder.
9. The method for preparing a hydrophilic ultrafiltration membrane containing a carboxyl polysulfate from a phenolphthalein copolymer sulfate as claimed in claim 1, wherein the aqueous acidic solution in step S3 is an aqueous hydrochloric acid solution and/or an aqueous sulfuric acid solution, wherein the concentration of the aqueous hydrochloric acid solution is 0.1 to 10 mol/L.
10. The method of claim 1, wherein the step S3 is carried out at a washing temperature of 90-170 ℃, a washing pressure of 0-1.5 Mpa, a washing time of 5-12 hours, and a drying manner of drying in a vacuum oven at 110-130 ℃ for 10-20 hours.
11. The method for preparing the hydrophilic ultrafiltration membrane containing the carboxyl polysulfate from the phenolphthalein copolymer sulfate as claimed in claim 1, wherein the water washing is finished in step S3 until the salinity in the water is less than 50 ppm.
12. The method for preparing a hydrophilic ultrafiltration membrane containing a carboxyl polysulfate from a phenolphthalein copolymer sulfate as claimed in claim 1, wherein the mass fraction of the polymer solution obtained by dissolving the copolymer sulfate in an organic solvent in step S4 is 15% to 30%.
13. The method for preparing the hydrophilic ultrafiltration membrane containing the carboxyl polysulfate from the phenolphthalein copolymerization type sulfuric ester according to claim 1, wherein the pore-forming additive is one or more of polyethylene glycol, polyvinylpyrrolidone, methanol, ethanol, isopropanol, glycerol, acetone, ethylene glycol, pluronic, tween, sodium dodecylbenzenesulfonate, deionized water, lithium chloride, lithium nitrate and an organic acid, and the organic acid is one or more selected from formic acid, acetic acid and propionic acid.
14. The method for preparing the hydrophilic ultrafiltration membrane containing the polysulfate carboxyl from the phenolphthalein copolymerization type sulfate according to claim 1, wherein the stirring condition in the step S4 is stirring at 120-130 ℃ for 3-5h, and the standing condition is standing and defoaming at 20-30 ℃ under vacuum condition for 15-24 h.
15. The method for preparing the hydrophilic ultrafiltration membrane containing the carboxyl polysulfate from the phenolphthalein copolymerized sulfate according to claim 1, wherein the ultrafiltration membrane is prepared by uniformly coating the defoamed membrane casting solution on a glass plate through a membrane scraping machine, then immersing the glass plate into deionized water to form a solid membrane at room temperature, and continuously immersing the solid membrane in the water for 20-30 hours to obtain the modified copolymerized sulfate flat membrane ultrafiltration membrane containing the carboxylic acid; or pouring the membrane casting solution after standing and defoaming into a spinning solution tank, extruding the spinning solution into an annular space of a spinneret plate through a metering pump under the pressure of 0.5-2 MPa, simultaneously quantitatively feeding an internal coagulating solution into an insertion pipe of the spinneret plate through the pump, and feeding nascent fibers into an external coagulating tank of deionized water for coagulation after the nascent fibers pass through 20-40cm in air to obtain the modified carboxyl-containing co-sulfated hollow fiber ultrafiltration membrane.
16. The method for preparing carboxyl-containing polysulfate hydrophilic ultrafiltration membrane from phenolphthalein copolymer sulfate according to claim 2, wherein the carboxyl-containing copolymer sulfate obtained in step S3 has the following structure:
wherein m is a positive integer, n is an integer greater than or equal to 0, and Ar is one or more of the following groups:
wherein denotes a connecting position of a sulfate ester bond on an aromatic ring.
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