CN108479432B - Preparation method of hydrophilic phenolphthalein polyether sulfone composite nanofiber ultrafiltration membrane - Google Patents
Preparation method of hydrophilic phenolphthalein polyether sulfone composite nanofiber ultrafiltration membrane Download PDFInfo
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Abstract
The invention relates to a preparation method of a hydrophilic phenolphthalein polyether sulfone composite nanofiber ultrafiltration membrane, which comprises the following steps: dissolving phenolphthalein polyethersulfone PES-C in an organic solvent to obtain a spinning solution, carrying out jet spinning on the solution, drying to obtain a PES-C nanofiber membrane, spraying a cross-linked polyvinylpyrrolidone PVPP solution on the surface of the PES-C nanofiber membrane, and carrying out hot pressing treatment to obtain the composite material. Compared with the widely used electrostatic spinning technology, the composite nanofiber ultrafiltration membrane prepared by the solution jet spinning method has the advantages of high production efficiency, low energy consumption, wide application object range, suitability for industrial production and the like; the prepared phenolphthalein polyether sulfone composite nanofiber ultrafiltration membrane has high hydrophilicity, thermal stability, acid and alkali corrosion resistance, high pollution resistance and durability, is beneficial to industrial production and has wide application prospects in the fields of microfiltration, ultrafiltration and the like.
Description
Technical Field
The invention belongs to the field of preparation of modified nanofiber membranes, and particularly relates to a preparation method of a hydrophilic phenolphthalein polyether sulfone composite nanofiber ultrafiltration membrane.
Background
Phenolphthalein polyether sulfone (PES-C) is a novel semi-crystalline aromatic thermoplastic engineering plastic independently developed in China, has the glass transition temperature of 263 ℃ and the heat-resistant temperature of more than 150 ℃, has a series of advantages of high strength and modulus, high temperature resistance, fatigue resistance, radiation resistance, corrosion resistance, good dimensional stability and the like, and is widely applied to the high-tech fields of space navigation, electronics, information, energy and the like.
Phenolphthalein polyethersulfone (PES-C) is a hydrophobic polymer material, so in the fields of sewage treatment and the like, in order to overcome the defects of poor hydrophobicity and pollution resistance and the like of the material, the membrane material needs to be modified. The membrane pollution is a process that the pollutant is deposited on the surface and inside of the membrane to reduce the membrane flux, researches prove that the hydrophilic surface can adsorb more water, the anti-pollution capacity of the membrane can be effectively improved, and the hydrophilic substance is added into the hydrophobic membrane in the modes of blending, grafting, coating and the like, so that the method is more effective.
In the existing literature reports, PES-C ultrafiltration membranes prepared by a phase inversion method or an immersion precipitation method are mostly modified in heat resistance and hydrophilicity, for example, CN201110430250 discloses a preparation method of a hydrophilic phenolphthalein based polyarylethersulfone alloy ultrafiltration membrane, but few researches on hydrophilic modification of PES-C nanofiber composite ultrafiltration membranes prepared by a solution-jet spinning method are mentioned.
As a novel technology for preparing the micro/nano fiber material, the solution jet spinning method has the advantages of simple process, low energy consumption, high production efficiency, high safety and the like compared with electrostatic spinning. The solution spraying method has low requirement on equipment, the preparation method is simpler and more convenient, the safety is high, and the method is not only suitable for most polymer materials, but also suitable for inorganic materials, and is the best mode for realizing industrial production of the nano fibers at present.
Adopt solution injection apparatus with hydrophilicity cortical material (PVPP) spraying to nanofiber membrane surface, can guarantee that the liquid drop can be more even spray the target object on, the spraying is efficient, high to the utilization ratio of raw and other materials, and to the thickness of coating easy control, strong adaptability to the kind of spraying, degree of automation is high, can be better overcome traditional casting membrane liquid to porous base film seepage and the difficult problem of coating thickness control, be favorable to the industrialization popularization.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a hydrophilic phenolphthalein polyether sulfone composite nanofiber ultrafiltration membrane, which is simple to operate, low in energy consumption, mild in condition and suitable for industrial production.
The invention relates to a preparation method of a hydrophilic phenolphthalein polyether sulfone composite nanofiber ultrafiltration membrane, which comprises the following specific steps:
(1) dissolving phenolphthalein polyethersulfone PES-C in an organic solvent to obtain a spinning solution, carrying out jet spinning on the solution, and drying to obtain a PES-C nanofiber membrane, wherein the concentration of the spinning solution is 15-35 wt%;
(2) and (2) spraying a cross-linked polyvinylpyrrolidone PVPP solution on the surface of the PES-C nanofiber membrane in the step (1), and performing hot-pressing treatment to obtain the hydrophilic phenolphthalein polyether sulfone composite nanofiber ultrafiltration membrane with a complete barrier layer.
The phenolphthalein polyethersulfone PES-C in the step (1) is synthesized according to the method described in patent CN85101721A (one-step method for synthesizing polyarylethersulfone with phthalein side groups), and the method comprises the following steps: adding 0.02M-0.50M of phenolphthalein and equimolar 4, 4' -dichlorodiphenyl sulfone into a reactor, adding a small amount of toluene and potassium carbonate which is 5% -100% of the stoichiometric relationship, adding dimethyl sulfoxide, sulfolane or diphenyl sulfone which is required by the solid content of 30% -70% as a solvent, introducing nitrogen for protection, evaporating toluene in the heating process, continuing heating to 170 ℃ -200 ℃ for polymerization for about 4-8 hours, cooling when the required viscosity is reached, adding a solvent for dilution, introducing methyl chloride gas at about 100 ℃ to seal a terminal group, cooling, filtering to remove salt, pouring into a precipitator for precipitation, washing with water, refluxing with ethanol, filtering, and drying to obtain a white flocculent polymer.
The inherent viscosity number of the phenolphthalein polyethersulfone PES-C is between 0.4 and 1.2g/dL, and preferably between 0.6 and 0.8 g/dL.
The organic solvent in the step (1) is DMF, DMAc or NMP.
The technological parameters of the solution jet spinning in the step (1) are as follows: the diameter of a spinneret orifice is 0.5-1.0 mm, the propelling speed is 1-5 ml/h per orifice, the spinning air pressure is 0.05-0.2 MPa, the receiving distance is 15-40 cm, the spinning time is 1-3 h, and the atmosphere used for spinning is nitrogen, argon or helium.
The preparation method of the PVPP solution in the step (2) comprises the following steps: dissolving polyvinylpyrrolidone (PVP) in water to obtain a PVP solution, adding an initiator, and crosslinking to obtain a PVPP solution, wherein the concentration of the PVP solution is 1 wt% -5 wt%, and the mass ratio of the initiator to the PVP is 1: 0.5-2.
The molecular weight of PVP is 1 x 104～130×104(ii) a The initiator is potassium persulfate, sodium persulfate or ammonium persulfate.
The crosslinking temperature is 70-90 ℃, and the crosslinking time is 1-5 h.
The spraying in the step (2) is performed by a solution spraying device.
The spraying process parameters in the step (2) are as follows: the diameter of a spinneret orifice is 0.5-1.0 mm, the propelling speed is 1-5 ml/h per hole, the spraying pressure is 0.05-0.2 MPa, the receiving distance is 15-40 cm, the spraying time is 1-3 h, and the atmosphere used for spraying is nitrogen, argon or helium.
The hot-pressing treatment temperature in the step (2) is 160-200 ℃, the hot-pressing treatment pressure is 0-10 Mpa and is not 0, and the hot-pressing treatment time is 0-60 min and is not 0.
The invention prepares the phenolphthalein polyether sulfone nanofiber membrane by a solution jet spinning method, then cross-linked PVP is sprayed on the surface of the nanofiber membrane by a solution spraying device to be used as a barrier layer of a composite membrane, and finally the composite PES-C nanofiber ultrafiltration membrane with permanent hydrophilicity and strong pollution resistance is formed by simple hot pressing treatment. The invention can simply and accurately control the thickness and uniformity of the barrier layer and obviously and durably improve the hydrophilicity of the composite film.
The phenolphthalein polyethersulfone composite nanofiber ultrafiltration membrane obtained by the method can effectively improve the hydrophobicity of the traditional polysulfone membrane, PVPP is sprayed on the surface of the nanofiber membrane through a solution spraying device, and simple heat treatment is carried out on the nanofiber membrane. The hydrophilicity of the membrane can be obviously increased only by attaching a very thin layer of PVPP on the surface of the fibrous membrane. Along with the extension of the spraying time, more and more PVPP (polyvinyl pyrrolidone) is attached to the surface of the fiber membrane, which is beneficial to the hydrophilicity of the membrane, but can cause the heat resistance of the membrane to be reduced, and the water flux of the membrane can be reduced while the retention rate is improved.
In the traditional film preparation process using PVP as an additive, as PVP is easily soluble in water, PVP can be continuously lost along with the prolonging of the use time in the preparation of the film and the subsequent filtration application, so that the hydrophilicity and the pollution resistance of the material are poor. After PVP is crosslinked, the PVP is not dissolved in water and other organic solvents while the hydrophilicity is ensured, and the PVP is firmly attached to the surface of the nanofiber membrane and is not easy to fall off after hot pressing treatment, so that a more stable composite nanofiber membrane structure is formed, and the durability of hydrophilic modification is ensured.
The water Flux Recovery Rate (FRR) of the membrane is generally used for representing the quality of the anti-pollution capability of the membrane, the value is between 0 and 1, and the closer to 1, the stronger the anti-pollution capability of the membrane is. The definition is shown as the following formula:
wherein, J0The initial water flux of the membrane, and J is the recovered water flux after the membrane filtration operation is finished and washed.
Advantageous effects
(1) Compared with the widely used electrostatic spinning technology, the composite nanofiber ultrafiltration membrane prepared by the solution jet spinning method has the advantages of high production efficiency, low energy consumption, wide application object range, suitability for industrial production and the like;
(2) the prepared phenolphthalein polyether sulfone composite nanofiber ultrafiltration membrane has high hydrophilicity, thermal stability, acid and alkali corrosion resistance and high pollution resistance, and meanwhile, PVPP attached to the surface of the fiber membrane is insoluble in water and common solvents, so that the durability of a hydrophilic modification effect is ensured, the industrial production is favorably realized, and the phenolphthalein polyether sulfone composite nanofiber ultrafiltration membrane can be widely applied to the fields of water filtration, gas filtration, food processing, medicines, purification and the like.
Drawings
FIG. 1 is a schematic view of a solution spraying apparatus of the present invention;
FIG. 2 is a scanning electron micrograph of the PES-C nanofiber membrane of example 1;
FIG. 3 is a scanning electron microscope image of the surface of the PES-C nanofiber-based composite film in example 1.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
All starting materials are commercially available products.
Example 1
(1) Dissolving phenolphthalein polyether sulfone with intrinsic viscosity of 1.0g/dL in DMF to prepare 15 wt% spinning solution, standing for defoaming, extruding the spinning solution out of a spinneret orifice through a metering pump, stretching and collecting through high-speed airflow to form a nanofiber membrane, wherein relevant process parameters are as follows: the diameter of a spinneret orifice is 0.8mm, the propelling speed is 5 ml/h.hole, the spinning air pressure is 0.08MPa, the receiving distance is 15cm, the spinning time is 2h, and the atmosphere used for spinning is nitrogen; and drying the obtained nanofiber membrane for 10 hours at the temperature of 80 ℃ in vacuum to obtain the PES-C nanofiber membrane.
(2) Preparing a PVPK 305 wt% solution, adding potassium persulfate serving as an initiator and the mass ratio of the potassium persulfate to the PVPK30 being 2:1, and heating to 80 ℃ for reaction for 5 hours to obtain a PVPP solution.
(3) Spraying the PVPP solution in the step (2) onto the surface of the PES-C nanofiber membrane in the step (1) through a solution spraying device to obtain a PES-C/PVPP composite initial nanofiber membrane, wherein the relevant process conditions are as follows: the diameter of a spinneret orifice is 0.5mm, the propelling speed is 4 ml/h.hole, the jetting pressure is 0.05MPa, the receiving distance is 25cm, the spraying time is 2h, the atmosphere used for spraying is nitrogen, the obtained composite membrane is immersed in water to remove impurities, and the composite membrane is dried for 10h at the temperature of 80 ℃ in vacuum.
(4) Clamping the composite film obtained in the step (3) by using release paper, and putting the composite film into a mould, wherein the base film (PES-C) faces upwards, the PVPP faces downwards, the temperature is adjusted to be 160 ℃, the pressure is 0.5MPa, the treatment time is 20min, and the PES-C nanofiber-based composite film is obtained, and the thickness of the PVPP blocking layer is about 7 mu m. The PVPP can melt and flow at a certain temperature so as to cover the whole surface of the fiber membrane, is firmly attached to the surface of the nanofiber membrane and is not easy to fall off, and the durability of hydrophilicity is ensured due to the cross-linked state of the PVPP.
The PES-C nanofiber-based composite membrane can be used in the field of ultrafiltration, and the pure water flux of a pressurized 50kPa test membrane is about 320L/m in average value2H, then 1g/L of the ovalbumin solution is filtered for 1h, then a simple rinsing is carried out for several minutes, and the recovery water flux is again tested to be about 282L/m2H, water flux recovery 88%.
FIG. 2 shows that: PES-C micro-nano level fibers can be prepared by a solution jet spinning method, the surfaces of the fibers are smooth, the diameters of the fibers are uniform, and the spinnability of the fibers is good.
FIG. 3 shows: PVPP is sprayed on the surface of the nanofiber membrane, and a PVPP barrier layer with a uniform and complete surface is obtained after simple heat treatment.
Example 2
(1) Dissolving phenolphthalein polyether sulfone with intrinsic viscosity of 0.65g/dL in DMF to prepare 25 wt% spinning solution, standing for defoaming, extruding the spinning solution out of a spinning pinhole through a metering pump, stretching and collecting through high-speed airflow to form a nanofiber membrane, wherein relevant process parameters are as follows: the diameter of a spinneret orifice is 0.7mm, the propelling speed is 4 ml/h.hole, the spinning air pressure is 0.12MPa, the receiving distance is 25cm, the spinning time is 2h, the spinning atmosphere is nitrogen, and the obtained nanofiber membrane is dried for 10h at the temperature of 80 ℃ in vacuum to obtain the PES-C nanofiber membrane.
(2) Preparing a PVPK 603 wt% solution, adding sodium persulfate serving as an initiator and the mass ratio of the sodium persulfate to the PVPK60 being 1:1, and heating to 70 ℃ for reaction for 4 hours to obtain a PVPP solution.
(3) Spraying the PVPP solution in the step (2) onto the surface of the nanofiber membrane in the step (1) through a solution spraying device to obtain the PES-C/PVPP composite initial nanofiber membrane, wherein relevant process conditions are as follows: the diameter of a spinneret orifice is 0.7mm, the propelling speed is 3 ml/h.hole, the jet pressure is 0.08MPa, the receiving distance is 30cm, the spraying time is 1.5h, the atmosphere used for spraying is nitrogen, the obtained composite membrane is immersed in water to remove impurities, and the composite membrane is dried for 10h at the temperature of 80 ℃ in vacuum.
(4) Clamping the composite film obtained in the step (3) by using release paper, putting the composite film into a mould, wherein the base film (PES-C) is upward, the PVPP is downward, the temperature is adjusted to be 180 ℃, the pressure is 3MPa, and the treatment time is 20min, so that the PES-C nanofiber-based composite film is obtained, and the thickness of a PVPP barrier layer is about 3 mu m.
The PES-C nanofiber-based composite membrane can be used in the field of ultrafiltration, and the pure water flux of a pressurized 50kPa test membrane is about 530L/m in average value2H, then 1g/L ovalbumin solution is filtered for 1h, then a few minutes of simple rinsing are carried out, and the recovery water flux of about 420L/m is tested again2H, water flux recovery 80%.
Example 3
(1) Dissolving phenolphthalein polyether sulfone with intrinsic viscosity of 0.5g/dL in DMF to prepare 30 wt% spinning solution, standing for defoaming, extruding the spinning solution out of a spinneret orifice through a metering pump, stretching and collecting through high-speed airflow to form a nanofiber membrane, wherein the relevant process parameters are as follows: the diameter of a spinneret orifice is 0.5mm, the propelling speed is 5 ml/h.hole, the spinning air pressure is 0.2MPa, the receiving distance is 40cm, the spinning time is 2h, the spinning atmosphere is nitrogen, and the obtained nanofiber membrane is dried for 10h at the temperature of 80 ℃ in vacuum to obtain the PES-C nanofiber membrane.
(2) Preparing a PVPK 902 wt% solution, adding ammonium persulfate serving as an initiator and having a mass ratio of 1:2 with the PVPK90, and heating to 90 ℃ for reaction for 2 hours to obtain a PVPP solution.
(3) Spraying the PVPP solution in the step (2) onto the surface of the PES-C nanofiber membrane in the step (1) through a solution spraying device to obtain a PES-C/PVPP composite initial nanofiber membrane, wherein the relevant process conditions are as follows: the diameter of a spinneret orifice is 1.0mm, the propelling speed is 2.5 ml/h.hole, the jet pressure is 0.1MPa, the receiving distance is 35cm, the spraying time is 2.5h, the atmosphere used for spraying is nitrogen, the obtained composite membrane is immersed in water to remove impurities, and the composite membrane is dried for 10h at the temperature of 80 ℃ in vacuum.
(4) Clamping the composite film obtained in the step (3) by using release paper, putting the composite film into a mould, wherein the base film (PES-C) faces upwards, the PVPP faces downwards, the temperature is adjusted to be 200 ℃, the pressure is 1MPa, and the treatment time is 5min, so that the PES-C nanofiber-based composite film is obtained, and the thickness of a PVPP blocking layer is about 5 mu m.
The PES-C nanofiber-based composite membrane can be used in the field of ultrafiltration, and the pure water flux of a pressurized 50kPa test membrane is about 400L/m in average value2H, then 1g/L of the ovalbumin solution is filtered for 1h, then a few minutes of simple rinsing are carried out, and the recovery water flux of about 340L/m is tested again2H, water flux recovery 85%.
Example 4
(1) Dissolving phenolphthalein polyether sulfone with intrinsic viscosity of 0.8g/dL in DMF to prepare 20 wt% spinning solution, standing for defoaming, extruding the spinning solution out of a spinneret orifice through a metering pump, stretching and collecting through high-speed airflow to form a nanofiber membrane, wherein the relevant process parameters are as follows: the diameter of a spinneret orifice is 0.6mm, the propelling speed is 3 ml/h.hole, the spinning air pressure is 0.15MPa, the receiving distance is 30cm, the spinning time is 2h, the spinning atmosphere is nitrogen, and the obtained nanofiber membrane is dried for 10h at the temperature of 80 ℃ in vacuum to obtain the PES-C nanofiber membrane.
(2) Preparing a PVPK 304 wt% solution, adding potassium persulfate serving as an initiator and the mass ratio of the potassium persulfate to the PVPK30 being 1:1, and heating to 80 ℃ for reaction for 5 hours to obtain a PVPP solution.
(3) Spraying the PVPP solution in the step (2) onto the surface of the PES-C nanofiber membrane in the step (1) through a solution spraying device to obtain a PES-C/PVPP composite initial nanofiber membrane, wherein the relevant process conditions are as follows: the diameter of a spinneret orifice is 0.8mm, the propelling speed is 3 ml/h.hole, the jet pressure is 0.15MPa, the receiving distance is 40cm, the spraying time is 2h, the atmosphere used for spraying is nitrogen, the obtained composite membrane is immersed in water to remove impurities, and the composite membrane is dried for 10h at the temperature of 80 ℃ in vacuum.
(4) Clamping the composite film obtained in the step (3) by using release paper, putting the composite film into a mould, wherein the base film (PES-C) faces upwards, the PVPP faces downwards, the temperature is adjusted to be 170 ℃, the pressure is 2MPa, and the treatment time is 10min, so that the PES-C nanofiber-based composite film is obtained, and the thickness of a PVPP blocking layer is about 6 mu m.
The PES-C nanofiber-based composite membrane can be used in the field of ultrafiltration, and the pure water flux of a pressurized 50kPa test membrane is about 350L/m2H, then 1g/L ovalbumin solution is filtered for 1h, then a few minutes of simple rinsing are carried out, and the recovery water flux of about 315L/m is tested again2H, water flux recovery 90%.
The embodiment shows that the composite nanofiber membrane obtained by taking PVPP as the barrier layer can be applied to the field of ultrafiltration, has better protein pollution resistance, is easy to realize large-scale production, and has wide application prospect in the field of membrane separation.
Claims (8)
1. A preparation method of a hydrophilic phenolphthalein polyether sulfone composite nanofiber ultrafiltration membrane comprises the following specific steps:
(1) dissolving phenolphthalein polyethersulfone PES-C in an organic solvent to obtain a spinning solution, carrying out jet spinning on the solution, and drying to obtain a PES-C nanofiber membrane, wherein the concentration of the spinning solution is 15-35 wt%;
(2) and (2) spraying a cross-linked polyvinylpyrrolidone PVPP solution on the surface of the PES-C nanofiber membrane in the step (1), and performing hot-pressing treatment to obtain the hydrophilic phenolphthalein polyether sulfone composite nanofiber ultrafiltration membrane.
2. The preparation method of the hydrophilic phenolphthalein polyethersulfone composite nanofiber ultrafiltration membrane according to claim 1, wherein the organic solvent in step (1) is DMF, DMAc or NMP.
3. The preparation method of the hydrophilic phenolphthalein polyethersulfone composite nanofiber ultrafiltration membrane according to claim 1, wherein the process parameters of the solution jet spinning in the step (1) are as follows: the diameter of a spinneret orifice is 0.5-1.0 mm, the propelling speed is 1-5 ml/h per orifice, the spinning air pressure is 0.05-0.2 MPa, the receiving distance is 15-40 cm, the spinning time is 1-3 h, and the atmosphere used for spinning is nitrogen, argon or helium.
4. The preparation method of the hydrophilic phenolphthalein polyethersulfone composite nanofiber ultrafiltration membrane according to claim 1, wherein the preparation method of the PVPP solution in the step (2) comprises the following steps: dissolving polyvinylpyrrolidone (PVP) in water to obtain a PVP solution, adding an initiator, and crosslinking to obtain a PVPP solution, wherein the concentration of the PVP solution is 1 wt% -5 wt%, and the mass ratio of the initiator to the PVP is 1: 0.5-2.
5. The method for preparing the hydrophilic phenolphthalein polyethersulfone composite nanofiber ultrafiltration membrane according to claim 4, wherein the molecular weight of PVP is 1 x 104～130×104(ii) a The initiator is potassium persulfate, sodium persulfate or ammonium persulfate.
6. The preparation method of the hydrophilic phenolphthalein polyethersulfone composite nanofiber ultrafiltration membrane according to claim 4, wherein the crosslinking temperature is 70-90 ℃ and the crosslinking time is 1-5 hours.
7. The preparation method of the hydrophilic phenolphthalein polyethersulfone composite nanofiber ultrafiltration membrane according to claim 1, wherein the spraying process parameters in the step (2) are as follows: the diameter of a spinneret orifice is 0.5-1.0 mm, the propelling speed is 1-5 ml/h per hole, the spraying pressure is 0.05-0.2 MPa, the receiving distance is 15-40 cm, the spraying time is 1-3 h, and the atmosphere used for spraying is nitrogen, argon or helium.
8. The preparation method of the hydrophilic phenolphthalein polyethersulfone composite nanofiber ultrafiltration membrane according to claim 1, wherein the hot-pressing treatment temperature in the step (2) is 160-200 ℃, the hot-pressing treatment pressure is 0-10 Mpa but not 0, and the hot-pressing treatment time is 0-60 min but not 0.
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