CN112495198A - Technology for preparing film by using poly (amino) sulfate polymer and application - Google Patents
Technology for preparing film by using poly (amino) sulfate polymer and application Download PDFInfo
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Abstract
The invention discloses a technology for preparing a membrane by using a poly (amino) sulfate polymer and application thereof, and discloses a separation membrane prepared by using the poly (amino) sulfate polymer and a modified polymer thereof as membrane preparation materials, which is used for separating gas, water and other substances. Compared with the prior art, the poly (amino) sulfate polymer simultaneously contains a large amount of polar sulfate and rigid aromatic ring group structures, so that the material has the characteristics of excellent chemical resistance, solvent resistance, pollution resistance and the like, and has potential application value in the field of membrane separation due to good film forming property.
Description
Technical Field
The invention discloses a separation membrane prepared from a polysulfate (ammonia) ester polymer and a modified polymer thereof, which uses the polysulfate polymer or the modified polymer thereof as a membrane preparation material and belongs to the field of membrane separation.
Background
The membrane technology is a new modern high-efficiency separation technology, and compared with the traditional separation technology, the membrane technology has the outstanding advantages of high separation efficiency, low energy consumption (no phase change), small occupied area, simple process (easy amplification and automatic control), convenient operation, no environmental pollution, convenient integration with other technologies and the like. The research and the application of the method are closely related to energy conservation, environmental protection, water resource development, utilization and regeneration. Under the conditions of energy and water resource shortage in the world and increasingly serious water and environmental pollution, research on science and technology of membrane separation is highly regarded by countries in the world, and becomes an important component part for realizing economic sustainable development strategy. The membrane technology is a high and new technology for improving the traditional industry and promoting the technical progress of the related industry. For example, petroleum and chemical industries are basic industries in China, but are energy-consuming households and environment-polluting households, and the production and processing processes of the petroleum and chemical industries all urgently need to modify the traditional method by a new method so as to improve the efficiency, reduce the energy consumption and reduce the environment pollution, which are closely related to the membrane technology.
In addition, the membrane technology shows unprecedented technical advantages and development prospects in the aspects of seawater desalination, turbidity reduction and sterilization of drinking water and beverages, concentration and purification of medicines, membrane type artificial organs, battery diaphragms, gas separation, domestic sewage treatment, reclaimed water recycling and the like. Therefore, the development of the membrane technology can effectively promote the technical progress and development of related industries in China. At present, the membrane separation technology has been effectively and widely applied in the fields of petrochemical industry, pharmacy, biochemistry, environment, energy, electronics, metallurgy, light industry, food, aerospace, seawater (brackish water) desalination, medical treatment (artificial lung and artificial kidney) and the like in China. The method not only develops at a speed of 14-30% per year, but also powerfully drives the technological progress of related industries, and becomes an important component part for realizing the sustainable development strategy of national economy in China. However, in terms of membrane materials and devices, which are key components of membrane separation technology, the gap between China and the advanced level of the world is still large (annual sales of around $ 100 billion for global separation membrane materials and devices), and many membrane materials (such as reverse osmosis Membranes, nanofiltration Membranes, ion exchange Membranes, gas separation Membranes, dialysis Membranes, and the like) still rely on import (Ho c., Zydney a.l., Protein Fouling of asymmetry and Composite Microfiltration Membranes, Industry & Engineering Chemistry Research 2001, 40: 1412-.
The polymer material has the characteristics of flexible molecular chain, good processability, low price, convenience for molecular design (synthesis, alloy blending, graft modification) and the like, thereby becoming the most widely applied membrane separation material.
The general high-end polysulfone membrane has wide application in water treatment and other toxic separation, and polysulfone is a very important engineering plastic and has wide application in automobile aerospace, plates and electronic materials. However, polysulfone treatment of strong chemical substances cannot be achieved (such as strong acid and strong base, corrosive raw materials and the like), polysulfate as a novel special engineering plastic has excellent chemical resistance, even some brands of polymers can be used in concentrated sulfuric acid and concentrated nitric acid, and the chemical environment has wider scope of application and stronger anti-pollution property in the field of membranes than polysulfone, so that the development of the polysulfate membrane material has very important scientific research value and marketization application prospect (Chengyang. a bisphenol A type polysulfate (ammonia) ester compound and a synthetic method thereof: China, 201310509899.5[ P ]. 2014-09-24.).
The invention discloses a method for preparing a film by using a polysulfate (amino) ester polymer and a modified polymer thereof, wherein the polysulfate (amino) ester film is prepared for the first time by using a phase transition method or general methods such as solution casting, stretching film forming and the like, and is used in the fields of water treatment, gas separation and the like.
Disclosure of Invention
The invention aims to disclose a separation membrane prepared from a polysulfate (amino) ester polymer and a modified polymer thereof, and the content of the polysulfate (amino) ester polymer or the modified polymer thereof as a membrane preparation material.
The invention discloses a polythio acid (ammonia) ester polymer and application of a modified polymer thereof in preparation of a separation membrane.
The use according to the present invention, wherein the separation membrane preferably comprises a porous support layer and a dense skin layer.
The use according to the present invention, wherein the polysulfate (urethane) based polymer and the modified polymer thereof are preferably used for the porous support layer or the dense skin layer.
The use of the present invention, wherein the polysulfate (amino) ester polymer preferably contains a sulfate ester bond (-SO)4-，-SO3NH-).
The use of the invention, wherein the structural general formula of the poly (amino) sulfate polymer is preferably as follows:
in the formula R1is-Me, -Et, -Ph, -iPr, or-H;
R2is-Me, -Et, -Ph, -iPr, or-H;
x is-C, -Si, or-O;
n is an integer of 10 to 1000.
The use of the present invention, wherein the polysulfate (amm) acid ester polymer is preferably prepared by at least one method selected from the group consisting of homopolymerization, polycondensation, and copolymerization with a third monomer.
The use according to the invention, wherein the preparation of the polysulfate (urethane) polymer preferably also comprises chemical modification.
The use of the present invention, wherein the polysulfate (amm) acid ester polymer preferably comprises at least one selected from the group consisting of polymers represented by the following formulae a to I:
the use of the invention, wherein the poly (amino) sulfate polymer preferably comprises a polymer constructed by two or more monomers containing hydroxyl or amino functional groups and monomers containing sulfuryl fluoride.
The use of the present invention, wherein the polysulfate-based polymer is preferably prepared by including bis-SO3Polymerizing the monomer of the F group and the dihydroxy compound under the catalysis of an alkaline catalyst to generate a polymer.
The use of the present invention, wherein the polythioamine ester polymer is preferably prepared by including bis-NSO3Polymerizing the monomer of the group and the dihydroxy compound under the catalysis of an alkaline catalyst to generate a polymer.
The use according to the invention, wherein the basic catalyst is preferably an organic and/or inorganic base.
The use of the present invention, wherein the organic base is preferably at least one selected from the group consisting of TEA, DIPEA, and DBU, and the inorganic base is preferably at least one selected from the group consisting of sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium fluoride.
The use of the present invention, wherein the separation membrane preferably comprises at least one selected from the group consisting of a nanofiltration membrane, a microfiltration membrane, an ultrafiltration membrane, a reverse osmosis membrane, an electrodialysis membrane, a pervaporation membrane, a gas separation membrane, and a biomedical separation membrane.
The use according to the present invention, wherein the separation membrane is preferably prepared by at least one method selected from the group consisting of an immersion precipitation method, a hot-melt extrusion-draw preparation method, a phase separation method, a nuclear track-etching method, a solution coating method, an interfacial polymerization method, a phase inversion method, a solution casting method, a draw film forming method, a wet spinning method, a lining reinforcement method, a hot-melt method, a spin coating method, and a water spreading method.
The use according to the present invention, wherein the film-forming medium preferably comprises at least one selected from the group consisting of dioxane, N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), and Dimethylacetamide (DMAC).
In the use of the present invention, in the phase transition method, the mass concentration of the polysulfate membrane is preferably 5 to 40%, and more preferably 10 to 25%.
The use according to the present invention, wherein the porogen additive preferably comprises at least one selected from the group consisting of high molecular compounds, small molecular compounds, and inorganic substances.
The use of the present invention, wherein the high molecular compound preferably comprises at least one selected from the group consisting of polyvinylpyrrolidone PVP, polyethylene glycol PEG, and polyvinyl alcohol PVA, the small molecular compound preferably comprises at least one selected from the group consisting of Span-80, diglyme, 1, 4-dioxane, acetone, γ -butyrolactone, and propionic acid, and the inorganic substance preferably comprises at least one selected from the group consisting of zinc chloride and lithium chloride.
The use of the present invention, wherein the porous support layer preferably comprises at least one selected from the group consisting of a polysulfate (ammonia) porous support layer, a polypropylene porous support layer, a polyethylene porous support layer, and a polyvinylidene fluoride porous support layer.
The use of the present invention, wherein the separation membrane is preferably used in at least one selected from the group consisting of sewage treatment, gas separation, liquid separation, electronic components, and medical devices.
In addition, the present invention can be described in detail as follows:
the polymer of poly (amino) sulfate and its modified polymer belong to organic high molecular engineering plastics, and are a kind of polymer containing sulfuric acid (amino) ester bond (-SO)4-,-NHSO3-) of a polymer. Compared with other traditional engineering plastics, the poly (amino) sulfate polymer has the characteristics of higher mechanical strength, wider chemical medium applicability, lower cost and the like.
The polythionic acid (ammonia) ester bond (-SO) of the invention4-，-SO3NH-) polymer, except the polymer of homo-polycondensation or third monomer copolymerization, also includes the polymer of polycondensation polymer through other chemical modification methods (such as sulfonation, ammoniation and other functional group modification), so that the polymer presents better application performance.
The polythioester polymer of the invention is synthesized into polythioester hybridized with different functional groups in a molecular chain according to different monomer types in the polymer, and is shown in the following chemical formula (partial polythioester material structures A-H): different hetero atoms and molecular structures in molecular chains endow the polymer with different properties (including the characteristics of flexibility, hydrophilicity and hydrophobicity, temperature resistance and the like of the polymer). Such as diphenyl ether type polysulfate B, due to the existence of ether bond, the polymer has higher hydrophilicity and pollution resistance, and shows excellent water flux and pollution resistance in the water treatment membrane material; the bisphenol S type polysulfate C tends to semi-crystalline polymer, has good temperature resistance and can be applied to high-temperature separation environment.
In addition to the self-polymerization type high molecular poly sulfate chain, the copolymer polymer is also constructed by the way of copolymerizing or gradually polycondensing two or more than two monomers containing hydroxyl or amino functional groups and sulfuryl fluoride-containing monomers. The partial copolymerization structure is shown as the following chemical formula:
the polysulfate polymer comprises a sulfuric (amino) ester bond (-SO)4-,-NHSO3-) as functional and chemical connecting bond, so that the polymer not only can present good solvent resistance and mechanical property, but also can be used as functional group in separation material, or used as metal ion moving medium (such as Li conductive)+Wait for speciallySex).
The characteristic groups of the poly (amino) sulfate polymers of different types also enable the polymers to obtain other performance advantages. Such as diphenyl ether type polysulfate, the polymer has good hydrophilicity and contamination resistance due to the existence of ether bond; the bisphenol S type polysulfate has good temperature resistance. Meanwhile, the polysulfate-based polymer also includes a copolymer of any two or more of them.
The foregoing polymers useful in preparing separation membranes include: a polythioester polymer, a polythioammonia polymer, and a polythioester-based and polythioammonia-based modified polymer. The molecular weight Mn (number average molecular weight) of the aromatic ring-containing copolymerized linear material of the polymer, which can be used for preparing the separation membrane, is usually in the range of 1000-300000. The molecular weight range of the aliphatic polyester material is 100000-700000. The molecular weight range of the star structure can be controlled to 10000-300000.
The synthesis method of the polysulfate polymer is to include double-SO4The monomer of the F group and the dihydroxy compound are polymerized to generate a polymer with high molecular weight under the catalysis of an alkaline catalyst. The general structural formula is as follows:
in the formula R1is-Me, -Et, -Ph, -iPr, or-H;
R2is-Me, -Et, -Ph, -iPr, or-H;
x is-C, -Si, or-O;
n is an integer of 10 to 1000.
The synthesis method of the polysulfate ammonia polymer is to comprise bis-NSO3Polymerizing the monomer of the group and the dihydroxy compound under the catalysis of an alkaline catalyst to generate a polymer with high molecular weight. The general structural formula is as follows:
in the formula R1is-Me, -Et, -Ph, -iPr, or-H;
R2is-Me, -Et, -Ph, -iPr, or-H;
x is-C, -Si, or-O;
n is an integer of 10 to 1000.
The modified poly (amine) sulfate is characterized in that on the basis of the original main poly (amine) sulfate homo-polymer or copolymer, the high polymer is subjected to chemical modification through chemical reaction, such as end-capping modification reaction and coupling reaction of the polymer, bromination, nitration, sulfonation and the like of a side chain, so that the polymer has more excellent chemical and physical properties according to different application scenes, and the application requirements of the polymer in the field of membrane separation are met.
The modification method described in the present invention is a type of reaction method, not limited to the above-mentioned several reactions, and modification based on polysulfate in the film industry is within the scope of this patent.
The types of the polysulfate polymer and the modified polymer thereof used for the separation membrane include: the method comprises the following steps of (1) dividing a nanofiltration membrane, a microfiltration membrane and an ultrafiltration membrane according to the size of a pore passage; according to the separation method, the membrane is divided into a reverse osmosis membrane, an electrodialysis membrane and a pervaporation membrane; the membrane is classified into a gas separation membrane and a biomedical separation membrane according to application scenarios.
The preparation method of the polysulfate polymer and the modified polymer thereof in the separation membrane comprises the following steps: the immersion precipitation method is used for preparing flat membrane and tubular membrane, the tubular membrane comprises hollow fiber membrane, capillary membrane, tubular membrane and the like, the hot melt extrusion-drawing preparation method is used for preparing microporous membrane, the heat induced phase separation method is used for preparing microporous membrane, and the nuclear track-etching method is used for preparing microporous membrane.
In the preparation of the polysulfate (ammonia) polymer and the modified polymer separation membrane thereof, the preparation method for preparing the high-molecular gas separation membrane comprises a phase separation method, preparing membrane casting solution with certain concentration, and forming the membrane casting solution on a base material (or without using the base material) or by using a hollow fiber nozzle to prepare the membrane skin layer with compact micropores.
In the preparation of the polysulfate (ammonia) polymer and the modified polymer separation membrane thereof, the prepared pervaporation membrane can be used for the separation of an organic mixture system, the dehydration of an organic solvent, the removal of a trace amount of the organic solvent in water and the like.
In the preparation of the polysulfate (ammonia) polymer and the modified polymer separation membrane thereof, the prepared ion exchange membrane comprises a homogeneous membrane, a semi-homogeneous membrane and a heterogeneous membrane, and a sheet-shaped film is prepared by mixing raw materials and an adhesive to prepare the functional polymer membrane with ion selective permeability.
In the preparation of the polysulfate (ammonia) polymer and the modified polymer separation membrane thereof, a phase separation method is generally used for preparing the nanofiltration membrane and the reverse osmosis membrane, for example, a membrane casting solution with a certain concentration is prepared, and the membrane casting solution is formed on a base material (or the base material is not used) or by using a hollow fiber nozzle to prepare a membrane layer with compact micropores; solution coating method; interfacial polymerization, and the like. The membrane-forming medium is usually an organic solvent that is easily soluble in water, such as dioxane, N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), and Dimethylacetamide (DMAC).
The porous support layer is a polysulfate (ammonia) porous support layer, a polypropylene porous support layer, a polyethylene porous support layer and a polyvinylidene fluoride porous support layer.
In the preparation of the polysulfate (amino) ester polymer and the modified polymer separation membrane thereof, the prepared pervaporation membrane can be used for the separation of an organic mixture system, the dehydration of an organic solvent, the removal of a trace amount of the organic solvent in water and the like.
In the preparation of the polysulfate (ammonia) -based polymer and the modified polymer separation membrane thereof, the morphological structure of the separation membrane can be determined by four methods, such as imaging, reflection, spectroscopy, ion beam and the like.
In the preparation of the polysulfate (ammonia) polymer and the modified polymer separation membrane thereof, the physical and chemical stability test parameters of the membrane comprise material types, the use pressure, the applicable temperature range, the pH value range, bacterial resistance, solvent resistance, oxidation resistance, mechanical properties and the like.
In the preparation of the polysulfate (ammonia) polymer and the modified polymer separation membrane thereof, the parameters related to the selective separation and permeation characteristics of the membrane comprise a pure water permeability constant, a solution osmotic pressure, a solvent permeation speed (water flux), a solute (salt) permeability constant, a solute rejection rate (desalination rate in a salt solution), a recovery rate, a membrane flow attenuation coefficient and the like.
The method for preparing the polysulfate (ammonia) -based polymer and the modified polymer separation membrane thereof is characterized in that: the prepared poly sulfuric acid (ammonia) ester film can be widely applied to the fields of sewage treatment, gas separation, electronic components, medical devices and the like.
In the preparation of the polysulfate (ammonio) polymer and the modified polymer separation membrane thereof according to the present invention, the polysulfate (ammonio) polymer may be used as a support layer or a dense skin layer, preferably a skin layer.
In the preparation of the polysulfate (ammonia) polymer and the modified polymer separation membrane thereof, in the phase transition membrane method, the pore-forming additive can be a macromolecule, a micromolecule or even an inorganic substance, such as polyvinylpyrrolidone (PVP), polyethylene glycol (PEG) and polyvinyl alcohol (PVA); surfactant Span-80, diglyme, 1, 4-dioxane, acetone, gamma-butyrolactone, inorganic salts zinc chloride, lithium chloride, propionic acid, etc., preferably PVP and PEG.
Drawings
FIG. 1 is a nuclear magnetic spectrum of bisphenol A type polysulfate.
FIG. 2 is an infrared spectrum of a bisphenol A type polysulfate polymer.
FIG. 3 is a graph of comparative anti-fouling performance data for example 2.
Fig. 4 is a hollow fiber membrane prepared from the polythioester polymer of example 3.
FIG. 5 is a comparison graph of water contact angles before and after sulfonation in example 4, the left graph is a water contact angle test graph of a bisphenol A type polysulfate flat membrane, and the right graph is a water contact angle test graph of a sulfonation modified bisphenol A type polysulfate flat membrane.
Fig. 6 is a high water flux membrane prepared from diphenyl sulfide ether type polysulfate in example 8.
FIG. 7 is a scanning electron microscope image of an electrospun film prepared from bisphenol A type polysulfate.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention thereto.
Example 1: the preparation method of the bisphenol A type polysulfate flat membrane comprises the following steps:
(1) preparation of high-concentration polymer solution: 4g of bisphenol A type polysulfate polymer (the polymer represented by the formula A, molecular weight: 30,000) was poured into 16g of N-methylpyrrolidone solution, heated to 80 ℃ and stirred to dissolve for more than 1 hour, cooled, left to stand and defoamed to obtain the desired polymer solution.
(2) The film forming process comprises the following steps: pouring the polymer solution after standing and defoaming on a clean glass plate, scraping the polymer solution into a film (the film is 50mm X10 mm, the thickness is 100 mu m) by using a film scraper, immersing the film into a pure water gel bath at normal temperature, standing for 10min, and drying the film in a hot air oven at 50 ℃ to obtain the bisphenol A type polysulfate reverse osmosis membrane. The obtained membrane was stored in pure water.
Testing a membrane, wherein the pure water flux of the obtained membrane is 40-55 NWP, and the BSA adsorption amount is 5mg/cm at 25 ℃ and 225psi operation pressure2The membrane performance is basically kept stable after being soaked in strong acid and strong alkali, and after being soaked in organic solvents such as dichloromethane and the like for 12 hours at normal temperature, the water flux is kept at 40-60 NWP, and the membrane is relatively stable in the solvents.
Comparative example 1: reverse osmosis membrane prepared by same method for polysulfone material
(1) Preparation of high-concentration polymer solution: 4g of polysulfone polymer (bisphenol A type basic grade polysulfone, molecular weight: 30,000) was poured into 16g of N-methylpyrrolidone solution, heated to 80 ℃ and stirred to dissolve for more than 1 hour, cooled, left to stand and defoamed to obtain the desired polymer solution.
(2) The film forming process comprises the following steps: pouring the polymer solution after standing and defoaming on a clean glass plate, scraping the polymer solution into a film (the film is 50mm X10 mm, the thickness is 100 mu m) by using a film scraper, immersing the film into a pure water gel bath at normal temperature, standing for 10min, and drying the film in a hot air oven at 50 ℃ to obtain the polysulfone reverse osmosis membrane. The obtained membrane was stored in pure water.
Testing the membrane, wherein the pure water flux of the obtained membrane is 40-50 NWP, and the BSA (bovine serum albumin) adsorption quantity is 7mg/cm at 25 ℃ and 225psi operation pressure2The membrane performance is basically kept stable after being soaked in strong acid and strong alkali, and the membrane structure is damaged after being soaked in organic solvents such as dichloromethane and the like for 12 hours at normal temperature, so that the membrane can not be used continuously.
Example 2: the diphenyl ether type polysulfate reverse osmosis membrane is prepared by the following steps:
(1) preparation of high-concentration polymer solution: 4g of a diphenyl ether type polysulfate polymer (a polymer represented by the formula B, molecular weight: 30,000) was poured into 16g of a N, N-dimethylformamide solution, heated to 80 ℃ and dissolved by stirring for more than 1 hour, cooled, left to stand and defoamed to obtain a desired polymer solution.
(2) And pouring the polymer solution subjected to standing deaeration on a metal plate supporting layer, scraping the polymer solution into a film by using a film scraper, immersing the film into a pure water gel bath at normal temperature, standing for 10min, and drying the film in a hot air oven at 50 ℃ to obtain the diphenyl ether type polysulfate reverse osmosis membrane. The obtained membrane was stored in pure water.
Testing a membrane, wherein the pure water flux of the obtained membrane is 60-80 NWP, and the BSA adsorption amount is 1mg/cm at 25 ℃ and 225psi operating pressure2. The anti-pollution performance is very good.
Comparative example 2: reverse osmosis membrane prepared by same method for polysulfone material
(1) Preparation of high-concentration polymer solution: 4g of polysulfone polymer (bisphenol A type base brand polysulfone, molecular weight: 30,000) was poured into a 16g N, N-dimethylformamide solution, heated to 80 ℃ and stirred to dissolve for more than 1 hour, cooled, left to stand and defoamed to obtain the desired polymer solution.
(2) And pouring the polymer solution subjected to standing deaeration on a metal plate supporting layer, scraping the polymer solution into a film by using a film scraper, immersing the film into a pure water gel bath at normal temperature, standing for 10min, and drying the film in a hot air oven at 50 ℃ to obtain the polysulfone reverse osmosis membrane. The obtained membrane was stored in pure water.
Testing a membrane, wherein the pure water flux of the obtained membrane is 40-50 NWP, and the BSA adsorption amount is 7mg/cm at 25 ℃ and 225psi operation pressure2. Resist againstThe pollution performance is inferior to that of a reverse osmosis membrane prepared under the same condition of diphenyl ether type poly-sulfate.
The data of the anti-contamination performance data of the reverse osmosis membranes obtained in example 2 and comparative example 2, which were compared with each other, are shown in fig. 3, in which the adsorption amount of bovine serum albumin and the recovery rate of water flux of the contaminated membrane after cleaning were measured, respectively. As shown in fig. 3, the BSA adsorption amount and the water flux recovery rate of the PSE membrane (diphenyl ether type polysulfate membrane) were higher than those measured under the same conditions.
Example 3: preparing a high-water-flux bisphenol A type polysulfate hollow fiber membrane according to a wet spinning method:
(1) preparation of high-concentration polymer solution: 4kg of bisphenol A type polysulfate polymer (the polymer represented by the formula A, the molecular weight: 60,000) is poured into 16L of N-methylpyrrolidone solution, heated until the solution is completely dissolved, 1% of PVP (polyvinyl pyrrolidone) is added as a pore-forming agent, and the mixture is uniformly stirred to obtain the required polymer solution.
(2) And filtering the prepared polymer solution, pumping the polymer solution into a spinning nozzle by using a pump, extruding the polymer solution through the spinning nozzle, drawing and stretching the polymer solution, immersing the polymer solution into a gel bath system, curing the polymer solution to obtain hollow fibers, and collecting the hollow fibers by using a godet wheel after washing treatment to obtain the required hollow fiber membrane.
Sampling tests gave data on membranes having pure water flux of 578.5Kg/m at 25 ℃ and 225psi operating pressure2H, the burst pressure is 0.388 MPa.
The hollow fiber membrane is shown in FIG. 4.
Example 4: preparation of bisphenol a type polysulfate ion separation membranes with high salt rejection by sulfonated polymers:
(1) bisphenol A type polymer (polymer shown in formula A, molecular weight: 80,000) is dissolved in DMF, concentrated sulfuric acid is added for sulfonation reaction for two hours to prepare sulfonated polysulfate with sulfonation degree of 15%, 10g of sulfonated material is dissolved in 50ml of DMSO solution, and heating, dissolving and standing are carried out for 24h for defoaming treatment.
(2) Pouring the polymer solution after standing and defoaming on clean non-woven fabrics, scraping to form a film, immersing in a normal-temperature gel bath, adding 1% of sodium dodecyl benzene sulfonate serving as a surfactant into the gel bath, standing for 10min, and drying in a hot air oven at 50 ℃ to obtain the bisphenol A type polysulfate ion separation membrane with high salt rejection rate.
Testing a membrane, wherein the pure water flux of the obtained membrane is 45-55 NWP, and the BSA adsorption amount is 5mg/cm at 25 ℃ and 225psi operating pressure2. The rejection rate of salt ions is 81.3%.
Comparative example 3: preparation of bisphenol A type polysulfate ion separation membrane from non-sulfonated polymer
(1) Dissolving 10g of non-sulfonated material in 50ml of DMSO solution, heating to dissolve the material clearly, standing for 24h, and defoaming;
(2) pouring the polymer solution after standing and defoaming on a clean glass plate, scraping the polymer solution into a film by using a film scraper, immersing the film into a normal-temperature gel bath, adding 1% of sodium dodecyl benzene sulfonate serving as a surfactant into the gel bath, standing for 10min, and drying the gel bath in a hot air oven at 50 ℃ to obtain the unsulfonated bisphenol A type polysulfate ion separation film.
Testing a membrane, wherein the pure water flux of the obtained membrane is 45-55 NWP, and the BSA adsorption amount is 3mg/cm at 25 ℃ and 225psi operating pressure2. The rejection rate of salt ions is 70.5%.
FIG. 5 is a comparison graph of water contact angles before and after sulfonation in example 4 and comparative example 3, the left graph is a water contact angle test graph of a bisphenol A type polysulfate flat sheet membrane, and the right graph is a water contact angle test graph of a sulfonation modified bisphenol A type polysulfate flat sheet membrane. As shown in FIG. 5, the water contact angle of the sulfonated membrane is reduced, and the hydrophilic property is obviously improved.
Example 5: preparing a hydroquinone type polysulfate sewage treatment membrane according to a lining enhancement method:
(1) preparing 25% concentration hydroquinone polysulfate polymer (polymer represented by formula I, molecular weight: 50,000) dimethyl sulfoxide solution, selecting polypropylene as weaving silk, and uniformly coating on the polypropylene weaving tube in coating equipment;
(2) the coated polypropylene braided tube enters a film forming channel area of equipment, the temperature of the film forming channel area is controlled to be about 50 ℃, the humidity is controlled to be about 60 percent, nitrogen is used as moisture conveying gas, and primary phase separation is carried out on an initial film;
(3) after staying for 15s averagely in the film forming channel region, the braided tube enters a coagulation bath water tank region, the first region of the coagulation bath water tank is a water mixed solution of 20% of dimethyl sulfoxide, the second region of the coagulation bath water tank is a circulating water bath, and after the coagulation bath, the lining-enhanced hollow fiber membrane is prepared.
A sample was taken and tested, and the membrane obtained had a pure water flux of 557.1Kg/m at 25 ℃ under an operating pressure of 225psi2H, the bursting pressure is 0.518Mpa, and the mechanical strength is greatly improved compared with that of the common hollow fiber membrane.
Example 6: preparing a p-hydroxybenzene sulfonate type polysulfate anion exchange membrane:
the p-hydroxybenzene sulfonate type polysulfonate polymer has good alkali resistance, excellent chemical stability, difficult swelling and good anion conduction capability. And thus can be used as an anion exchange membrane in a battery.
(1) Preparation of membrane solution: mixing 20g of p-hydroxybenzene sulfonyl fluoride monomer, a catalyst 1, 8-diazabicycloundec-7-ene and an N, N-dimethylacetamide solvent to prepare a membrane solution with the monomer concentration of 0.75 mol/L;
(2) taking non-woven fabrics as a base material, putting the non-woven fabrics into the membrane solution obtained in the step 1, and vacuumizing to remove air bubbles in the system;
(3) and (3) placing the fully soaked non-woven fabric at 60-150 ℃ to initiate polymerization reaction, and stripping a film formed on the non-woven fabric to obtain the anion exchange membrane.
The membrane is taken for testing, the obtained membrane thickness is 0.16mm, and the exchange capacity is 1.7mg g-1Water content of 20%, film surface resistance of 2.2 omega cm-2The transference number was about 0.96.
Example 7: preparing a bisphenol A type polysulfate flat film according to a hot melting method:
(1) crushing a bisphenol A type polysulfate polymer to obtain polymer powder, pouring the polymer into a feed inlet of hot melt-film forming equipment, heating to 200-250 ℃, melting the polymer powder, and extruding by the equipment to obtain a hard elastic flat membrane with the thickness of about 0.01 mm;
(2) slowly stretching the hard flat membrane, controlling the temperature within the range of 180-220 ℃, and carrying out heat setting on the stretched membrane to obtain the bisphenol A type polysulfate microporous membrane with a microporous structure.
And testing a membrane, wherein the pure water flux of the obtained membrane is 80-100 NWP at 25 ℃ and 225psi operation pressure.
Example 8: preparing a diphenyl sulfide type polysulfate flat membrane according to a polymer solution precipitation phase conversion method:
(1) 10g of a diphenyl sulfide type polysulfate copolymer polymer (polymer represented by the formula C, molecular weight: 60,000) was dissolved in 50ml of methylene chloride, and the resulting concentrated solution was drawn on an inorganic support glass plate, and the inorganic substance for support was selected to have micropores.
(2) And (3) placing the system in a ventilation device to quickly evaporate the solvent, and placing the system at 60-80 ℃ for heating for 24h after almost the solvent on the flat plate remains to obtain a uniform and compact polymer membrane skin layer with the thickness of about 100 mu m.
And testing a membrane, wherein the pure water flux of the obtained membrane is 70-95 NWP at 25 ℃ and 225psi operation pressure.
The high water flux membrane prepared from the diphenyl sulfide type polysulfate of example 8 is illustrated in figure 6.
Example 9: the preparation method comprises the following steps of preparing a piperazine type poly-ammonia sulfate flat membrane by using a ceramic substrate:
(1) immersing the ceramic microfiltration membrane into a chitosan solution with the pH value of 4, adjusting the pH value of the solution to 7, wherein chitosan molecules exist in pores of the ceramic membrane in the form of suspension, taking out the ceramic membrane after immersing the ceramic membrane in the solution for one day, and drying.
(2) The modified ceramic membrane was coated with 0.1% piperazine-type polydimethylaminosulfate, dried at 100 ℃ for 12 hours or more, and then immersed in an ice bath at PH 4 to dissolve chitosan in the pores of the ceramic membrane, and removed therefrom. The desired ceramic coating film is obtained.
And testing a membrane, wherein the pure water flux of the obtained membrane is 65-75 NWP at 25 ℃ and 225psi operating pressure.
Example 10: preparing a polysulfate gas separation membrane according to an overwater development method:
1g of bisphenol A type polysulfate polymer was dissolved in 20ml of DMF solution, heated to 100 ℃ until completely dissolved, and then allowed to stand for cooling.
1ml of polymer solution is dripped into a pure water coagulation bath, the polymer is quickly spread on the water surface to form a film layer due to the surface tension of water, and a solid film with the thickness of about 10nm is obtained after the solvent is evaporated.
The resulting multilayer film was coated on a porous support layer (ceramic support layer) to prepare a buildup film having a thickness of about 100 nm. Used for gas separation.
Sampling and testing to obtain a gas separation membrane capable of separating nitrogen from carbon dioxide (N)2/CO2) Is separated, the permeability coefficient of the nitrogen gas in the test sample is 4.42X 10-11cm3·cm/(cm2S · cmHg), separation rate 9.14%; the permeability coefficient of carbon dioxide gas in the test sample was 8.23X 10-10cm3·cm/(cm2S · cmHg), the separation rate was 82.56%.
Example 11 preparation of hollow fiber membranes from polyethylene glycol-added diphenyl ether type polysulfate:
(1) 20 parts (mass fraction (Mn is 15.2 ten thousand) of diphenyl ether type polysulfate (polymer represented by the formula B, molecular weight is 60,000) are dissolved in 58 parts of DMAc solvent at 80 ℃, 10 parts of polyvinylpyrrolidone, 10 parts of polyethylene glycol PEG-800 and 10 parts of deionized water are added to prepare a transparent solution with the concentration of the polysulfate polymer being 20%, the polymer is pressed into a spinning tank, is kept still for defoaming for 30 hours, is extruded out from a silk head under certain pressure and temperature to form a hollow fiber membrane, passes through a three-stage coagulation bath, reaches a winder for winding, is taken down, is soaked in ultrafiltration water for 24 hours, is then soaked in 20% glycerol water for 20 hours, and is subjected to an airing test.
The water flux test is 45-50L/h.m2。
Example 12 preparation of hollow fiber Membrane from Polyethyleneglycol modified Diphenyl Ether type Polysulfate
(1) Polyethylene glycol-modified diphenyl ether type polysulfate: dissolving polyethylene glycol PEG 8008 g in dry dichloromethane, adding 2.0eqv TDI (toluene diisocyanate) dropwise, keeping the reaction temperature at 0-5 deg.C, stirring at room temperature for 30min, and completely converting the raw materials to obtain diisocyanate-modified polyethylene glycol prepolymer.
(2) And dissolving 10g of diphenyl ether type polysulfate (polymer shown as a formula B, the molecular weight is 60,000) with the end group of hydroxyl in 50mL of dry dichloromethane, adding 0.5g of modified prepolymer, stirring and refluxing until the viscosity is increased to a certain degree, stopping the reaction by using methanol, precipitating the modified polymer, repeatedly dissolving, precipitating, washing and drying to obtain the modified diphenyl ether type polysulfate.
(3) Preparation of hollow fiber membrane from modified Polymer: dissolving 20 parts (mass fraction) of modified diphenyl ether type polysulfate in 58 parts of DMAc solvent at 80 ℃, adding 10 parts of polyvinylpyrrolidone, 10 parts of polyethylene glycol PEG-800, 10 parts of and 2 parts of deionized water to prepare a transparent solution with the concentration of the PEG modified polysulfate polymer being 20%, pressing the polymer into a spinning tank, standing and defoaming for 30 hours, extruding the polymer from a silk-like head under certain pressure and temperature to form a hollow fiber membrane, passing through a three-stage coagulation bath, winding the hollow fiber membrane in a winder, finally taking down the hollow fiber membrane, soaking the hollow fiber membrane in ultrafiltration water for 24 hours, soaking the hollow fiber membrane in 20% glycerol water for 20 hours, and carrying out airing test.
The water flux test is 55-65L/h.m2。
EXAMPLE 13 preparation of electrospun film of bisphenol A type polysulfate
(1) Bisphenol a type polysulfate (polymer represented by formula a, Mn ═ 8.2 ten thousand) was vacuum-dried at 80 ℃ for 24 hours, the dried polymer, PEG800 was dissolved in dry DMAc to prepare a clear solution with a polymer mass concentration of 20% and a PEG concentration of 6%, a syringe containing the polysulfate solution was fixed to a microinjection pump, spinning was started on a high-voltage power supply, and spinning was received with clean tin foil, vacuum-dried in a vacuum drying oven for 24 hours, the spun yarn was immersed in 100mL of deionized water, and shaken on an oscillator for 24 hours. Taking out the membrane, wiping the membrane with filter paper, and continuously drying the membrane in vacuum to obtain the electrospun membrane. The scanning electron micrograph is shown in FIG. 7.
The test shows that: the porosity was 35% and the average pore diameter was 2.5. mu.m.
Example 14 Synthesis of microporous covalent organic framework Polysulphate composite Membrane Using interfacial Process
(1) The bisphenol a type polysulfate film prepared in example 1 was used as a substrate for secondary synthesis, and the specific method was as follows, the bisphenol a type polysulfate film was cut into 3cm x 3cm base film, placed in a glass sealed tube, added with 0.1mL mesitylene, 1mL dioxane, 16mg trimesic aldehyde and 16mg p-phenylenediamine, slowly added dropwise with 0.2mL 3M/L acetic acid, and shaken well. And (3) freezing the glass sealed tube by using liquid nitrogen, vacuumizing for 3 times, standing in an oven with the temperature of 80 ℃ for crystallization reaction, cooling by using acetone, washing and drying after 3 days to finally obtain the covalent organic framework material polysulfate composite membrane covered with the yellow surface.
Specific surface area detection Bet 260m2The bovine serum albumin retention rate is improved to more than 98%, and the pure water flux of the obtained membrane is 45-60 NWP at 25 ℃ and 225psi operation pressure.
Example 15 preparation of a polyamide reverse osmosis membrane using bisphenol a type polysulfate as a base support layer:
(1) bisphenol A in example 1 is processed by preparing a flat membrane to obtain a bisphenol A type porous support layer, and the support layer is dried.
(2) Preparing cyclohexane solution A (the concentration is 0.3%) of isophthaloyl dichloride, and uniformly stirring for later use.
(3) Taking 1, 2, 4-triaminobenzene aqueous solution (with the concentration of 3 percent), stirring uniformly, and then adding 1 percent of N-methyl pyrrolidone, 2 percent of triethylamine and 5 percent of camphoric acid by weight of the total solution to prepare solution B for later use.
And (3) contacting the bisphenol A type polysulfate porous support layer film with the solution B for 20S, then contacting with the solution A, and then putting into a 60 ℃ oven for 30min to prepare the polyamide polysulfate composite film. The water flux test is as follows: 40-65L/h.m2。
Claims (21)
1. The use of a polysulfate polymer and modified polymers thereof in the preparation of separation membranes.
2. The use according to claim 1, wherein the separation membrane comprises a porous support layer and a dense skin layer.
3. The use according to claim 1, wherein the polysulfate-based polymer and modified polymers thereof are used in the porous support layer or the dense skin layer.
4. The use according to claim 1, wherein the poly (amino) sulfate-based polymer is a polymer containing sulfate ester bonds (-SO)4-，-SO3NH-).
5. The use according to claim 1, wherein the poly (urethane) sulfate based polymer has the general structural formula:
in the formula R1is-Me, -Et, -Ph, -iPr, or-H;
R2is-Me, -Et, -Ph, -iPr, or-H;
x is-C, -Si, or-O;
n is an integer of 10 to 1000.
6. The use according to claim 1, wherein the poly (urethane) sulfate-based polymer is prepared by at least one method selected from the group consisting of homopolymerization, polycondensation, and copolymerization with a third monomer.
7. The use according to claim 6, wherein the preparation of the poly (urethane) sulfate-based polymer further comprises chemical modification.
8. The use according to claim 4, wherein the poly (urethane) sulfate-based polymer comprises at least one selected from the group consisting of polymers represented by the following formulas A to I:
9. the use of claim 4, wherein the poly (urethane) sulfate polymer comprises a polymer constructed from two or more hydroxyl-or amine-functional monomers and sulfonyl fluoride-containing monomers.
10. The use of claim 1, wherein the polysulfate-based polymer is prepared by comprising bis-SO3Polymerizing the monomer of the F group and the dihydroxy compound under the catalysis of an alkaline catalyst to generate a polymer.
11. The use of claim 1, wherein the polythioamide ester polymer is prepared by comprising bis-NSO3Polymerizing the monomer of the group and the dihydroxy compound under the catalysis of an alkaline catalyst to generate a polymer.
12. Use according to claim 10 or 11, wherein the basic catalyst is an organic and/or inorganic base.
13. The use of claim 12, wherein the organic base is at least one selected from the group consisting of TEA, DIPEA, and DBU, and the inorganic base is at least one selected from the group consisting of sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium fluoride.
14. The use according to claim 1, wherein the separation membrane comprises at least one selected from the group consisting of a nanofiltration membrane, a microfiltration membrane, an ultrafiltration membrane, a reverse osmosis membrane, an electrodialysis membrane, a pervaporation membrane, a gas separation membrane, and a biomedical separation membrane.
15. The use according to claim 1, wherein the separation membrane is prepared by at least one method selected from the group consisting of an immersion precipitation method, a hot-melt extrusion-draw preparation method, a phase separation method, a nuclear track-etching method, a solution coating method, an interfacial polymerization method, a phase inversion method, a solution casting method, a draw film forming method, a wet spinning method, a lining reinforcement method, a hot-melt method, a spin coating method, and a water spreading method.
16. The use according to claim 15, wherein the film-making medium comprises at least one selected from the group consisting of dioxane, N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), and Dimethylacetamide (DMAC).
17. Use according to claim 15, wherein the mass concentration of the polysulfate membrane in the phase transition process is between 5 and 40%.
18. Use according to claim 17, wherein the porogenic additive comprises at least one selected from the group consisting of high molecular compounds, small molecular compounds, and inorganic substances.
19. The use of claim 18, wherein the high molecular compound comprises at least one selected from the group consisting of polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), and polyvinyl alcohol (PVA), the small molecular compound comprises at least one selected from the group consisting of Span-80, diglyme, 1, 4-dioxane, acetone, gamma-butyrolactone, and propionic acid, and the inorganic substance comprises at least one selected from the group consisting of zinc chloride and lithium chloride.
20. The use of claim 2, wherein the porous support layer comprises at least one selected from the group consisting of a polysulfate (ammonia) porous support layer, a polypropylene porous support layer, a polyethylene porous support layer, and a polyvinylidene fluoride porous support layer.
21. The use of claim 1, wherein the separation membrane is used in at least one selected from the group consisting of sewage treatment, gas separation, liquid separation, electronic components, and medical devices.
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| CN113509848A (en) * | 2021-04-27 | 2021-10-19 | 北京工业大学 | Method for preparing polyether block amide pervaporation composite membrane based on liquid-liquid interface |
| CN113509846A (en) * | 2021-04-27 | 2021-10-19 | 北京工业大学 | Method for preparing polydimethylsiloxane composite membrane by water surface spreading method and application |
| CN113817169A (en) * | 2021-11-01 | 2021-12-21 | 白银图微新材料科技有限公司 | High-temperature-resistant block polysulfate and preparation method thereof |
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