CN111167321B - Self-luminous high-molecular ultrafiltration membrane and preparation method thereof - Google Patents

Self-luminous high-molecular ultrafiltration membrane and preparation method thereof Download PDF

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CN111167321B
CN111167321B CN202010018587.4A CN202010018587A CN111167321B CN 111167321 B CN111167321 B CN 111167321B CN 202010018587 A CN202010018587 A CN 202010018587A CN 111167321 B CN111167321 B CN 111167321B
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luminous
ultrafiltration membrane
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rare earth
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CN111167321A (en
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樊凯
林学山
冉江权
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Chongqing College of Electronic Engineering
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components

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Abstract

The invention discloses a self-luminous high-molecular ultrafiltration membrane and a preparation method thereof, wherein the preparation method comprises the following steps: adding the rare earth aluminate self-luminous material into a homogeneous solution containing a film-making polymer raw material and a pore-forming agent under an anaerobic condition, uniformly dispersing the rare earth aluminate self-luminous material into the homogeneous solution by stirring and ultrasonic vibration to prepare a stable suspension solution, and preparing a flat ultrafiltration membrane or a hollow ultrafiltration membrane by using the prepared suspension solution. Compared with the traditional high-molecular membrane material, the surface contact angle of the self-luminous high-molecular ultrafiltration membrane prepared by the invention is obviously reduced, and the hydrophilicity is effectively improved, so that the self-luminous high-molecular ultrafiltration membrane has good pollution resistance; and the rare earth aluminate self-luminous material endows the macromolecular ultrafiltration membrane with the self-luminous characteristic, so that the macromolecular ultrafiltration membrane can intelligently respond to membrane pollution based on the self-luminous characteristic, and the evaluation and the determination of the pollution degree of the macromolecular ultrafiltration membrane are facilitated.

Description

Self-luminous high-molecular ultrafiltration membrane and preparation method thereof
Technical Field
The invention relates to the technical field of high-molecular ultrafiltration membranes, in particular to a preparation method of a high-molecular ultrafiltration membrane.
Background
Membrane separation utilizes a material having selective permeability, and under the external driving force, the driving force comprises: pressure difference, potential difference, temperature difference and concentration difference, etc. to separate, purify and concentrate the mixture. Due to the difference of application, membrane-making material and membrane-making process, there are various methods for classifying membrane materials, and classification can be made according to material, membrane structure, application and action mechanism. If the separation membranes are classified according to their structures and uses, the membranes can be classified into five major categories, such as reverse osmosis, nanofiltration, ultrafiltration, microfiltration, and electrodialysis. The ultrafiltration membrane is a physical pore size screening method fundamentally, the pore size of the ultrafiltration membrane is generally limited to 1-50nm, and the effective separation of suspended particles, fibers, bacteria, viruses and other macromolecules with different sizes is realized by limiting the pore size. Common raw materials for preparing the polymeric ultrafiltration membrane include polyvinylidene fluoride (PVDF), Polyethersulfone (PES), polytetrafluoroethylene (Teflon or PTFE), and the like.
However, the conventional polymeric ultrafiltration membrane has some obvious defects in the using process. The most prominent problem is two, the first: polyvinylidene fluoride, polyether sulfone and polytetrafluoroethylene have strong hydrophobic property, which greatly restricts the wide application of the polyvinylidene fluoride, polyether sulfone and polytetrafluoroethylene. If the water inlet end of the commonly used polyvinylidene fluoride, polyether sulfone and polytetrafluoroethylene ultrafiltration membrane is not well pretreated, some solid suspended matters, bacteria and macromolecular proteins are attached to the surface and in membrane pores of the membrane to cause the problem of membrane pollution, so that the service life of the membrane is influenced; secondly, the method comprises the following steps: the pollution degree of the ultrafiltration membrane cannot be accurately evaluated and measured in the using process. The conventional method for judging membrane pollution at present is to integrally judge the pollution condition of a membrane component through flux and pressure difference, and the membrane component is generally dismounted and replaced integrally when polluted to a certain degree. In fact, the degree of membrane fouling varies at different locations of the membrane module and at different transmembrane pressure differences, resulting in material waste and increased labor costs for the entire membrane module replacement.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a self-luminous polymeric ultrafiltration membrane and a self-luminous polymeric ultrafiltration membrane, so as to solve the technical problems that the existing polymeric ultrafiltration membrane has strong hydrophobicity and is easy to cause membrane pollution, and the pollution degree of the polymeric ultrafiltration membrane is difficult to accurately evaluate and measure.
The invention discloses a preparation method of a self-luminous high-molecular ultrafiltration membrane, which comprises the following steps: adding the rare earth aluminate self-luminous material into a homogeneous solution containing a film-making polymer raw material and a pore-forming agent under an anaerobic condition, uniformly dispersing the rare earth aluminate self-luminous material into the homogeneous solution by stirring and ultrasonic vibration to prepare a stable suspension solution, and preparing a flat ultrafiltration membrane or a hollow ultrafiltration membrane by using the prepared suspension solution.
Preferably, the mass ratio of the high molecular raw material to the rare earth aluminate self-luminous material is 10: 0.05-10: 0.2; the mass ratio of the high polymer raw material to the pore-forming agent is 10: 0.1-10: 1; the dosage of the rare earth aluminate self-luminous material in the homogeneous solution is 0.1-10 wt%.
Preferably, the mass ratio of the polymer raw material to the pore-forming agent is 10: 0.1-10: 1; the dosage of the rare earth aluminate self-luminous material in the homogeneous solution is 1.6-4 wt%.
Preferably, the mass ratio of the high molecular raw material to the rare earth aluminate self-luminous material is 10:0.15, the dosage of the rare earth aluminate self-luminous material in the homogeneous solution is 2.4 wt% or 3.2 wt%.
Preferably, the rare earth aluminate self-luminous material is SrAl2O4·Tb3+、SrAl2O4·Dy3+And SrAl2O4·Eu2+One of (1); the polymer raw material is one of polyvinylidene fluoride, polyether sulfone and polytetrafluoroethylene.
Preferably, the solvent of the homogeneous solution is one or more of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethylsulfoxide.
Preferably, the pore former is polyethylene glycol.
Preferably, the weight average molecular weight of the polymer raw material is 20000-200000.
A macromolecular ultrafiltration membrane prepared by the preparation method of the self-luminous macromolecular ultrafiltration membrane.
The invention has the beneficial effects that:
1. compared with the traditional high molecular membrane material, the surface contact angle of the modified self-luminous high molecular ultrafiltration membrane prepared by the preparation method of the self-luminous high molecular ultrafiltration membrane is obviously reduced, and the hydrophilicity is effectively improved, so that the modified self-luminous high molecular ultrafiltration membrane has good pollution resistance; and the rare earth aluminate self-luminous material endows the macromolecular ultrafiltration membrane with the self-luminous characteristic, the rare earth material is uniformly distributed in the membrane, the luminous performance is stable, and based on the self-luminous characteristic, the macromolecular ultrafiltration membrane can intelligently respond to membrane pollution, thereby facilitating the evaluation and determination of the pollution degree of the macromolecular ultrafiltration membrane.
2. According to the preparation method of the self-luminous high-molecular ultrafiltration membrane, the molecular rigidity of the high-molecular membrane material is effectively improved by adding the rare earth aluminate self-luminous material, so that the compressive strength of the prepared high-molecular ultrafiltration membrane is effectively improved.
Drawings
FIG. 1 is a view showing the film-forming suspension obtained in example 1 under different light conditions.
As can be seen from FIG. 1, the prepared film-forming suspension had a self-luminescent property, and stable emission of light intensity was measured both by a luminometer and by visual observation in the absence of light, and the luminescence intensity at 542nm measured by the luminometer reached 29.8 Lux.
FIG. 2 is an observation view of the self-luminous polymeric ultrafiltration membrane prepared in example 1 under different illumination conditions.
As can be seen from FIG. 2, the prepared self-luminous polymeric ultrafiltration membrane has self-luminous characteristics, stable light emission can be measured by a luminometer and visual observation under the condition of no light, and the light intensity at 542nm measured by the luminometer reaches 29.8 Lux.
FIG. 3 is a contact angle detection diagram of a self-luminous polymeric ultrafiltration membrane.
As can be seen from fig. 3, the contact angle of the polymeric ultrafiltration membrane (containing 0 rare earth aluminate self-luminescent material) obtained in the comparative example is the largest, indicating that the membrane has strong hydrophobicity. With the continuous addition of the rare earth material, the contact angle is continuously reduced, which shows that the hydrophilicity of the modified self-luminous film material is effectively improved.
FIG. 4 is a graph showing the anti-contamination performance of the self-luminous polymeric ultrafiltration membrane and the polymeric ultrafiltration membrane obtained in the comparative example under the illumination condition. Fig. 4 corresponds to a self-luminous polymeric ultrafiltration membrane prepared in the ninth example, fig. 4 corresponds to b in the fifth example, fig. 4 corresponds to c in the second example, and fig. 4 corresponds to d in the comparative example. As can be seen from FIG. 4, the polymeric ultrafiltration membrane obtained in the comparative example was the least resistant to contamination. Along with the continuous addition of the rare earth material, the pollution resistance of the modified membrane material is effectively improved.
Detailed Description
The invention is further described below with reference to the figures and examples.
In the following examples, before preparing a homogeneous solution, the polymer material was pretreated by the following method: the polymer material is washed by deionized water, soaked in the deionized water for more than one week, changed for a plurality of times during the soaking, and then dried to constant weight under the conditions of vacuum and 70 ℃. The macromolecule ultrafiltration membranes prepared in the embodiments adopt a contact angle meter to detect the hydrophilicity effect, and utilize illuminometer testing and membrane anti-pollution experiments to detect the anti-pollution condition of the membranes and intelligently respond to the membrane pollution condition.
Comparative example:
accurately weighing 10g of pretreated polyether sulfone (PES) powder, dissolving the powder in 89.6g of Dimethylformamide (DMF) solvent, adding 0.6g of polyethylene glycol (PEG) pore-forming agent (the mass ratio of PES to PEG is 10:0.6), stirring for 24 hours at the temperature of 60 ℃ to obtain a homogeneous solution, taking out the homogeneous solution, and scraping the homogeneous solution by using a film scraping machine to form a film, thus obtaining the high-molecular ultrafiltration membrane.
The first embodiment is as follows:
accurately weighing 10g of pretreated polyether sulfone (PES) powder, dissolving the powder in 89.6g of Dimethylformamide (DMF) solvent, adding 0.1g of polyethylene glycol (PEG) according to the mass ratio of PES to PEG of 10:0.1, and stirring at 60 ℃ for 24 hours to obtain a homogeneous solution. Introduction of N2The homogeneous solution was isolated from air and 0.05g of SrAl was added2O4·Tb3+(PES and SrAl)2O4·Tb3+The mass ratio of 10:0.05) is added into the homogeneous phase solution, a magnetic stirring device is controlled to stir the homogeneous phase solution and the ultrasonic vibration homogeneous phase solution at the rotating speed of 2500 rpm, the magnetic stirring and the ultrasonic vibration are stopped after 48 hours, the mixture is kept stand for 5 minutes to prepare a stable suspension solution, and then the suspension solution is taken out and scraped into a film by a film scraping machine, so that the self-luminous high-molecular ultrafiltration film is obtained.
Placing the just prepared self-luminous high-molecular ultrafiltration membrane in deionized water for more than 24 hours, and changing water once every 3 hours in the period; then, the contact angle, the anti-pollution condition and the intelligent response membrane pollution condition of the macromolecular ultrafiltration membrane in the embodiment and the comparative embodiment are tested in a comparative way, and the obtained macromolecular ultrafiltration membrane has the contact angle reduction rate of 5.17%, the effective anti-pollution time is prolonged by 38.7% and the luminous intensity of 27.9 Lux.
Example two: accurately weighing 10g of pretreatedDissolving polyether sulfone (PES) powder in 89.6g of Dimethylformamide (DMF) solvent, adding 0.6g of polyethylene glycol (PEG) according to the mass ratio of PES to PEG of 10:0.6, and stirring at 60 ℃ for 24 hours to obtain a homogeneous solution. Introduction of N2Isolating the homogeneous solution from air, 0.1g SrAl2O4·Tb3+(PES and SrAl)2O4·Tb3+The mass ratio of the components is 10:0.1), adding the mixture into the homogeneous phase solution, controlling a magnetic stirring device to stir the homogeneous phase solution and the ultrasonic vibration homogeneous phase solution at the rotation speed of 2500 rpm, stopping the magnetic stirring and the ultrasonic vibration after 48 hours, standing for 5 minutes to prepare a stable suspension solution, taking out the suspension solution, and scraping the suspension solution by a film scraping machine to form a film, thus obtaining the self-luminous polymeric ultrafiltration film.
Placing the just prepared self-luminous high-molecular ultrafiltration membrane in deionized water for more than 24 hours, and changing water once every 3 hours in the period; then, the contact angle, the anti-pollution condition and the intelligent response membrane pollution condition of the polymeric ultrafiltration membrane in the embodiment and the comparative embodiment are tested in a comparative way, and the decrease rate of the contact angle of the polymeric ultrafiltration membrane prepared in the embodiment is 5.38%, the effective anti-pollution time is prolonged by 38.81%, and the luminous intensity is 29.8 Lux.
Example three:
accurately weighing 10g of pretreated PES powder, dissolving the PES powder in 89.6g of DMF solvent, adding 0.8g of PEG (the mass ratio of PES to PEG is 10:0.8), and stirring at 60 ℃ for 24h to obtain a homogeneous solution; introduction of N2Isolating the homogeneous solution from air, 0.1g SrAl2O4·Tb3+(PES and SrAl)2O4·Tb3+The mass ratio of the components is 10:0.1), adding the mixture into the homogeneous phase solution, controlling a magnetic stirring device to stir the homogeneous phase solution and the ultrasonic vibration homogeneous phase solution at the rotation speed of 2500 rpm, stopping the magnetic stirring and the ultrasonic vibration after 48 hours, standing for 5 minutes to prepare a stable suspension solution, taking out the suspension solution, and scraping the suspension solution by a film scraping machine to form a film, thus obtaining the self-luminous polymeric ultrafiltration film.
Placing the just prepared self-luminous high-molecular ultrafiltration membrane in deionized water for more than 24 hours, and changing water once every 3 hours in the period; then, the contact angle, the anti-pollution condition and the intelligent response membrane pollution condition of the polymeric ultrafiltration membrane in the embodiment and the comparative embodiment are tested in a comparative way, and the decrease rate of the contact angle of the polymeric ultrafiltration membrane prepared in the embodiment is 5.21%, the effective anti-pollution time is prolonged by 35.78%, and the luminous intensity is 28.8 Lux.
Example four:
accurately weighing 10g of pretreated PES powder, dissolving the PES powder in 89.6g of DMF solvent, adding 1.0g of PEG (the mass ratio of PES to PEG is 10:1.0), and stirring at 60 ℃ for 24h to obtain a homogeneous solution; introduction of N2Isolating the homogeneous solution from air, 0.1g SrAl2O4·Tb3+(PES and SrAl)2O4·Tb3+The mass ratio of the components is 10:0.1), adding the mixture into the homogeneous phase solution, controlling a magnetic stirring device to stir the homogeneous phase solution and the ultrasonic vibration homogeneous phase solution at the rotation speed of 2500 rpm, stopping the magnetic stirring and the ultrasonic vibration after 48 hours, standing for 5 minutes to prepare a stable suspension solution, taking out the suspension solution, and scraping the suspension solution by a film scraping machine to form a film, thus obtaining the self-luminous polymeric ultrafiltration film.
Placing the just prepared self-luminous high-molecular ultrafiltration membrane in deionized water for more than 24 hours, and changing water once every 3 hours in the period; then, the contact angle, the anti-pollution condition and the intelligent response membrane pollution condition of the polymeric ultrafiltration membrane in the embodiment and the comparative embodiment are tested in a comparative way, and the decrease rate of the contact angle of the polymeric ultrafiltration membrane prepared in the embodiment is 5.44%, the effective anti-pollution time is prolonged by 35.78%, and the luminous intensity is 32.60 Lux.
Example five:
accurately weighing 10g of pretreated PES powder, dissolving the PES powder in 89.6g of DMF solvent, adding 0.6g of PEG pore-forming agent (the mass ratio of PES to PEG is 10:0.6), and stirring at 60 ℃ for 24 hours to obtain a homogeneous solution; introduction of N2Isolating the homogeneous solution from air, 0.15g SrAl2O4·Tb3+(PES and SrAl)2O4·Tb3+The mass ratio of 10:0.15) is added into the homogeneous phase solution, then a magnetic stirring device is controlled to stir the homogeneous phase solution and the ultrasonic vibration homogeneous phase solution at the rotating speed of 2500 rpm, the magnetic stirring and the ultrasonic vibration are stopped after 48 hours, the mixture is kept stand for 5 minutes to prepare a stable suspension solution, and then the suspension solution is taken out and utilized by a film scraping machineScraping to form a membrane, and obtaining the self-luminous macromolecular ultrafiltration membrane.
Placing the just prepared self-luminous high-molecular ultrafiltration membrane in deionized water for more than 24 hours, and changing water once every 3 hours in the period; then, the contact angle, the pollution resistance and the intelligent response membrane pollution of the polymeric ultrafiltration membrane in the embodiment and the comparative embodiment are tested in a comparative way, so that the decrease rate of the contact angle of the polymeric ultrafiltration membrane prepared in the embodiment is 8.63%, the effective pollution resistance time is prolonged by 58.31%, and the luminous intensity is 45.28 Lux.
EXAMPLE six
Accurately weighing 10g of pretreated PES powder, dissolving the PES powder in 89.6g of DMF solvent, adding 0.8g of PEG pore-forming agent (the mass ratio of PES to PEG is 10:0.8), and stirring at 60 ℃ for 24 hours to obtain a homogeneous solution; introduction of N2Isolating the homogeneous solution from air, 0.15g SrAl2O4·Tb3+(PES and SrAl)2O4·Tb3+The mass ratio of 10:0.15) is added into the homogeneous phase solution, a magnetic stirring device is controlled to stir the homogeneous phase solution and the ultrasonic vibration homogeneous phase solution at the rotation speed of 2500 rpm, the magnetic stirring and the ultrasonic vibration are stopped after 48 hours, the mixture is kept stand for 5 minutes to prepare a stable suspension solution, and then the suspension solution is taken out and scraped into a film by a film scraping machine, so that the self-luminous high-molecular ultrafiltration film is obtained.
Placing the just prepared self-luminous high-molecular ultrafiltration membrane in deionized water for more than 24 hours, and changing water once every 3 hours in the period; then, the contact angle, the anti-pollution condition and the intelligent response membrane pollution condition of the polymeric ultrafiltration membrane in the embodiment and the comparative embodiment are tested in a comparative way, and the decrease rate of the contact angle of the polymeric ultrafiltration membrane prepared in the embodiment is 8.73%, the effective anti-pollution time is prolonged by 57.42%, and the luminous intensity is 43.75 Lux.
EXAMPLE seven
Accurately weighing 10g of pretreated PES powder, dissolving the PES powder in 89.6g of DMF solvent, adding 1.0g of PEG pore-forming agent (the mass ratio of PES to PEG is 10:1.0), and stirring at 60 ℃ for 24 hours to obtain a homogeneous solution; introduction of N2Isolating the homogeneous solution from air, 0.15g SrAl2O4·Tb3+(PES and SrAl)2O4·Tb3+The mass ratio of 10:0.15) is added into the homogeneous phase solution, a magnetic stirring device is controlled to stir the homogeneous phase solution and the ultrasonic vibration homogeneous phase solution at the rotation speed of 2500 rpm, the magnetic stirring and the ultrasonic vibration are stopped after 48 hours, the mixture is kept stand for 5 minutes to prepare a stable suspension solution, and then the suspension solution is taken out and scraped into a film by a film scraping machine, so that the self-luminous high-molecular ultrafiltration film is obtained.
Placing the just prepared self-luminous high-molecular ultrafiltration membrane in deionized water for more than 24 hours, and changing water once every 3 hours in the period; then, the contact angle, the pollution resistance and the intelligent response membrane pollution of the polymeric ultrafiltration membrane in the embodiment and the comparative embodiment are tested in a comparative way, so that the decrease rate of the contact angle of the polymeric ultrafiltration membrane prepared in the embodiment is 8.64%, the effective pollution resistance time is prolonged by 54.32%, and the luminous intensity is 44.61 Lux.
Example eight
Accurately weighing 10g of pretreated PES powder, dissolving the PES powder in 89.6g of DMF solvent, adding 0.6g of PEG pore-forming agent (the mass ratio of PES to PEG is 10:0.6), and stirring at 60 ℃ for 24 hours to obtain a homogeneous solution; introduction of N2Isolating the homogeneous solution from air, 0.2g SrAl2O4·Tb3+(PES and SrAl)2O4·Tb3+The mass ratio of the components is 10:0.2), stirring the homogeneous solution and the ultrasonic vibration homogeneous solution at the rotation speed of 2500 rpm by controlling a magnetic stirring device, stopping magnetic stirring and ultrasonic vibration after 48 hours, standing for 5 minutes to prepare a stable suspension solution, taking out the suspension solution, and scraping the suspension solution by using a film scraping machine to form a film, thus obtaining the self-luminous polymeric ultrafiltration film.
Placing the just prepared self-luminous high-molecular ultrafiltration membrane in deionized water for more than 24 hours, and changing water once every 3 hours in the period; then, the contact angle, the pollution resistance and the intelligent response membrane pollution of the polymeric ultrafiltration membrane in the embodiment and the comparative embodiment are tested in a comparative way, so that the decrease rate of the contact angle of the polymeric ultrafiltration membrane prepared in the embodiment is 10.98%, the effective pollution resistance time is prolonged by 74.80%, and the luminous intensity is 71.33 Lux.
Example nine
Accurately weighing 10g of pretreated PES powder, and dissolving in89.6g of DMF solvent, adding 0.8g of PEG (the mass ratio of PES to PEG is 10:0.8), and stirring at 60 ℃ for 24 hours to obtain a homogeneous solution; introduction of N2Isolating the homogeneous solution from air, 0.2g SrAl2O4·Tb3+(PES and SrAl)2O4·Tb3+The mass ratio of the components is 10:0.2), stirring the homogeneous solution and the ultrasonic vibration homogeneous solution at the rotation speed of 2500 rpm by controlling a magnetic stirring device, stopping magnetic stirring and ultrasonic vibration after 48 hours, standing for 5 minutes to prepare a stable suspension solution, taking out the suspension solution, and scraping the suspension solution by using a film scraping machine to form a film, thus obtaining the self-luminous polymeric ultrafiltration film.
Placing the just prepared self-luminous high-molecular ultrafiltration membrane in deionized water for more than 24 hours, and changing water once every 3 hours in the period; then, the contact angle, the pollution resistance and the intelligent response membrane pollution of the polymeric ultrafiltration membrane in the embodiment and the comparative embodiment are tested in a comparative way, so that the decrease rate of the contact angle of the polymeric ultrafiltration membrane prepared in the embodiment is 11.04%, the effective pollution resistance time is prolonged by 78.31%, and the luminous intensity is 71.38 Lux.
Example ten
Accurately weighing 10g of pretreated PES powder, dissolving the PES powder in 89.6g of DMF solvent, adding 1.0g of PEG (the mass ratio of PES to PEG is 10:1.0), and stirring at 60 ℃ for 24h to obtain a homogeneous solution; introduction of N2Isolating the homogeneous solution from air, 0.2g SrAl2O4·Tb3+(PES and SrAl)2O4·Tb3+The mass ratio of the components is 10:0.2), then a magnetic stirring device is controlled to stir the homogeneous solution and the ultrasonic vibration homogeneous solution at the rotation speed of 2500 rpm, after 48 hours, the magnetic stirring and the ultrasonic vibration are stopped, the mixture is kept stand for 5 minutes to prepare a stable suspension solution, and then the suspension solution is taken out and scraped into a membrane by a membrane scraping machine, so that the self-luminous high-molecular ultrafiltration membrane is obtained.
Placing the just prepared self-luminous high-molecular ultrafiltration membrane in deionized water for more than 24 hours, and changing water once every 3 hours in the period; then, the contact angle, the pollution resistance and the intelligent response membrane pollution of the polymeric ultrafiltration membrane in the embodiment and the comparative embodiment are tested in a comparative way, so that the decrease rate of the contact angle of the polymeric ultrafiltration membrane prepared in the embodiment is 12.31%, the effective pollution resistance time is prolonged by 77.61%, and the luminous intensity is 72.65 Lux.
In specific implementation, the mass ratio of the polymer raw material to the rare earth aluminate self-luminous material can be 10: 0.05-10: other values within 0.2; the mass ratio of the polymer raw material to the pore-forming agent can be 10: 0.1-10: other values within 1; the dosage of the rare earth aluminate self-luminous material in the homogeneous solution can also be other values within the range of 0.1-10 wt%.
The rare earth aluminate self-luminous material SrAl in the above embodiment2O4·Tb3+Can also consist of SrAl2O4·Dy3+Or SrAl2O4·Eu2+Replacement; the polyethersulfones in the above examples may also be replaced with polyvinylidene fluoride or polytetrafluoroethylene.
The N, N-dimethylformamide in the above-described examples may be further replaced by N-methylpyrrolidone, N-dimethylacetamide, or dimethylsulfoxide or by two or more of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, and dimethylsulfoxide.
In addition, the suspension liquid in the above embodiments is scraped into a film by a film scraping machine, and an extruder can be used instead to prepare a hollow film.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.

Claims (8)

1. A preparation method of a self-luminous high-molecular ultrafiltration membrane is characterized by comprising the following steps: the method comprises the following steps: adding a rare earth aluminate self-luminous material into a homogeneous solution containing a film-making polymer raw material and a pore-forming agent under an anaerobic condition, uniformly dispersing the rare earth aluminate self-luminous material into the homogeneous solution by stirring and ultrasonic vibration to prepare a stable suspension solution, and preparing a flat ultrafiltration membrane or a hollow ultrafiltration membrane by using the prepared suspension solution;
the mass ratio of the high molecular raw material to the rare earth aluminate self-luminous material is 10: 0.05-10: 0.2; the mass ratio of the high polymer raw material to the pore-forming agent is 10: 0.1-10: 1; the dosage of the rare earth aluminate self-luminous material in the homogeneous solution is 0.1-10 wt%.
2. The method for preparing the self-luminous high-molecular ultrafiltration membrane according to claim 1, wherein the method comprises the following steps: the mass ratio of the high polymer raw material to the pore-forming agent is 10: 0.1-10: 1; the dosage of the rare earth aluminate self-luminous material in the homogeneous solution is 1.6-4 wt%.
3. The method for preparing the self-luminous high-molecular ultrafiltration membrane according to claim 2, wherein the method comprises the following steps: the mass ratio of the high molecular raw material to the rare earth aluminate self-luminous material is 10:0.15, the dosage of the rare earth aluminate self-luminous material in the homogeneous solution is 2.4 wt% or 3.2 wt%.
4. The method for preparing a self-luminous high-molecular ultrafiltration membrane according to claim 1, 2 or 3, wherein: the rare earth aluminate self-luminous material is SrAl2O4·Tb3+、SrAl2O4·Dy3+And SrAl2O4·Eu2+One of (1); the polymer raw material is one of polyvinylidene fluoride, polyether sulfone and polytetrafluoroethylene.
5. The method for preparing a self-luminous high-molecular ultrafiltration membrane according to claim 1, 2 or 3, wherein: the solvent of the homogeneous solution is one or more of N-methyl pyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide.
6. The method for preparing a self-luminous high-molecular ultrafiltration membrane according to claim 1, 2 or 3, wherein: the pore-forming agent is polyethylene glycol.
7. The method for preparing a self-luminous high-molecular ultrafiltration membrane according to claim 1, 2 or 3, wherein: the weight average molecular weight of the high polymer raw material is 20000-200000.
8. A self-luminous polymeric ultrafiltration membrane produced by the production method according to any one of claims 1 to 7.
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