CN103788364A - Carboxyl-containing polyethersulfone, ultrafiltration membrane, and preparation methods of the carboxyl-containing polyethersulfone and the ultrafiltration membrane - Google Patents
Carboxyl-containing polyethersulfone, ultrafiltration membrane, and preparation methods of the carboxyl-containing polyethersulfone and the ultrafiltration membrane Download PDFInfo
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- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 92
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- 238000002360 preparation method Methods 0.000 title claims abstract description 35
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Abstract
The invention provides carboxyl-containing polyethersulfone, a preparation method of the carboxyl-containing polyethersulfone, an ultrafiltration membrane containing the carboxyl-containing polyethersulfone, and a preparation method of the ultrafiltration membrane. The carboxyl-containing polyethersulfone has a structure shown as the formula (I), wherein R1-R8 and R11-R18 are independently hydrogen atom or C1-C5 alkyl, R9 is nonexistent or C1-C5 alkylidene, R10 is hydrogen atom, C1-C5 alkylidene carboxylic acid or C1-C5 alkyl, and n is not less than 2. The ultrafiltration membrane prepared from the carboxyl-containing polyethersulfone has good hydrophilicity and stain resistance and has good industrial prospect. The formula (I) is described in the specification.
Description
Technical Field
The invention relates to a preparation method of carboxyl-containing polyether sulfone and carboxyl-containing polyether sulfone, an ultrafiltration membrane prepared from the carboxyl-containing polyether sulfone, and a preparation method of the ultrafiltration membrane.
Background
The polyether sulfone is a special engineering plastic with excellent comprehensive performance, has excellent heat resistance, radiation resistance, insulativity, aging resistance and the like, and has wide application in the fields of electronic instruments, mechanical instruments, aerospace and the like due to excellent mechanical performance, thermal stability and chemical stability. However, with the development of high-tech fields, the existing polyethersulfone species have been unable to meet the requirements of more application fields. Therefore, the development of polyethersulfones with novel structures becomes a research hotspot.
Membrane separation is a new technique of separation that emerged at the beginning of the 20 th century and rises rapidly after the 60's of the 20 th century. Because the membrane separation technology has the functions of separation, concentration, purification and refining, and has the characteristics of high efficiency, energy conservation, environmental protection, molecular-level filtration, simple filtration process, easy control and the like, the membrane separation technology is widely applied to the fields of food, medicine, biology, environmental protection, chemical industry, metallurgy, energy, petroleum, water treatment, electronics, bionics and the like at present, generates great economic benefit and social benefit, and becomes one of the most important means in the separation science at present. The core of membrane separation technology is the separation membrane. The porous membrane can be classified into a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane and a reverse osmosis membrane according to the pore size of the membrane. Porous membranes with effective pore sizes between 1nm and 0.2um are generally considered ultrafiltration membranes. Ultrafiltration membranes are mostly asymmetric membranes and tend to contain a relatively large and thick support layer and a relatively small and thin separation layer which determines the flux and rejection properties of the membrane. Due to the specific pore diameter characteristic, the ultrafiltration membrane can realize the separation of macromolecular substances, colloidal substances and small molecular solvents, and is widely applied to the fields of food industry, pharmaceutical industry, textile industry, paper industry, leather industry and the like, such as milk concentration, whey protein recovery, bovine serum separation, drinking water purification and the like. In the application process of the ultrafiltration membrane, different requirements are put forward on the performance of the ultrafiltration membrane according to different treatment objects, different operation conditions and different pretreatment and cleaning modes of the membrane. For example, in sewage treatment processes, the membrane materials used are required to have good resistance to acid and alkali corrosion and contamination, as well as excellent mechanical properties and thermal stability.
Most industrial ultrafiltration membranes are made by a phase inversion process. Phase inversion is a process by which a polymer changes from a liquid state to a solid state in some controlled manner. This solidification process is usually initiated by the transition of a homogeneous liquid to two liquid states in a liquid-liquid separation. When the delamination reaches a certain degree, one of the liquid phases solidifies, forming the solidification host, while the other liquid phase (polymer-poor phase) becomes the mesopores of the film. Phase inversion methods include vapor phase precipitation, thermal precipitation, immersion precipitation, controlled evaporation precipitation, and the like. Immersion precipitation is the process of scraping a casting solution comprising a polymer and a solvent into a primary film, and then immersing the film in a non-solvent having a certain temperature. The concentration of the polymer solution is increased due to the rapid permeation of the solvent into the non-solvent, resulting in the occurrence of phase separation until the solvent is completely removed to form a polymer film.
At present, the materials for preparing the ultrafiltration membrane mainly comprise inorganic ceramics and organic polymer materials. Although the inorganic ceramic membrane has high mechanical strength, high temperature resistance and corrosion resistance, the excessive production cost is not favorable for large-scale popularization. In contrast, the organic polymer membrane is low in price and cost, and is beneficial to large-scale production and utilization. Therefore, a large number of organic polymer membranes have been commercialized and applied to the field of ultrafiltration separation. The membrane materials mainly comprise polysulfone, polyethersulfone, cellulose acetate, polyacrylonitrile, polyvinylidene fluoride and the like. These membranes are generally less hydrophilic and are more prone to contamination, which not only reduces the separation efficiency of the membrane, but also increases the operating cost of the membrane.
Disclosure of Invention
The invention aims to overcome the defects of poor hydrophilicity and stain resistance of the conventional ultrafiltration membrane, and provides carboxyl-containing polyethersulfone with good hydrophilicity and stain resistance, a preparation method of the carboxyl-containing polyethersulfone, an ultrafiltration membrane prepared from the carboxyl-containing polyethersulfone and a preparation method of the ultrafiltration membrane.
The invention provides a polyether sulfone containing carboxyl, wherein the polyether sulfone containing carboxyl has a formula (I)
The structure shown is as follows:
wherein R is1-R8、R11-R18Each independently is hydrogen or C1-C5Alkyl of R9Is absent or is C1-C5Alkylene of (A), R10Is hydrogen, C1-C5Alkylene carboxylic acid or C1-C5N is not less than 2.
The invention also provides a preparation method of the carboxyl-containing polyether sulfone, wherein the method comprises the steps of reacting a bisphenol monomer with a structure shown in a formula (II) with a diphenyl sulfone monomer with a structure shown in a formula (III) under a condensation reaction condition in the presence of a catalyst to obtain the carboxyl-containing polyether sulfone with a structure shown in a formula (I);
wherein R is1-R8、R11-R18Each independently is hydrogen or C1-C5Alkyl of R9Is absent or is C1-C5Alkylene of (A), R10Is hydrogen, C1-C5Alkylene carboxylic acid or C1-C5Alkyl of R19And R20Is halogen, n is more than or equal to 2.
The invention also provides an ultrafiltration membrane prepared from the carboxyl-containing polyether sulfone.
In addition, the invention also provides a preparation method of the ultrafiltration membrane, which comprises the steps of uniformly coating the casting solution containing the carboxyl polyether sulfone and the organic solvent on a substrate to form a primary membrane, and converting the primary membrane into the ultrafiltration membrane by adopting a phase inversion method.
The inventor of the invention finds that the ultrafiltration membrane containing the carboxyl-containing polyether sulfone with the structure shown in the formula (I) has stronger hydrophilicity and pollution resistance, and has great industrial prospect.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a nuclear magnetic hydrogen spectrum of polyether sulfone containing carboxyl group obtained from preparation example 1;
FIG. 2 is a scanning electron micrograph of an ultrafiltration membrane obtained in example 1.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The polyether sulfone containing carboxyl provided by the invention has a structure shown in a formula (I),
wherein R is1-R8、R11-R18Each independently is hydrogen or C1-C5Alkyl of R9Is absent or is C1-C5Alkylene of (A), R10Is hydrogen, C1-C5Alkylene carboxylic acid or C1-C5N is not less than 2. Preferably, R1-R8、R11-R18Is hydrogen, R9Is C1-C3Alkylene of (A), R10Is C1-C3N is more than or equal to 40 and less than or equal to 100. From the viewpoint of availability of raw materials, it is particularly preferable that the carboxyl group-containing polyethersulfone is composed of the following specific R1-R18The components of the formula are as follows:
R1-R8and R11-R18Is hydrogen, R9Is ethylene, R10Is methyl; or,
R1-R8and R11-R18Is hydrogen, R9Is ethylene, R10Is ethyl; or,
R1-R8and R11-R18Is hydrogen, R9Is ethylene, R10Is propyl.
According to the invention, said C1-C5Specific examples of the alkyl group of (a) may be, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl and neopentyl; said C is1-C5Specific examples of alkylene groups of (a) may be, but are not limited to: methylene, ethylene, propylene, butylene, and pentylene.
The preparation method of the carboxyl-containing polyether sulfone comprises the steps of reacting a bisphenol monomer with a structure shown in a formula (II) with a diphenyl sulfone monomer with a structure shown in a formula (III) under the condensation reaction condition and in the presence of a catalyst to obtain the carboxyl-containing polyether sulfone with a structure shown in a formula (I);
wherein R is1-R8、R11-R18Each independently is hydrogen or C1-C5Alkyl of R9Is absent or is C1-C5Alkylene of (A), R10Is hydrogen, C1-C5Alkylene carboxylic acid or C1-C5Alkyl of R19And R20Is halogen, n is more than or equal to 2; preferably, R1-R8、R11-R18Is hydrogen, R9Is C1-C3Alkylene of (A), R10Is C1-C3Alkyl of R19And R20Each independently being fluorine or chlorine, 40. ltoreq. n.ltoreq.100.
As described above, the C1-C5Specific examples of the alkyl group of (a) may be, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl and neopentyl; said C is1-C5Specific examples of alkylene groups of (a) may be, but are not limited to: methylene, ethylene, propylene, butylene, and pentylene.
According to the present invention, the bisphenol monomer may be any of various materials having a structure represented by formula (II) known in the art, and for example, may be selected from one or more of 4,4 ' -bis (4-hydroxyphenyl) -2-pentanoic acid, 4 ' -bis (4-hydroxyphenyl) -3-hexanoic acid, and 4,4 ' -bis (4-hydroxyphenyl) -4-heptanoic acid. From the viewpoint of availability of raw materials, the bisphenol monomer is particularly preferably 4, 4' -bis (4-hydroxyphenyl) -2-pentanoic acid.
According to the present invention, the diphenyl sulfone monomer may be any of the existing ones having a structure represented by formula (iii), and for example, may be selected from one or more of 4,4 ' -dichlorodiphenyl sulfone, 4 ' -difluorodiphenyl sulfone, and 4,4 ' -dibromodiphenyl sulfone. From the viewpoint of availability of raw materials, the diphenyl sulfone monomer is particularly preferably 4,4 '-dichlorodiphenyl sulfone and/or 4, 4' -difluorodiphenyl sulfone.
The amount of the bisphenol monomer and the diphenyl sulfone monomer used in the present invention is not particularly limited as long as the carboxyl group-containing polyethersulfone having the structure represented by formula (i) can be obtained, and for example, the molar ratio of the bisphenol monomer to the diphenyl sulfone monomer may be 0.8 to 1.2: 1.
the amount of the catalyst used according to the present invention may be conventionally selected in the art, and for example, the amount of the catalyst may be 1 to 2.5mol, preferably 1.5 to 2mol, based on 1mol of the bisphenol monomer. The catalyst may be any of various catalysts known to those skilled in the art that can be used for the condensation reaction, and for example, the catalyst may be selected from one or more of potassium carbonate, sodium carbonate, calcium carbonate, potassium hydroxide, sodium hydroxide, calcium hydroxide, and calcium hydride. From the viewpoint of catalytic effect, the catalyst is preferably potassium carbonate and/or sodium carbonate.
According to the present invention, in order to bring the bisphenol monomer and the diphenylsulfone monomer into contact more sufficiently and to control the degree of polymerization of the resulting carboxyl group-containing polyethersulfone having the structure represented by formula (i), it is preferable that the contact is carried out in the presence of an organic solvent and an azeotropic dehydrating agent. The organic solvent may be any organic solvent capable of dissolving the bisphenol monomer, the diphenyl sulfone monomer, and the carboxyl group-containing polyether sulfone, and may be one or more selected from the group consisting of sulfolane, N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone, for example. The azeotropic dehydrating agent may be any of various existing substances which are capable of azeotroping with water produced in the reaction system and bringing the water out of the reaction system at an azeotropic temperature, and for example, the azeotropic dehydrating agent may be one or more selected from the group consisting of toluene, xylene and chlorobenzene.
In addition, the amounts of the organic solvent and the azeotropic dehydrating agent can be selected and varied within a wide range, and for example, the amount of the organic solvent can be 1500 mL-450 mol and the amount of the azeotropic dehydrating agent can be 600 mL-200 mol based on 1mol of the diphenylsulfone monomer, which can facilitate the reaction.
According to the present invention, the condensation reaction conditions may be conventional in the art. For example, the condensation reaction conditions include a reaction temperature and a reaction time, the reaction temperature can be performed in a wide temperature range, and in general, the reaction temperature is preferably 120-220 ℃ in order to further facilitate the reaction. The extension of the reaction time is advantageous for the improvement of the conversion rate of the reactant or the yield of the reaction product, but the extension of the reaction time is not significant for the improvement of the conversion rate of the reactant or the yield of the reaction product, and therefore, the reaction time is preferably 4 to 10 hours in consideration of efficiency and effect.
According to the present invention, the boiling point of the azeotropic dehydrating solvent is generally low, so that the reaction cannot be carried out under a high temperature condition. Therefore, in order to improve the conversion rate of reactants and the yield of reaction products, the preparation method of the carboxyl group-containing polyether sulfone provided by the invention preferably further comprises distilling off the azeotropic dehydrating agent after the reaction for a period of time, and continuing the reaction of the rest materials. Accordingly, the condensation reaction comprises two stages carried out in sequence, wherein the first stage is carried out in the presence of an azeotropic dehydrating agent and the second stage is carried out under conditions to remove the azeotropic dehydrating agent. The reaction conditions of the first stage comprise a temperature of 120-150 ℃ and a reaction time of 1.5-4 hours, and the reaction conditions of the second stage comprise a temperature of 150-220 ℃ and a reaction time of 2.5-6 hours, so that the two condensation reaction stages are better cooperated.
After the condensation reaction is completed, the reaction product is usually gummy due to the relatively high molecular weight of the carboxyl group-containing polyethersulfone. In addition, the reaction product also contains residual catalyst, organic solvent and azeotropic dehydrating agent. Therefore, in order to crush and purify the carboxyl group-containing polyethersulfone in the reaction product, the preparation method of the carboxyl group-containing polyethersulfone provided by the invention preferably further comprises the steps of contacting the reaction product with an acidic solution, crushing and filtering the contact product by using a crusher, then boiling and washing by using distilled water, filtering, and drying the solid-phase product. The kind of the acidic solution is well known to those skilled in the art, and may be, for example, hydrochloric acid, a sulfuric acid solution, a phosphoric acid solution, or the like. The concentration of the acidic solution may be generally 0.5 to 2 mol/L.
The invention also provides an ultrafiltration membrane of the polyether sulfone containing the carboxyl group, which is prepared from the polyether sulfone containing the carboxyl group.
As known to those skilled in the art, the pure water flux of an ultrafiltration membrane and the retention rate of Bovine Serum Albumin (BSA) are important indexes for evaluating the performance of the ultrafiltration membrane, wherein the pure water flux refers to the pure water permeation amount of the ultrafiltration membrane in unit area in unit time under certain temperature and operating pressure, and the retention rate of the BSA refers to the ratio of the concentration difference between the concentration of the solution of the BSA and the concentration of the solution of the BSA permeating the ultrafiltration membrane to the concentration of the solution of the BSA under certain temperature and operating pressure.
According to the invention, the pure water flux of the ultrafiltration membrane is preferably 125-210L/m at a pressure of 0.2MPa and a temperature of 25 DEG C2H, a retention rate of 75-98% for bovine serum albumin at a concentration of 1 mg/mL. The pure water flux can be measured by the following method: loading the ultrafiltration membrane into a cup-type ultrafilter, prepressing at 0.1MPa for 2 hr, and measuring pure water permeation of the ultrafiltration membrane at 25 deg.C under 0.2MPa for 1 hrThe amount is calculated by the following formula:
j = Q/(A.t), wherein J is pure water flux, Q is pure water permeability (L), and A is effective membrane area (m) of ultrafiltration membrane2) And t is time (h).
The retention rate of the ultrafiltration membrane on bovine serum albumin can be obtained by the following test method: the ultrafiltration membrane is put into a cup type ultrafilter (purchased from Shanghai Spiro plate membrane company, model SCM type), pre-pressed for 2h under 0.1MPa, and the change of concentration (weight average molecular weight of 67000, purchased from national drug group chemical reagent Co., Ltd.) in bovine serum albumin raw solution and bovine serum albumin permeate is measured within 1h under the conditions of pressure of 0.2MPa and temperature of 25 ℃, and is calculated by the following formula:
R=（Cp-Cf）/Cpx 100%, wherein R is the rejection rate, CpAs concentration of bovine serum albumin in stock solution, C in the test of the present inventionpIs 1mg/mL, CfThe concentration of bovine serum albumin in the permeate was used. CpAnd CfAll measurements were performed using an ultraviolet-visible spectrophotometer (model UV-7502PC, from Shanghai Xinmao instruments Co., Ltd.).
In addition, the invention also provides a preparation method of the ultrafiltration membrane, which comprises the steps of uniformly coating the casting solution containing the carboxyl polyether sulfone and the organic solvent on a substrate to form a primary membrane, and converting the primary membrane into the ultrafiltration membrane by adopting a phase inversion method.
As is well known to those skilled in the art, the casting solution may also typically contain additives to improve the film-forming and water permeability of the casting solution. The kind of the additive is well known to those skilled in the art, and may be various existing additives that can be used for preparing an ultrafiltration membrane, for example, the additive may be selected from one or more of polyvinylpyrrolidone, polyethylene glycol, and lithium chloride.
The content of the components in the membrane casting solution according to the present invention may be selected and varied within wide limits, for example the content of the carboxyl group-containing polyethersulfone may be in the range of 10-30 wt% and the content of the additive may be in the range of 1-15 wt%, based on the total weight of the membrane casting solution. In addition, the weight ratio of the carboxyl group-containing polyether sulfone to the additive is preferably 2-10: 1.
as is well known to those skilled in the art, ultrafiltration membranes typically comprise a relatively large and thick support layer and a relatively small and thin separation layer. The ultrafiltration membrane prepared by the method of the invention has a matrix which is a supporting layer, and the membrane casting solution is a separating layer after phase inversion. The substrate may be any of various existing substrates having a certain pore size and strength and capable of being used as a support layer of an ultrafiltration membrane, and may be a polyester nonwoven fabric, which is known to those skilled in the art and will not be described herein again.
As is well known to those skilled in the art, in a composite ultrafiltration membrane, the separation layer may have a thickness of, for example, 30 to 150 microns, and the support layer may have a thickness of, for example, 50 to 150 microns. Accordingly, the amount of the casting solution used is such that the thickness of the obtained separation layer is within the above range and the support layer having the above thickness is selected.
According to the present invention, the method of converting the primary membrane into an ultrafiltration membrane using a phase inversion method is well known to those skilled in the art, and may be, for example, a gas phase gel method, a solvent evaporation gel method, a thermal gel method, or an immersion gel method. The phase inversion process of the present invention is preferably a dip-gel process. Specifically, the method comprises soaking the primary membrane in water at 20-40 ℃ for 20-30 hours.
According to the present invention, in order to provide an ultrafiltration membrane with better water permeability, preferably, the preparation method of an ultrafiltration membrane provided by the present invention further comprises filtering the membrane casting solution to obtain a filtrate before the membrane casting solution is uniformly coated on a substrate to form a primary membrane, and defoaming the filtrate in vacuum. The method and conditions for vacuum defoamation are well known to those skilled in the art, and are generally performed in a vacuum defoamer, which will not be described herein.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
(1) the polymerization degree n of the carboxyl-containing polyether sulfone is calculated by adopting the ratio of the number average molecular weight to the molecular weight of a structural unit, wherein the number average molecular weight is measured by adopting a Gel Permeation Chromatograph (GPC) which is available from WATERS company of America and is of an ALLIANCE2690 model, THF is used as a mobile phase, narrow-distribution polystyrene is used as a standard sample, and the temperature is 25 ℃;
(2) the pure water flux of the ultrafiltration membrane is measured by the following method: the ultrafiltration membrane is loaded into a cup type ultrafilter (purchased from Shanghai Spiro plate membrane company, model SCM), pre-pressed for 2h under 0.1MPa, and the pure water permeability of the ultrafiltration membrane is measured under the conditions of pressure of 0.2MPa and temperature of 25 ℃ within 1h and calculated by the following formula:
j = Q/(A.t), wherein J is pure water flux, Q is pure water permeability (L), and A is effective membrane area (m) of ultrafiltration membrane2) T is time;
(3) the retention rate of the ultrafiltration membrane on bovine serum albumin is obtained by the following test method: the ultrafiltration membrane is put into a cup type ultrafilter (purchased from Shanghai Spiro plate membrane company, model SCM type), pre-pressed for 2h under 0.1MPa, and the change of concentration (weight average molecular weight of 67000, purchased from national drug group chemical reagent Co., Ltd.) in bovine serum albumin raw solution and bovine serum albumin permeate is measured within 1h under the conditions of pressure of 0.2MPa and temperature of 25 ℃, and is calculated by the following formula:
R=（Cp-Cf）/Cpx 100%, wherein R is the rejection rate, CpAs concentration of bovine serum albumin in stock solution, C in the test of the present inventionpIs 1mg/mL, CfThe concentration of bovine serum albumin in the permeate was used. CpAnd CfAll adopt UV-visible spectrophotometer (from Shanghai Xinmao instruments Co., Ltd.)Model number UV-7502 PC).
Preparation example 1
The preparation example is used for illustrating the carboxyl-containing polyether sulfone and the preparation method thereof provided by the invention.
0.03mol of 4,4 '-bis (4-hydroxyphenyl) -2-pentanoic acid, 0.03mol of 4, 4' -dichlorodiphenyl sulfone and 0.054mol of anhydrous potassium carbonate were added to a three-necked flask equipped with mechanical stirring, thermometer. Adding 40mL of N-methylpyrrolidone and 20mL of toluene under the protection of nitrogen, heating to 140 ℃ for reaction for 4 hours, evaporating the toluene, heating to 190 ℃ for reaction for 8 hours, pouring the reaction solution into 1mol/L dilute hydrochloric acid aqueous solution, crushing by using a crusher, filtering, boiling and washing the polymer by using distilled water, filtering, repeating the steps for 6 times, and drying in an oven to obtain 14.25g of carboxyl-containing polyether sulfone D1, wherein the polymerization degree N is 80, and the yield is 95%.
Nuclear magnetic hydrogen spectrum given in fig. 1 (a)1H NMR) shows that various hydrogen attributes in the carboxyl-containing polyether sulfone D1, particularly, a signal peak represents a hydrogen atom on a carboxyl group, three signal peaks of b, c and D respectively correspond to the hydrogen atom on an aliphatic side chain, 1 and 2 signal peaks represent the hydrogen atom on a diphenolic acid benzene ring, and 3 and 4 signal peaks represent the hydrogen atom on a diphenyl sulfone benzene ring, which indicates that the carboxyl-containing polyether sulfone is successfully synthesized.
Preparation example 2
The preparation example is used for illustrating the carboxyl-containing polyether sulfone and the preparation method thereof provided by the invention.
0.024mol of 4,4 '-bis (4-hydroxyphenyl) -2-pentanoic acid, 0.03mol of 4, 4' -difluorodiphenyl sulfone and 0.054mol of anhydrous sodium carbonate were added to a three-necked flask equipped with mechanical stirring, thermometer. Adding 40mL of N, N-dimethylformamide and 20mL of chlorobenzene under the protection of nitrogen, heating to 140 ℃ for reaction for 4 hours, evaporating toluene, heating to 190 ℃ for reaction for 8 hours, pouring the reaction solution into 1mol/L dilute hydrochloric acid aqueous solution, crushing by a crusher, filtering, boiling and washing the polymer by distilled water, filtering, repeating for 6 times, and drying in an oven to obtain 14.25g of carboxyl-containing polyether sulfone D2, wherein the polymerization degree N is 50, and the yield is 95%.
1H NMR analysis: the signal peak with the chemical shift of 12.5ppm corresponds to the hydrogen atom on the carboxyl, the signal peak with the chemical shift of 7.9ppm represents the hydrogen atom on the ortho position of the sulfuryl, and the signal peak with the chemical shift of 7.0-7.5ppm corresponds to the hydrogen atom on other positions on the benzene ring, which indicates that the polyether sulfone containing the carboxyl is successfully synthesized.
Preparation example 3
The preparation example is used for illustrating the carboxyl-containing polyether sulfone and the preparation method thereof provided by the invention.
0.03mol of 4,4 '-bis (4-hydroxyphenyl) -2-pentanoic acid, 0.024mol of 4, 4' -dichlorodiphenyl sulfone and 0.054mol of sodium hydroxide were added to a three-necked flask equipped with mechanical stirring, thermometer. Adding 40mL of dimethyl sulfoxide and 20mL of xylene under the protection of nitrogen, heating to 140 ℃, reacting for 4 hours, evaporating toluene, heating to 190 ℃, reacting for 8 hours, pouring the reaction solution into 1mol/L dilute hydrochloric acid aqueous solution, crushing by a crusher, filtering, boiling and washing the polymer by distilled water, filtering, repeating for 6 times, and drying in an oven to obtain 14.25g of carboxyl-containing polyether sulfone D3, wherein the polymerization degree n is 48, and the yield is 95%.
1H NMR analysis: the signal peak with the chemical shift of 12.2ppm corresponds to the hydrogen atom on the carboxyl, the signal peak with the chemical shift of 7.7ppm represents the hydrogen atom on the ortho position of the sulfuryl, and the signal peak with the chemical shift of 7.0-7.5ppm corresponds to the hydrogen atom on other positions on the benzene ring, which indicates that the polyether sulfone containing the carboxyl is successfully synthesized.
Preparation example 4
The preparation example is used for illustrating the carboxyl-containing polyether sulfone and the preparation method thereof provided by the invention.
A carboxyl group-containing polyethersulfone was prepared in accordance with the procedure of preparation example 1 except that said 4,4 '-bis (4-hydroxyphenyl) -2-pentanoic acid was replaced with the same number of moles of 4, 4' -bis (4-hydroxyphenyl) -4-heptanoic acid and said 4,4, -dichlorodiphenyl sulfone was replaced with the same number of moles of difluorodiphenyl sulfone to give 15.15g of carboxyl group-containing polyethersulfone D4 in a yield of 96%.
1H NMR analysis: the signal peak at the chemical shift of 11.0ppm corresponds to the hydrogen atom on the carboxyl, the signal peak at the chemical shift of 7.7-7.9ppm represents the hydrogen atom at the ortho position of the sulfuryl, the signal peak within the chemical shift range of 6.6-7.6ppm corresponds to the hydrogen atom at other positions on the benzene ring, and the chemical shift of 1.3-2.2 is the hydrogen atom on the fat side chain, which indicates that the polyether sulfone containing the carboxyl is successfully synthesized.
Example 1
This example serves to illustrate an ultrafiltration membrane and a method of making the same according to the present invention.
Under magnetic stirring, 20g of carboxyl-containing polyether sulfone D1, 2g of additive polyvinylpyrrolidone (PVPK 30) and 78g of solvent N, N-dimethylformamide are uniformly mixed to obtain the casting solution. And filtering and defoaming the membrane casting solution, and then coating the membrane casting solution on polyester non-woven fabric by using a scraper to form a nascent membrane, wherein the temperature of a membrane scraping chamber is 25 ℃ and the humidity is 20%. Then, the scraped nascent membrane is immediately soaked in deionized water at 25 ℃ for 24h, and finally the ultrafiltration membrane M1 is obtained.
The microstructure of the ultrafiltration membrane M1 was observed by scanning electron microscopy, and the result is shown in FIG. 2. It can be seen from fig. 2 that the ultrafiltration membrane has a relatively dense separation layer having a thickness of 62 microns and a support layer having a relatively large pore size having a thickness of 90 microns.
After pre-pressing for 2h at 0.1MPa, the pure water flux of the ultrafiltration membrane M1 is 230.0L/M under the conditions of 0.2MPa of pressure and 25 ℃ of temperature2H, the retention rate of bovine serum albumin was 76.5%, and it was found that the ultrafiltration membrane had better hydrophilicity. Further, after continuous operation for 12 hours under these conditions, the pure water flux was 228.7L/m2H, the retention rate of bovine serum albumin was 76.3%, from which it was found that the ultrafiltration membrane M1 had a pure water flux and a serum retention rate after 12 hours of continuous operationThe retention rate of protein is almost unchanged, and the protein has better pollution resistance.
Example 2
This example serves to illustrate an ultrafiltration membrane and a method of making the same according to the present invention.
Under magnetic stirring, 20g of polyether sulfone D2 containing carboxyl, 5g of additive polyvinylpyrrolidone (PVPK 30) and 75g of solvent N, N-dimethylformamide are uniformly mixed to obtain the casting solution. And filtering and defoaming the membrane casting solution, and then coating the membrane casting solution on polyester non-woven fabric by using a scraper to form a nascent membrane, wherein the temperature of a membrane scraping chamber is 25 ℃ and the humidity is 20%. Then, the scraped nascent membrane was immediately soaked in deionized water at 25 ℃ for 24h to finally obtain ultrafiltration membrane M2 with separation layer thickness of 56 microns and support layer thickness of 90 microns.
After pre-pressing for 2h at 0.1MPa, the pure water flux of the ultrafiltration membrane M2 is measured to be 209.1L/M under the conditions that the pressure is 0.2MPa and the temperature is 25 DEG C2H, the retention rate of bovine serum albumin was 86.8%, and it was found that the ultrafiltration membrane had better hydrophilicity. Further, after continuous operation for 12 hours under these conditions, the pure water flux was 208.6L/m2H, the retention rate of bovine serum albumin was 86.0%, and it was found that the pure water flux and the retention rate of serum albumin of the ultrafiltration membrane M2 were almost unchanged after 12 hours of continuous operation, which had better contamination resistance.
Example 3
This example serves to illustrate an ultrafiltration membrane and a method of making the same according to the present invention.
Under magnetic stirring, 20g of carboxyl-containing polyether sulfone D3, 8g of additive polyvinylpyrrolidone (PVPK 30) and 72g of solvent N, N-dimethylformamide are uniformly mixed to obtain the casting solution. And filtering and defoaming the membrane casting solution, and then coating the membrane casting solution on polyester non-woven fabric by using a scraper to form a nascent membrane, wherein the temperature of a membrane scraping chamber is 25 ℃ and the humidity is 20%. The scraped nascent membrane was then immediately soaked in 25 ℃ deionized water for 24h to yield final ultrafiltration membrane M3 with a separation layer thickness of 58 microns and a support layer thickness of 90 microns.
After pre-pressing for 2h at 0.1MPa, the pure water flux of the ultrafiltration membrane M3 is measured to be 125.4L/M at 25 ℃ and under the pressure of 0.2MPa2H, the retention rate of bovine serum albumin was 97.2%, and it was found that the ultrafiltration membrane had better hydrophilicity. Further, after continuous operation for 12 hours under these conditions, the pure water flux was 124.1L/m2H, the retention rate of bovine serum albumin was 96.8%, and it was found that the pure water flux and the retention rate of serum albumin of the ultrafiltration membrane M3 were almost unchanged after 12 hours of continuous operation, which had better contamination resistance.
Example 4
This example serves to illustrate an ultrafiltration membrane and a method of making the same according to the present invention.
An ultrafiltration membrane was prepared by following the procedure of example 1 except that the carboxyl group-containing polyethersulfone D1 was replaced with the carboxyl group-containing polyethersulfone D4 prepared in preparation example 4 to finally obtain an ultrafiltration membrane M4.
After pre-pressing for 2h at 0.1MPa, the pure water flux of the ultrafiltration membrane M3 is 156.7L/M measured at 25 ℃ and under the pressure of 0.2MPa2H, the retention rate of bovine serum albumin was 96.2%, and it was found that the ultrafiltration membrane had better hydrophilicity. Further, after continuous operation for 12 hours under these conditions, the pure water flux was 155.3L/m2H, the retention rate of bovine serum albumin was 95.6%, and it was found that the pure water flux and the retention rate of serum albumin of the ultrafiltration membrane M4 were almost unchanged after 12 hours of continuous operation, which had better contamination resistance.
Comparative example 1
This comparative example serves to illustrate a reference ultrafiltration membrane according to the invention and a method for its preparation.
An ultrafiltration membrane was prepared according to the method of example 1 except that the carboxyl group-containing polyethersulfone D1 was replaced with a non-carboxyl group-containing polyethersulfone (available from Solvay under the designation P3500) to finally yield an ultrafiltration membrane DM 1.
After pre-pressing for 2h at 0.1MPa, the pure water flux of the ultrafiltration membrane DM1 is measured to be 320.7L/m under the conditions of 0.2MPa of pressure and 25 ℃ of temperature2H, the retention rate of bovine serum albumin was 95.3%, and it was found that the ultrafiltration membrane had better hydrophilicity. Further, after continuous operation for 12 hours under these conditions, the pure water flux was 140.6L/m2H, the retention rate of bovine serum albumin was 94.9%, and it was found that the pure water flux of the ultrafiltration membrane DM1 was significantly decreased after 12 hours of continuous operation, and the contamination resistance was poor.
Because the polyether sulfone containing the carboxyl group has the hydrophilic carboxyl group, the ultrafiltration membrane prepared by the polyether sulfone has larger pure water flux, namely, the ultrafiltration membrane has stronger hydrophilicity. In addition, as can be seen from the results of the above examples and comparative examples, after the continuous operation for 12 hours, the pure water flux and the retention rate of bovine serum albumin of the ultrafiltration membrane prepared from the carboxyl group-containing polyethersulfone hardly change, while the pure water flux of the ultrafiltration membrane DM1 obtained from the comparative example is remarkably reduced, so that the ultrafiltration membrane provided by the invention has strong pollution resistance and has great industrial prospect.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (16)
1. A carboxyl group-containing polyethersulfone, wherein the carboxyl group-containing polyethersulfone has the structure shown in formula (i):
wherein R is1-R8、R11-R18Each independently is hydrogen or C1-C5Alkyl of R9Is absent or is C1-C5Alkylene of (A), R10Is hydrogen, C1-C5Alkylene carboxylic acid or C1-C5N is not less than 2.
2. The carboxyl-containing polyethersulfone of claim 1, wherein R is1-R8、R11-R18Is hydrogen, R9Is C1-C3Alkylene of (A), R10Is C1-C3N is more than or equal to 40 and less than or equal to 100.
3. The carboxyl-containing polyethersulfone of claim 2,
R1-R8and R11-R18Is hydrogen, R9Is ethylene, R10Is methyl; or,
R1-R8and R11-R18Is hydrogen, R9Is ethylene, R10Is ethyl; or,
R1-R8and R11-R18Is hydrogen, R9Is ethylene, R10Is propyl.
4. A preparation method of carboxyl-containing polyether sulfone comprises the steps of reacting a bisphenol monomer with a structure shown in a formula (II) with a diphenyl sulfone monomer with a structure shown in a formula (III) in the presence of a catalyst under condensation reaction conditions to obtain carboxyl-containing polyether sulfone with a structure shown in a formula (I);
wherein R is1-R8、R11-R18Each independently is hydrogen or C1-C5Alkyl of R9Is absent or is C1-C5Alkylene of (A), R10Is hydrogen, C1-C5Alkylene carboxylic acid or C1-C5Alkyl of R19And R20Is halogen, n is more than or equal to 2.
5. The method of claim 4, wherein R1-R8、R11-R18Is hydrogen, R9Is C1-C3Alkylene of (A), R10Is C1-C3Alkyl of R19And R20Each independently being fluorine or chlorine, 40. ltoreq. n.ltoreq.100.
6. The production method according to claim 4 or 5, wherein the molar ratio of the bisphenol monomer to the diphenyl sulfone monomer is 0.8-1.2: 1; preferably, the bisphenol monomer is selected from one or more of 4,4 ' -bis (4-hydroxyphenyl) -2-pentanoic acid, 4 ' -bis (4-hydroxyphenyl) -3-hexanoic acid and 4,4 ' -bis (4-hydroxyphenyl) -4-heptanoic acid; preferably, the diphenyl sulfone monomer is selected from one or more of 4,4 ' -dichlorodiphenyl sulfone, 4 ' -difluorodiphenyl sulfone and 4,4 ' -dibromodiphenyl sulfone.
7. The production method according to claim 4 or 5, wherein the catalyst is used in an amount of 1 to 2.5mol based on 1mol of the bisphenol monomer; preferably, the catalyst is selected from one or more of potassium carbonate, sodium carbonate, calcium carbonate, potassium hydroxide, sodium hydroxide, calcium hydroxide and calcium hydride.
8. The production method according to claim 4 or 5, wherein the reaction of the bisphenol monomer with the diphenylsulfone monomer is carried out in the presence of an organic solvent and an azeotropic dehydrating agent; preferably, the organic solvent is selected from one or more of sulfolane, N-dimethylformamide, dimethylsulfoxide and N-methylpyrrolidone; preferably, the azeotropic dehydrating agent is selected from one or more of toluene, xylene and chlorobenzene.
9. The preparation method according to claim 8, wherein the condensation reaction conditions include a reaction temperature of 120 ℃ and a reaction time of 4-10 hours; preferably, the condensation reaction comprises two stages carried out in sequence, the first stage being carried out in the presence of an azeotropic dehydrating agent and the second stage being carried out under conditions to remove the azeotropic dehydrating agent; preferably, the reaction conditions of the first stage include a reaction temperature of 120-150 ℃ and a reaction time of 1.5-4 hours, and the reaction conditions of the second stage include a reaction temperature of 150-220 ℃ and a reaction time of 2.5-6 hours.
10. An ultrafiltration membrane prepared from the carboxyl group-containing polyethersulfone of claim 1, 2 or 3.
11. An ultrafiltration membrane according to claim 10, wherein the pure water flux of said ultrafiltration membrane is 125-210L/m at a pressure of 0.2MPa and a temperature of 25 ℃2H, a retention rate of 75-98% for bovine serum albumin at a concentration of 1 mg/mL.
12. A method for producing an ultrafiltration membrane, which comprises uniformly coating a casting solution containing the carboxyl group-containing polyethersulfone of claim 1, 2 or 3 and an organic solvent on a substrate to form a primary membrane, and converting the primary membrane into an ultrafiltration membrane by a phase inversion method.
13. The preparation method according to claim 12, wherein the casting solution further contains an additive selected from one or more of polyvinylpyrrolidone, polyethylene glycol and lithium chloride.
14. A preparation method according to claim 13, wherein the content of the carboxyl group-containing polyethersulfone is 10-30 wt% and the content of the additive is 1-15 wt%, based on the total weight of the membrane casting solution; preferably, the weight ratio of the carboxyl-containing polyether sulfone to the additive is 2-10: 1.
15. the production method according to claim 12, 13 or 14, wherein the method of converting the primary membrane into the ultrafiltration membrane using the phase inversion method comprises soaking the primary membrane in water at 20 to 40 ℃ for 20 to 30 hours.
16. The production method according to claim 15, further comprising filtering the dope solution before uniformly coating the dope solution on a substrate to form a primary membrane, and vacuum-defoaming the obtained filtrate.
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