CN114768560A - Polydimethylsiloxane/polysulfone ultrathin composite membrane, preparation method and application - Google Patents
Polydimethylsiloxane/polysulfone ultrathin composite membrane, preparation method and application Download PDFInfo
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Classifications
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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
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- 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
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- 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
- B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the technical field of gas-liquid two-phase gas separation membranes, and relates to a polydimethylsiloxane/polysulfone ultrathin composite membrane, a preparation method and application thereof. The invention uses a phase inversion method to prepare polysulfone base membrane: dissolving polysulfone in N, N-dimethylacetamide with a mass fraction of about 14-15%, scraping the membrane, and soaking the membrane in deionized water for at least 24 h. And dissolving PDMS in isooctane, and preparing the composite membrane by adopting a wet membrane dip-coating method. And (3) placing the coated membrane in an oven at 85 ℃ for 2h to complete crosslinking to obtain the composite membrane. The invention is applied to preparing high CO2/O2SelectingThe composite membrane material has the advantages of good performance, high gas permeability and good pollution resistance. The invention has simple integral membrane preparation process and low raw material price, compared with the polysulfone membrane, the membrane material coated by the silicon rubber greatly reduces the membrane pollution speed and prolongs the service life of the membrane. The prepared composite membrane can resist high temperature and high pressure and has great application potential.
Description
Technical Field
The present invention belongs to a gas-liquid two-phase gas separation membrane for separating gas from liquidThe composite membrane is a composite membrane which takes polysulfone as a porous supporting layer as a base membrane and takes a polydimethylsiloxane compact membrane as a separation layer, and can act on a gas-liquid phase interface to realize gas and liquid O2And CO2The exchange of (2).
Background
Beginning in 1829, human exploration for gas membrane separation processes has been conducted for over a century. China began to research gas separation membranes and related applications thereof in the 80 s of the 20 th century. The gas separation membrane is a process of enriching and separating different gases on two sides of the membrane by utilizing the difference of permeation rates of gas molecules in the membrane under the drive of certain pressure. The process has the characteristics of low energy consumption, no pollution, capability of finishing the enrichment and separation of two gases without any operation and the like, and is widely applied to various industries, such as the collection of hydrogen in synthetic ammonia tail gas, the enrichment of oxygen in air, the separation of gases such as hydrogen, carbon monoxide and the like from petroleum cracking mixed gas, the capture of carbon dioxide, the recovery of VOCs and the like. Membrane separation technology has been widely recognized as one of the most promising new separation technologies in the future.
The ideal gas separation membrane material has good gas permeability, proper gas selectivity and pollution resistance, and simultaneously prevents the phenomena of liquid leakage and the like generated in the using process. However, the gas separation membrane simultaneously faces a plurality of conditions in practical application environment, such as membrane pollution and aging prevention, and the development of the membrane separation technology is always restricted. Meanwhile, the membrane separation technology is continuously applied in new fields, such as preparation of a membrane which is positioned at a gas-liquid phase interface and used as a two-phase separated interface and has good gas permeability, proper gas selectivity, pollution resistance and other performances, and challenges are provided for the whole membrane science and technical disciplines. The current membranes used for gas-liquid phase interfaces and meeting the above requirements mainly use poly-4-methyl-1-pentene (PMP) membranes, and the production chain (propylene dimer-PMP resin-PMP hollow fiber membranes) of the material poly-4-methyl-1-pentene (PMP) is monopolized by foreign companies and the preparation cost is high. It is therefore highly desirable to explore new gas separation membrane materials to promote the growth of this area.
Polydimethylsiloxane (PDMS) is a high molecular polymer with a siloxane structure as a main chain, and has an empirical formula of (C2H6OSi) n. The organic silicon material has optical transparency, is considered to be non-toxic and inert under general conditions, is a hydrophobic organic silicon material widely used at present, and has the following structure.
Because of its excellent physical properties, polydimethylsiloxane is widely used in food, chemical, electronic products, etc. The existence of siloxane bonds leads to a high level of viscoelasticity of the flexible polymer chains, and a great deal of research has been carried out to show that PDMS materials have high gas permeability and superior material stability. Higher gas permeability corresponds to higher CO2And O2The requirement of special membrane material of infiltration volume, material stability again is favorable to its long-term existence in the environment of gas-liquid two-phase contact, can not release harmful substance, causes the harm to the liquid phase solution. And secondly, the PDMS material is independently produced in China and is low in price, and compared with PMP materials which are technically monopolized in China and are high in price by foreign companies serving as core technologies, the excellent performance of the PDMS material gradually draws attention of people.
But the application of the PDMS is greatly influenced by the limitations of the PDMS material itself, especially the strong hydrophobicity and the low mechanical strength. The preparation of the composite membrane is relatively simple, and the composite membrane is made of two materials, so that the compact skin layer can prevent the liquid leakage, and has good gas permeability and high CO content2/O2The polysulfone base membrane has good mechanical supporting performance, can be regulated and controlled according to actual conditions, overcomes the problems of difficulty in preparing PMP gradient micropores, liquid leakage and the like, realizes national autonomous production, and has great advantage in price.
Disclosure of Invention
Aiming at the application limitation of the PDMS material, the invention provides a means with simple process and low cost, and the polysulfone is used as a base film to carry the PDMS material, wherein the polysulfone used as the base film is safe and nontoxic, can be directly contacted with various solutions or mixtures, and is not easy to decompose under the conventional high-temperature high-pressure sterilization environment. The compactness of the PDMS material can prevent the problems of liquid leakage, air embolism and the like. The invention adopts a composite membrane form, the strong mechanical support of the base membrane effectively solves the problem that PDMS is difficult to form a membrane, the existence of the coating obviously improves the pollution resistance of the polysulfone membrane, and simultaneously realizes better gas selectivity.
The technical scheme of the invention is as follows:
a polydimethylsiloxane/polysulfone ultrathin composite membrane comprises a polysulfone base membrane and a coating mode; the base film of the composite film is made of polysulfone material, and the coating layer is made of PDMS material; coating the prepared membrane liquid on the prepared polysulfone membrane; the thickness of the PDMS compact separation layer in the polydimethylsiloxane/polysulfone ultrathin composite membrane can be regulated and controlled to be 0.4-5 mu m according to requirements, and the whole thickness of the polydimethylsiloxane/polysulfone ultrathin composite membrane can be regulated and controlled to be 100-150 mu m. Wherein the polysulfone based membrane is in a loose finger-shaped hole state, the inner cavity of the polysulfone based membrane is larger, the surface of the polysulfone based membrane is distributed with micropores, and the thickness of the PDMS coating is increased along with the increase of the concentration of the coating liquid.
A method for preparing a polydimethylsiloxane/polysulfone ultrathin composite membrane comprises the following steps:
preparation of a PSF porous supporting base membrane: preparing a PSF porous supporting base membrane by adopting a phase conversion method; preparing a membrane solution by taking PSF as a base membrane material, polyethylene glycol as an additive and N, N-dimethylacetamide as a solvent, wherein the mass ratio of PSF to PEG to DMAc in the membrane solution is 3: 2: 15, stirring and dissolving at the temperature of 65-75 ℃; a flat film scraper and a film scraper are used for scraping the film, the film after the scraping is finished is placed in deionized water for at least 24 hours, and finally, phase splitting and curing are carried out to generate a PSF porous supporting base film;
coating of PDMS dense separation layer: preparing a polydimethylsiloxane/polysulfone ultrathin composite membrane by using a wet membrane dip-coating method; firstly, preparing a coating liquid, taking a PDMS (polydimethylsiloxane) toluene solution with the mass fraction of 35% as a solute and isooctane as a solvent, calculating the adding mass of the PDMS toluene solution and the isooctane according to the required PDMS concentration in the coating liquid, stirring until the PDMS toluene solution and the isooctane are completely dissolved, and adding a cross-linking agent and a catalyst; wherein the mass ratio of the cross-linking agent to the PDMS is 1: 10, the mass ratio of the catalyst to the PDMS is 1: 100, respectively; to prevent local crosslinking, the crosslinking agent and the catalyst should be added slowly drop by drop; standing and defoaming the coating solution, pouring the coating solution into a tank, and immersing the smooth surface of the PSF porous support base film into the coating solution to enable the coating solution to be evenly and uniformly coated on the surface of the PSF base film, wherein the contact time of the film and the coating solution is 2-3 s; and drying the coated membrane at 85 ℃ for 2h, and flattening to obtain the polydimethylsiloxane/polysulfone ultrathin composite membrane.
The polydimethylsiloxane/polysulfone ultrathin composite membrane is applied to a gas-liquid phase interface and is used as a membrane material for gas exchange.
The beneficial effect of this application: the invention is applied to preparing CO2/O2The composite membrane material has high selectivity, stable chemical performance and pollution resistance. The invention has simple integral membrane preparation process, improves the limitation of lower mechanical strength of coating materials by selecting polysulfone with higher mechanical strength as a base membrane, prepares a composite membrane with an ultrathin selection layer and greatly improves the gas flux. Meanwhile, the existence of the compact skin layer can prevent the problems of air embolism and feed liquid leakage. Polysulfone and PDMS are non-toxic and will not be affected when contacting the liquid phase. The technology enhances the mechanical strength of PDMS while keeping the original property of PDMS, and improves the adsorption performance of polysulfone materials. Meanwhile, two materials with lower price are selected, the preparation cost of the special film material is greatly reduced, the application range of the equipment is popularized, the short plate of the high-end film material manufacturing industry in China is effectively supplemented, the manufacturing technology of the special film material is completely matched with the major strategic requirements of the national public safety guarantee, the preparation of the downstream related medical industry is recommended, the independent control of high-end medical equipment is realized, for example, the monopoly of the oxygen composite film foreign technology for ECMO is broken, and powerful guarantee is provided for the health and life safety of people.
Drawings
FIG. 1 is a scanning electron microscope image of polysulfone-based membranes and PDMS/PSF composite membranes. (a) FIG. is a cross-section of a polysulfone based film; (b) the figure is an enlarged view of the upper surface of the cross section of the prepared PDMS/PSF composite membrane; (c) FIG. is a top view of a polysulfone based film; (d) the figure is the upper surface of the PDMS/PSF composite membrane.
FIG. 2 is an energy dispersive spectrometer spectrum of the prepared PDMS/PSF composite film.
FIG. 3 shows the contact angle measurement results of polysulfone-based membranes and PDMS/PSF composite membranes prepared therefrom. (a) The figure is the result of measuring antenna of polysulfone basal membrane; (b) the graph shows the contact angle measurement result of the PDMS/PSF composite film.
FIG. 4 shows a PDMS/PSF composite membrane and a PDMS/PSF composite membrane CO after high-temperature and high-pressure sterilization2Gas permeability and CO2/O2The selectivity is shown as a function of the coating solution concentration. (a) The figure is a PDMS/PSF composite membrane CO2Gas permeability and CO2/O2The selectivity varies with the concentration of the coating solution; (b) the figure shows a PDMS/PSF composite membrane CO after high-temperature and high-pressure sterilization treatment2Gas permeability and CO2/O2The selectivity is shown as a function of the coating solution concentration.
FIG. 5 is a schematic diagram showing the change in the concentration of the coating liquid for protein adsorption amount in the bovine serum albumin adsorption experiment.
Detailed Description
In order to make the technical solutions and advantages clearer, the technical solutions will be described clearly and completely by way of examples.
Example 1:
PSF (P-3500) was purchased from Suwei (USA) and dried in an oven at 105 ℃ for 24 hours after being washed with deionized water before use. And preparing the PSF base film by adopting a dry-wet phase conversion method. PSF is used as a base membrane material, polyethylene glycol is used as an additive, and N, N-dimethylacetamide is used as a solvent to prepare a membrane liquid. Weighing 9g of dried PSF material, 6g of PEG (Mn400) and 45g of DMAC (dimethylacetamide) and mixing to form a basement membrane liquid, wherein the mass ratio of each component of the membrane liquid is 3/2/15(PSF/PEG/DMAc), adding a magnetic stirrer, sealing and stirring. Stirring at 60 ℃ until PSF is completely dissolved to obtain a membrane liquid. The film is scraped by using a flat film scraper and a film scraping knife, a glass plate is preheated in an air-blowing drying oven at 40 ℃ in advance and then is fixed on the film scraper, the film scraping knife is placed on the glass plate, and the thickness of the scraper is adjusted to be 250 mu m. Pouring the membrane liquid into a material groove of a membrane scraping knife, starting a membrane scraping machine to enable the membrane scraping knife to move on a glass plate at a constant speed, uniformly spreading the membrane liquid on the surface of the glass plate, immediately placing the glass plate coated with the membrane liquid into deionized water for at least 24 hours, slowly placing the glass plate in the process without exciting water marks, disturbing the phase conversion process of the membrane surface due to the existence of the water marks, forming ripple-shaped marks on the membrane surface, and affecting related performances. And finally, phase splitting and curing to generate the PSF base membrane after the solvent of the membrane liquid is dissolved in water. The environmental humidity needs to be strictly controlled to be 30% -40% in the preparation process of the base film, if the air humidity is higher, the polysulfone material is subjected to incomplete phase transformation in the air, the coating process of the base film and the PDMS layer can be influenced, and the phenomenon of pore permeation is caused.
Preparing a PDMS composite film: PDMS used in this work was from Wacker Chemicals, Inc. and was matched with a solution of low molecular weight methyl hydrosilicone rubber and chloroplatinic acid isopropyl alcohol as a catalyst and a crosslinking agent, respectively. The PDMS composite film was prepared using a wet film dip coating method. Firstly, preparing a coating liquid, taking a PDMS (polydimethylsiloxane) toluene solution with the mass fraction of 35% as a solute and isooctane as a solvent, calculating the mass of the PDMS solution and the isooctane according to the expected PDMS concentration and the total mass of the coating liquid, and adding the mass of a cross-linking agent and the PDMS into a reagent bottle, wherein the mass ratio of the cross-linking agent to the PDMS is 1: 10, the mass ratio of the catalyst to the PDMS is 1: 100. the composite membrane with the concentration of 2 percent of coating solution is prepared, and the dosage of PDMS toluene solution is 3.428g, the dosage of low molecular weight methyl hydrogen-containing silicon rubber, namely the cross-linking agent, is 0.12g, the dosage of chloroplatinic acid isopropanol solution, namely the catalyst, is 0.012g, and the dosage of isooctane is 56.44 g. After PDMS is completely dissolved in isooctane, a crosslinking agent is dripped by using a difference method, and attention needs to be paid to the fact that each dripping needs to wait for a moment to uniformly mix the solution, so that the phenomenon of implosion caused by overhigh local concentration is prevented. The catalyst addition step is the same as for the crosslinker. Standing for 5min, and coating. Wiping water drops on the surface of the film by using filter paper, standing and defoaming the coating solution, pouring the coating solution into a tank, carefully immersing the smooth surface of the PSF base film into the coating solution, and flatly and uniformly coating the coating solution on the surface of the PSF base film, wherein the contact time between the film and the coating solution is 2-3 s. And (3) drying the coated membrane in an oven at 85 ℃ for 2h, cooling the membrane after the PDMS material finishes the crosslinking process, and flattening to obtain the PDMS composite membrane.
In order to explore the microstructure of the prepared material, the microstructure of the PDMS/PSF composite film prepared in example 1, including the surface morphology and the cross-sectional morphology, was observed using a scanning electron microscope. The membrane samples were fixed on a conductive gel and gold sprayed on the surface prior to characterization. The cross section of the film sample is frozen and broken in liquid nitrogen to ensure sharp brittle fracture, and the fracture surface is kept flat without forceps holding traces. All samples were subjected to current sputtering for a fixed time before observation to produce a thin gold conductivity. SEM analysis also provided the thickness of the surface and bottom layers and the phase change formed microporous structure.
Since the selective layer occupies a small thickness of the whole membrane, a PDMS characteristic peak cannot be generated or only a small characteristic peak is generated by using an infrared spectroscopy, so that the PDMS/PSF composite membrane prepared in example 1 is analyzed by using an elemental analysis method to know whether the PDMS material forms a dense layer on the surface of the polysulfone.
The surface properties of a material are typically evaluated by measuring the contact angle of a drop of water. The water contact angle of the membrane can directly reflect the strength of hydrophilicity and hydrophobicity. The water contact angle of the PDMS/PSF composite film prepared in example 1 was measured using a contact angle meter with a camera. Fixing the PDMS composite membrane to be detected on the surface of a device platform by using an adhesive tape, dripping deionized water on the surface of the membrane by using a micro sampler, photographing, and obtaining water contact angle data through correlation calculation. The experiments were performed at room temperature. To ensure the accuracy of the experimental results, all contact angle test results were determined by averaging the measurements at three different locations on each sample surface.
Example 2:
in order to measure the pure gas permeability of the prepared composite membrane, a PDMS/PSF composite membrane which is prepared by the method in the embodiment 1 and has 2% -8% of total membrane coating liquid concentration and has 7 membrane coating liquid concentrations is taken as an experimental material, and the measurement is not carried out because the surface of the membrane with the concentration of 1% has defects. The permeability of pure gas is measured by a self-made stainless steel membrane permeation device, a membrane pool is pressurized from the coating side, the transmembrane pressure of a composite membrane is 0.1-0.5 MPa, the temperature of a water bath is controlled to be constant, and the humidity is controlled to be 35-40% by a dehumidifier. The prepared composite membrane is embedded in a stainless steel die set, and the membrane area is kept constant.Pure gas is introduced to purge the upper gas circuit and the lower gas circuit for about 10min, so that the rest gas in the gas circuits is completely exhausted, and the permeability of carbon dioxide and oxygen gas is respectively measured. After the gas flow is stabilized, the prepared membrane is placed in a soap bubble flowmeter to measure the gas permeation volume flow. J is a unit ofiWith a GPU (1 GPU-10)-6cm3/cm2s cmHg) is determined by the following equation:
wherein J is gas permeability, GPU; Δ V is the volume of gas passing through the flowmeter and is 3cm3(ii) a T is room temperature 25 ℃; a is the membrane area calculated to be 11.34cm2(ii) a t is the time, s, of the gas passing through the flowmeter; Δ p is the test differential pressure, MPa. Each data was run in 3 replicates and averaged.
Example 3:
in order to measure the membrane material anti-membrane contamination performance, the PDMS/PSF composite membrane with 0% -8% of total 9 membrane coating liquid concentrations prepared by the method in example 1 is taken as an experimental material, each membrane coating liquid concentration membrane sample is respectively placed into a centrifuge tube, a certain amount of normal saline is added, after incubation in a constant temperature water bath at 37 ℃ for a period of time, the normal saline is poured out, a certain amount of PBS buffer solution is added, and after incubation in a constant temperature water bath at 37 ℃ for a period of time, the buffer solution is poured out. The membrane was taken out and soaked with 1mg/mL BSA solution at 37 ℃ for 2h, then washed with PBS solution, and then soaked in the same volume of 2 wt% SDS solution, and gently stirred at 37 ℃ to elute the adsorbed protein. The elution rate of the protein adsorbed on the surface of the membrane can reach more than 95%, and the eluted solution is measured by an ultraviolet spectrophotometer, and BSA solutions with different concentration gradients are used for drawing a standard curve. Comparing the absorbance values of the samples with the standard curve, the concentration of the protein solution (mu g/cm) after elution of different membrane samples can be determined2) Thus obtaining the protein adsorption quantity of the membrane surface. The calculation formula is as follows
Wherein Pr is the protein adsorption amount, mu g/cm2；CBSAFor the BSA concentration of the eluted solution, μ g/ml, against a BSA standard curve; vSDSVolume of SDS solution; a. themIs the membrane area. The above experiment was repeated three times and the final results were averaged.
In order to observe the appearance of the base film prepared in example 1, the base film was quenched with liquid nitrogen, subjected to a gold spraying operation, and observed with a scanning electron microscope. As shown in fig. 1(a), the PSF base film is thick, having a total thickness of about 100 μm. The overall shape is loose finger-shaped holes. After phase change, the thickness of the base film is significantly less than the thickness adjusted by the doctor blade. The results show that the phase change of the film in the deionized water phase is complete. After replacement, most of the solvent in the membrane is dissolved in water. The pore at the lower end of the composite membrane is large and has a large cavity structure. Presumably, this is due to the eventual contact with deionized water during the phase change. As shown in fig. 1(c), as can be seen from the enlarged view of the upper surface, the surface of the polysulfone membrane is rough and has a pore structure, and no large ripples exist, so that the structure is favorable for being tightly combined with the PDMS material, and the subsequent coating process is convenient.
Observing the apparent morphology of the PDMS/PSF composite membrane prepared in the embodiment 1, quenching the whole composite membrane with liquid nitrogen, spraying gold, and observing with a scanning electron microscope. As shown in FIG. 1(b), the overall cross-sectional morphology of the composite membrane is not much different from that of the basement membrane, but the upper surface thereof has a dense cortex having a thickness of about 0.6 μm, and the cortex is bonded to the upper portion of the basement membrane. As can be seen from FIG. 1(d), the surface of the composite membrane after PDMS coating is smooth and flat, has no defect and coarse structure, and the surface roughness thereof is obviously different from the surface of polysulfone material.
In order to determine whether the components on the surface of the base film are PDMS components, the surface of the PDMS/PSF composite film prepared in example 1 was tested by infrared spectroscopy, but the PDMS layer occupies a small amount of the composite film, and the infrared spectroscopy test result cannot show the characteristic peak of the PDMS material. The surface of the PDMS/PSF composite film prepared in example 1 was analyzed by EDS spectroscopy, the EDS spectrum of the composite film is shown in fig. 2, and the characterization results are shown in table 1. As can be seen from the EDS characterization results, the prepared composite film contains C, O and Si elements in a high proportion, and contains S elements in a small amount. Wherein, the silicon element accounts for the maximum mass percent of the composite film and is 46.16 percent. In terms of atomic percentage, C atoms are the framework of an organic substance, accounting for 41.45%. Since polysulfone does not contain Si element, the Si element of the composite film is considered to originate from the PDMS coating layer. From the results of EDS characterization, PDMS has been successfully coated on the PSF base film surface.
TABLE 1 elemental analysis results of composite films
The hydrophilicity and hydrophobicity of the surface of the membrane material have great influence on the property of the membrane material. This work measured the water contact angle between the PSF-based film material and the PDMS/PSF composite film prepared in example 1. The water contact angle between the PSF-based membrane surface and the composite membrane surface is shown in fig. 3. In general, surfaces with a contact angle greater than 90 ° may be considered hydrophobic surfaces. The test result shows that the contact angle of the polysulfone material is 45.8 degrees, the hydrophobicity of the PDMS coating film is greatly increased to 105 degrees, and the original hydrophilic performance of the PDMS coating film is changed. For the operating environment of the membrane, the high hydrophilicity can cause the leakage problem of the feed liquid in the use process, thereby reducing the service life of the membrane and ensuring the long-term operation of the product. The coating of PDMS will change the hydrophilicity and hydrophobicity of the membrane surface and solve the feed liquid leakage problem to a certain extent.
FIG. 4(a) is a graph showing the gas transmission and CO of a PDMS/PSF composite membrane prepared by the method of example 1, wherein the PDMS/PSF composite membrane has a total concentration of 7 coating solutions of 2% -8%2/O2The selectivity graph shows that the highest permeability reaches about 2900GPU, and as the membrane thickness is increased, the permeability is increased, and CO is added2/O2The selectivity is always kept around 6.1. The surface of the 1% concentration composite membrane has defects, so that the 1% concentration composite membrane has almost no selectivity, and compared with other concentration membranes, the 8% concentration composite membrane has reduced air permeability due to larger thickness, and is not suitable for environments with larger required air permeability. To ensure the filmIs gas-permeable and is free of defects, and thus the thickness of the dense separation layer is adjusted to 0.4 to 5 μm as required. FIG. 4(b) is the gas permeability and CO of the prepared composite membrane after high temperature and high pressure sterilization2/O2The selectivity graph shows that the membrane permeation of each concentration and CO are reduced to 4 except that the composite membrane permeation of 2 percent concentration is reduced to 2400GPU and the selectivity is reduced to 42/O2The selectivity is consistent with that of a sterilization membrane. The composite film has better heat resistance, can bear higher temperature and keep the structure unchanged.
And (3) testing the protein adsorption performance of the composite membrane material: after two times of incubation by physiological saline and PBS buffer solution, the material is placed in protein for incubation for 2 hours, the absorbance of the material is measured, and the protein adsorption capacity of the material is obtained according to a standard curve drawn in advance. The results of measuring the protein adsorption amount of the PDMS/PSF composite membrane prepared by the method of example 1 and having a total of 9 coating liquid concentrations of 0% to 8% are shown in FIG. 5. It can be seen that the protein adsorption amount of the PDMS-based membrane after coating is obviously reduced, and the protein adsorption amount is reduced along with the increase of the concentration of PDMS. It can be seen that the increase of PDMS concentration can enhance the anti-pollution performance of the membrane material, thereby prolonging the service life of the composite membrane. The quality of the protein adsorbed after the material contacts the protein solution has a decisive effect on the formation of a membrane pollution layer, and the less the quality of the adsorbed protein is, the better the anti-pollution effect of the material is.
The preparation method of the polydimethylsiloxane/polysulfone heat-resistant ultrathin composite membrane provided by the invention respectively regulates and controls the base membrane and the selective layer by adopting a composite membrane form. The existence of the base membrane provides mechanical support for coating the ultrathin PDMS layer, and the existence of the PDMS layer makes up the defect of low selectivity for the polysulfone base membrane. Meanwhile, the air permeability, the hydrophilic and hydrophobic performance and the pollution resistance of the prepared composite membrane meet various standards through tests. And the used base film and coating material are relatively cheap, can be produced at home by oneself, and have good practicability and economy.
Claims (3)
1. A polydimethylsiloxane/polysulfone ultrathin composite membrane is characterized by comprising a PDMS compact separation layer and a PSF porous supporting base membrane; the thickness of the PDMS compact separation layer in the polydimethylsiloxane/polysulfone ultrathin composite membrane can be regulated and controlled to be 0.4-5 mu m according to requirements, and the whole thickness of the polydimethylsiloxane/polysulfone ultrathin composite membrane can be regulated and controlled to be 100-150 mu m.
2. A method for preparing a polydimethylsiloxane/polysulfone ultrathin composite membrane is characterized by comprising the following steps:
preparing a PSF porous supporting base membrane: preparing a PSF porous supporting base membrane by adopting a phase conversion method; preparing a membrane solution by taking PSF as a base membrane material, polyethylene glycol as an additive and N, N-dimethylacetamide as a solvent, wherein the mass ratio of PSF to PEG to DMAc in the membrane solution is 3: 2: 15, stirring and dissolving at the temperature of 65-75 ℃; a flat film scraper and a film scraper are used for scraping the film, the film after the scraping is finished is placed in deionized water for at least 24 hours, and finally phase splitting and curing are carried out to generate the PSF porous supporting base film;
coating a PDMS dense separation layer: preparing a polydimethylsiloxane/polysulfone ultrathin composite membrane by using a wet membrane dip-coating method; firstly, preparing a coating liquid, taking a PDMS toluene solution with the mass fraction of 35% as a solute and isooctane as a solvent, calculating the adding mass of the PDMS toluene solution and the isooctane according to the required PDMS concentration in the coating liquid, stirring until the PDMS toluene solution and the isooctane are completely dissolved, and then adding a cross-linking agent and a catalyst; wherein the mass ratio of the cross-linking agent to the PDMS is 1: 10, the mass ratio of the catalyst to the PDMS is 1: 100, respectively; to prevent local crosslinking, the crosslinking agent and the catalyst should be added slowly drop by drop; standing and defoaming the coating solution, pouring the coating solution into a tank, and immersing the smooth surface of the PSF porous support base film into the coating solution to enable the coating solution to be evenly and uniformly coated on the surface of the PSF base film, wherein the contact time of the film and the coating solution is 2-3 s; and drying the coated membrane for 2h at the temperature of 85 ℃, and flattening to obtain the polydimethylsiloxane/polysulfone ultrathin composite membrane.
3. The polydimethylsiloxane/polysulfone ultrathin composite membrane prepared by the preparation method of claim 2 is applied to a gas-liquid phase interface and used as a membrane material for gas exchange.
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| CN102451621A (en) * | 2010-10-27 | 2012-05-16 | 中国科学院大连化学物理研究所 | Polyether-b-polyamide multilayer composite film and preparation method thereof |
| CN113509847A (en) * | 2021-04-27 | 2021-10-19 | 北京工业大学 | Method for preparing porous nano particle/polydimethylsiloxane membrane by spreading on water surface |
| CN113509845A (en) * | 2021-04-27 | 2021-10-19 | 北京工业大学 | Preparation method of graphene oxide-cage type oligomeric silsesquioxane hybrid membrane for preferential alcohol permeation |
| CN113509846A (en) * | 2021-04-27 | 2021-10-19 | 北京工业大学 | Method for preparing polydimethylsiloxane composite membrane by water surface spreading method and application |
| CN114225710A (en) * | 2021-12-23 | 2022-03-25 | 华中科技大学 | Viscoelastic composite membrane and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102451621A (en) * | 2010-10-27 | 2012-05-16 | 中国科学院大连化学物理研究所 | Polyether-b-polyamide multilayer composite film and preparation method thereof |
| CN113509847A (en) * | 2021-04-27 | 2021-10-19 | 北京工业大学 | Method for preparing porous nano particle/polydimethylsiloxane membrane by spreading on water surface |
| CN113509845A (en) * | 2021-04-27 | 2021-10-19 | 北京工业大学 | Preparation method of graphene oxide-cage type oligomeric silsesquioxane hybrid membrane for preferential alcohol permeation |
| CN113509846A (en) * | 2021-04-27 | 2021-10-19 | 北京工业大学 | Method for preparing polydimethylsiloxane composite membrane by water surface spreading method and application |
| CN114225710A (en) * | 2021-12-23 | 2022-03-25 | 华中科技大学 | Viscoelastic composite membrane and preparation method and application thereof |
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