CN109731479B - Preparation method of super-hydrophobic nanofiber membrane and super-hydrophobic nanofiber membrane - Google Patents
Preparation method of super-hydrophobic nanofiber membrane and super-hydrophobic nanofiber membrane Download PDFInfo
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Abstract
The invention discloses a preparation method of a super-hydrophobic nanofiber membrane and the super-hydrophobic nanofiber membrane, which comprises the steps of dissolving monomer biphenyltetracarboxylic dianhydride and p-phenylenediamine in N, N-dimethylformamide, reacting at low temperature to synthesize PAA, preparing the PAA into a PAA nanofiber membrane through electrostatic spinning, and imidizing to obtain a PI membrane; and carrying out layer-by-layer self-assembly and PDMS solution dip-coating modification by adopting ferric trichloride and phytic acid to obtain the super-hydrophobic nanofiber membrane. The invention realizes the utilization of a layer-by-layer self-assembly structure, introduces the silane coupling agent on the basis, and combines the silane coupling agent and the silane coupling agent to obtain the oil-water separation membrane with super-hydrophobic, super-oleophylic and wettable properties. The nano structure with the rough surface has the advantages that the oil-water separation performance is improved, the separation efficiency of the membrane can reach more than 99%, and the membrane can be recycled through verification.
Description
Technical Field
The invention belongs to the technical field of oil-water separation membrane preparation, and particularly relates to a preparation method of a super-hydrophobic nanofiber membrane and the super-hydrophobic nanofiber membrane.
Background
The traditional oil-water separation method comprises biological treatment, condensation, air floatation and adsorption, but the methods have the limitations of low separation efficiency, high energy consumption, complex process, easy generation of secondary pollutants and the like. Therefore, the development of an effective oil-water separation technology is urgently needed.
In recent years, the membrane separation method is recognized as an alternative technology for separating oil-water mixture due to the advantages of simple operation, high separation efficiency, low manufacturing cost, good flexibility, controllable environment and the like. Accordingly, increasing research efforts have focused on polymer-based membrane separation techniques, such as ultrafiltration and microfiltration membranes of Polysulfone (PSF), Cellulose Triacetate (CTA), polyvinylidene fluoride (PVDF), Cellulose Acetate (CA), and the like. Unfortunately, most conventional ultrafiltration and microfiltration membranes still suffer from low flux and a tendency to be prone to fouling.
Due to the overlapping and separation of single fibers and the like, the fiber membrane prepared by electrostatic spinning has poor mechanical properties, and practical application of the fiber membrane in oil-water separation is limited. In addition, long-term durability of nanofiber membranes currently used in harsh environments remains a significant challenge. Therefore, the nanofiber membrane prepared by electrospinning needs to be further modified before being applied to practice, so that the mechanical property and the application range of the nanofiber membrane are improved.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made in view of the above-mentioned technical drawbacks.
Therefore, as one aspect of the present invention, the present invention overcomes the disadvantages in the prior art, and provides a method for preparing a superhydrophobic nanofiber membrane.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of a super-hydrophobic nanofiber membrane comprises the following steps,
dissolving monomer biphenyl tetracarboxylic dianhydride and p-phenylenediamine in N, N-dimethylformamide, reacting at low temperature to synthesize PAA, preparing the PAA into a PAA nanofiber membrane by electrostatic spinning, and imidizing to obtain a PI membrane;
and carrying out layer-by-layer self-assembly and PDMS solution dip-coating modification by adopting ferric trichloride and phytic acid to obtain the super-hydrophobic nanofiber membrane.
As a preferred scheme of the preparation method of the super-hydrophobic nanofiber membrane, the preparation method comprises the following steps: the PAA is synthesized by reacting at low temperature, wherein the PAA is obtained by continuously mechanically stirring in a nitrogen environment at-5 ℃ and terminating the reaction after the substances in the reactor become viscous liquid and the pole climbing phenomenon occurs.
As a preferred scheme of the preparation method of the super-hydrophobic nanofiber membrane, the preparation method comprises the following steps: the PAA is prepared into the PAA nanofiber membrane through electrostatic spinning, and comprises adding lwt per thousand of cetyltrimethylammonium bromide in the PAA before electrostatic spinning.
As a preferred scheme of the preparation method of the super-hydrophobic nanofiber membrane, the preparation method comprises the following steps: the PAA is prepared into the PAA nanofiber membrane through electrostatic spinning, wherein the electrostatic spinning conditions comprise spinning in a high-voltage electrostatic field of 15kV, the propelling speed of an injector is 1.0mL/h, the spinning distance is 10cm, and the rotating speed of a roller is 1500 rpm.
As a preferred scheme of the preparation method of the super-hydrophobic nanofiber membrane, the preparation method comprises the following steps: and the imidization is carried out, namely, the PAA nanofiber membrane is placed in a tubular furnace, and the temperature is gradually increased to 350 ℃ for imidization.
As a preferred scheme of the preparation method of the super-hydrophobic nanofiber membrane, the preparation method comprises the following steps: the method comprises the steps of carrying out layer-by-layer self-assembly by adopting ferric trichloride and phytic acid and carrying out dip-coating modification by adopting PDMS solution to obtain the super-hydrophobic and super-oleophilic oil-water separation membrane, wherein the step of immersing the PI membrane into FeCl3In solution, obtaining positively charged Fe3+a/PI membrane. Removing excessive FeCl on the surface of the fiber membrane by using distilled water3Solution of positively charged Fe3Soaking the +/-PI film in phytic acid to obtain PA-Fe with negative charges3+the/PI membrane is thoroughly washed by distilled water to remove excessive PA, a self-assembly cycle is completed, and curing and drying are carried out in a vacuum oven。
As a preferred scheme of the preparation method of the super-hydrophobic nanofiber membrane, the preparation method comprises the following steps: the concentration of the ferric trichloride is 0.01mol/L, and the concentration of the phytic acid is 0.013 mol/L.
As a preferred scheme of the preparation method of the super-hydrophobic nanofiber membrane, the preparation method comprises the following steps: the method comprises the steps of carrying out layer-by-layer self-assembly by adopting ferric trichloride and phytic acid and carrying out dip-coating modification by adopting PDMS solution to obtain the super-hydrophobic and super-lipophilic oil-water separation membrane, drying and then carrying out PA-Fe3+And immersing the PI membrane into an ethyl acetate solution of 2 wt% PDMS prepolymer for curing, and drying in a vacuum drying oven to obtain the super-hydrophobic nanofiber membrane.
As another aspect of the invention, the invention overcomes the defects in the prior art, and provides the super-hydrophobic nanofiber membrane prepared by the preparation method of the super-hydrophobic nanofiber membrane.
In order to solve the technical problems, the invention provides the following technical scheme: the super-hydrophobic nanofiber membrane prepared by the preparation method of the super-hydrophobic nanofiber membrane is characterized in that: the separation flow rate of the super-hydrophobic nanofiber membrane is higher than 7935 L.m-2h-1The separation efficiency reaches more than 99 percent, and the drainage angle reaches more than 150 degrees.
The invention has the beneficial effects that: the invention realizes the utilization of a layer-by-layer self-assembly structure, introduces the silane coupling agent on the basis, and combines the silane coupling agent and the silane coupling agent to obtain the oil-water separation membrane with super-hydrophobic, super-oleophylic and wettable properties. The nano structure with rough surface improves the oil-water separation performance, the separation efficiency of the membrane can reach more than 99 percent, and the separation flux is higher than 7935 L.m-2·h-1The hydrophobic angle reaches more than 150 degrees, and the hydrophobic membrane can be circularly and repeatedly used after being verified.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is a scheme for constructing FeCl3Schematic representation of PA/PDMSPI nanofiber membranes.
FIG. 2 is a surface topography and elemental composition diagram. (a) SEM image of pristine PI nanofiber membrane. (b) Five-time layer-by-layer self-assembly modified PA-Fe3+SEM image of/PI film. (c) Super-hydrophobic PDMS/PA-Fe modified by 2 wt% PDMS solution3+SEM image of/PI film. (d) PDMS/PA-Fe3+EDS spectrogram of/PI nanofiber membrane surface.
FIG. 3 is a representation. (a) PI film, PA-Fe3+[ solution ] PI film, PDMS/PA-Fe3+FTIR spectrum of/PI film. (b) PI film, PA-Fe3+[ solution ] PI film, PDMS/PA-Fe3+TGA profile of/PI film. (c) PI film, PA-Fe3+[ solution ] PI film, PDMS/PA-Fe3+XPS spectrum of/PI film. (d) PI film, PA-Fe3+[ solution ] PI film, PDMS/PA-Fe3+XRD spectrum of/PI film.
Fig. 4 is a condition selection diagram. (a) PDMS/PA-Fe modified by PDMS with different concentrations3+Water contact angle of the/PI film. (b) PDMS/PA-Fe subjected to layer-by-layer autonomous installation for different times3+Water contact angle of the/PI film.
FIG. 5 shows FeCl prepared by the method of the present invention3And (3) testing the contact angle of the oil-water separation fiber membrane of the PI substrate with the PA/PDMS modified layer-by-layer self-assembly structure under different conditions. (a) Test pattern of water contact angle in air. (b) Water contact angle test pattern of organic solvent/salt solution. (c) Water contact angle test pattern after different time of ultraviolet irradiation. (d) Water contact angle test plots at different temperatures.
FIG. 6 is a diagram showing the separation process and the evaluation of the separation effect. (a1-a4) photographs of the procedure for the separation of dichloromethane/water PDMS/PA-Fe3+a/PI nanofiber membrane. (b) The oil-water mixture passes through PDMS/PA-Fe3+Permeability flux and separation efficiency of PI nanofiber membranes. (c) Recycling 20 times of PDMS/PA-Fe3+Change in permeation flux and separation efficiency of PI nanofiber membranes.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1:
is provided with a mechanical stirrer, a thermometer and N2A100 mL three-necked round-bottomed flask having an inlet and outlet was charged with 0.01mol of BPDA and 0.01mol of PDA, and the mixture was uniformly mixed. Under vigorous mechanical stirring, 40ml of ldmac solution was added. The reaction temperature was controlled to-5 ℃ using a low temperature reactor. The flask was then connected to a nitrogen cylinder at N2After reacting for 24 hours under the environment, the phenomenon of climbing a rod in the flask is found, namely the reaction can be exposed in the air to finish the reaction, and the PAA polymer is obtained.
Preparation of Polyamic acid (PAA) nanofiber membrane PAA polymer obtained above was dissolved in DMAc to obtain a DMAc solution containing 3 wt% of PAA, l ‰ (wt%) of cetyltrimethylammonium bromide was added to enhance its conductivity, and the mixture was stirred for 1h under a magnetic stirrer to obtain a uniformly mixed solution. Spinning in a high-voltage electrostatic field of 15kV, wherein the distance from the needle point to the roller is about 10cm, the collector is a grounded flywheel with adjustable rotating speed, the rotating speed is 1500rpm, and the electrospinning speed is 1.0 mL/h. In N2Imidizing the electrospun PAA fiber membrane in a protected tube furnace, wherein the imidization is as follows: heating the PAA nanofiber membrane to 150 ℃ according to the heating rate of 1 ℃/min, preserving heat for 1h, then heating to 200 ℃ and preserving heat for 1h, then heating to 250 ℃ and preserving heat for 1h, and then carrying out heat preservation on the PAA nanofiber membraneThen heating to 300 ℃ and preserving heat for 1h, finally heating to 350 ℃ and preserving heat for 0.5h, imidizing to obtain the polyimide nano fiber membrane (PI membrane) and removing low molecular weight residues (water and organic solvent) in the polyimide nano fiber membrane.
Example 2:
(1) the PI film (2 cm. times.2 cm) prepared in example 1 was placed in ethanol and deionized water solution and sequentially subjected to ultrasonic treatment for 30min to remove surface impurities.
(2) 2.7029g of ferric trichloride hexahydrate solid is accurately weighed, dissolved by deionized water and subjected to constant volume to obtain 0.01mol/L FeCl3And (3) solution.
(3) Immersing the cleaned PI film into FeCl3Obtaining Fe with positive charge in the solution for 2min3+a/PI membrane, then removing excessive FeCl on the surface of the membrane by using distilled water3。
(4) The obtained Fe with positive charge3+Soaking the PI film in 0.013mol/L Phytic Acid (PA) solution for 2min to obtain PA-Fe with negative charge3+the/PI membrane was then rinsed thoroughly with distilled water to remove excess PA solution. In this manner, a self-assembly cycle is completed and the process is repeated to achieve the desired number of self-assembly cycles on the PI nanofiber membrane.
(5) The sample obtained above was dried at 60 ℃ for 2 hours and then immersed in a solution of 2 wt% PDMS prepolymer in ethyl acetate for 2 min. Finally, the mixture is placed under vacuum (80 ℃) for drying for 2 hours to obtain the PDMS/PA-Fe with super hydrophobicity and super lipophilicity3+The whole process is shown in figure 1.
Example 3:
the PI film, PA-Fe, prepared in example 2 was observed by a field emission scanning electron microscope (S-4800, Hitachi electronics, Japan)3+(ii) PI film, PDMS/PA-Fe3+The surface morphology of the/PI film can clearly see that the three-dimensional porous structure on the fiber is combined with the micro/nano-scale protrusions to form a double rough structure which is very similar to the lotus leaf surface. The field emission scanning electron microscope used this time has the function of analyzing elements, and the successful modification of the film is confirmed by confirming the elements on the surface of the film through EDS analysis equipped, as shown in FIG. 2.
By using NThe PI film prepared in example 2, PA-Fe, was identified separately by icolet 360FT-IR spectrometer3+(ii) PI film, PDMS/PA-Fe3+The functional groups and the structural properties of the/PI membrane are shown in FIG. 3 a. One of the adsorption peaks of the PI fiber is 1771cm-1It can be attributed to the tensile vibration of the-CONH functional group, which proves the successful imidization of PAA fibers. In addition, 1717cm-1,1356cm-1The adsorption peaks at (A) correspond to-COOH and C-N functional groups respectively, which are characteristic peaks of polyimide. Through FeCl3And after phytic acid treatment, at 1652cm-1And 1100cm-1A new characteristic peak appears, which is respectively assigned to the stretching vibration of the P ═ O functional group and-HPO 43-Characteristic peak of (2). PA-Fe3+After soaking the/PI film in the PDMS solution, 1261cm-1and 810cm-1New characteristic peaks appear and are respectively assigned to Si-CH3Bending vibration of the bond and stretching vibration of the Si-O-Si bond.
The thermal stability of the film was characterized using a thermogravimetric analyzer (TGA Q5000-IR), TA USA, with a temperature rise rate of 1 deg.C per minute, cut off from room temperature to 800 deg.C. From the curve of the change of the mass with the temperature, the super-hydrophobic fiber membrane prepared by the method of the invention has thermal stability, and the membrane still keeps stable above 500 ℃, as shown in figure 3 b.
The morphology of the fiber produced in example 2 was examined by X-ray powder diffraction (XRD) (Ultima IV, Rigaku, japan). All samples showed similar XRD patterns with broad diffraction peaks around 18 °, 21 ° and 25 °, respectively. This means that the film PDMS/PA-Fe3+The micro/nanostructures of the/PI film are amorphous and retain the fiber structure during surface modification, as shown in fig. 3 c.
The different elements on the surface of the film prepared in example 2 were respectively detected by x-ray photoelectron spectroscopy (XPS) (AXIS Ultra DLD, UK), and XPS measurement spectrum showed that the PI film is composed of element C1s(285eV)，N1s(399eV) and O1s(532 eV). After layer-by-layer self-assembly, at 745eV (Fe)2p) New peak appears, indicating N1sThe signal intensity of (a) is reduced, meaning that the PI nanofiber membrane is PA-Fe3+Completely covering, further modifying with PDMS, and making into new productPeaks appear at 100.4eV and 167.7eV, which are ascribed to the hybrid orbital Si2sAnd Si2pFurther indicating that PDMS successfully coated the PI nanofiber membrane as shown in fig. 3 d.
A contact angle measuring instrument (JC2000D1) is adopted, and the wettability of PDMS solutions with different concentrations and the surface of a nanofiber membrane which is autonomously modified layer by layer for different times is tested by Shanghai Zhongchen company in China. The film is laid on a test bench, a camera is aligned to a platform to ensure that a complete picture can be captured, a sample injection needle is filled with deionized water, 2 microliters of deionized water is pushed out every time, a liquid drop is stopped on the surface of the film, the tangent point of the liquid drop and the surface of the film and the highest point of the liquid drop are manually determined by adopting the principle of three-point circle, the wettability of the surface of the film can be determined by automatically generating a contact angle by a measuring instrument, the contact angle reaches 153.64 +/-11.6 degrees, and the test result is shown in figure 4.
Example 4:
to further evaluate the environmental resistance of the nanofiber membrane prepared in example 2. We chose layer-by-layer self-assembly for 5 times, 2 wt% PDMS modified PI nanofiber membranes for further study. The contact angle measuring instrument (JC2000D1) is adopted, and the water solution, strong acid/alkali/high-concentration salt solution (CaCl) under different pH values are measured by Shanghai Zhongchen company in China2，KCl，Zn(NO3)2And MgSO4) PDMS/PA-Fe in medium and organic solvent (n-hexane, acetone, toluene, ether, dimethyl sulfoxide and chloroform) under different ultraviolet irradiation time and temperature3+The water contact angles of the/PI films were tested and the results showed that the contact angles of the films were all higher than 150 °, confirming that the nanofiber film prepared in example 2 has very good tolerance, as shown in fig. 5.
Example 5:
and (3) separating the oil-water mixture by adopting a measuring cylinder type filter, and calculating the separation efficiency and the flux by recording the mass of liquid before and after separation. A mixture of water and Dichloromethane (DCM) (50% v/v, water and DCM were stained with methyl blue and Sudan III, respectively, for easy observation) was poured into the top tube. It was observed that DCM could penetrate the membrane and fall into the beaker below. At the same time, water is trapped above the membrane.After the separation was completed, almost all DCM was collected below, showing excellent oil/water separation performance. The other four oil-water mixtures (trichloromethane-water, dichloroethane-water, bromobenzene-water and carbon tetrachloride-water) were also successfully separated, and the separation efficiency of all the products was higher than 99%. Meanwhile, the film exhibits good recyclability and durability after separating various oil-water mixtures. For example, after 20 times of separation, the separation flux and separation efficiency of DCM-water mixture have little change in repeated process, and the separation flux is always higher than 7935 L.m-2·h-1The separation efficiencies were all above 99%, as shown in fig. 6.
The invention realizes the utilization of a layer-by-layer self-assembly structure, introduces the silane coupling agent on the basis, and combines the silane coupling agent and the silane coupling agent to obtain the oil-water separation membrane with super-hydrophobic, super-oleophylic and wettable properties. The nano structure with the rough surface has the advantages that the oil-water separation performance is improved, the separation efficiency of the membrane can reach more than 99%, and the membrane can be recycled through verification.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and 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 on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (2)
1. A preparation method of a super-hydrophobic nanofiber membrane is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
dissolving monomer biphenyltetracarboxylic dianhydride and p-phenylenediamine in N, N-dimethylformamide, continuously mechanically stirring in a nitrogen environment at the temperature of-5 ℃, and stopping reaction after the substances in the reactor become viscous liquid and a rod climbing phenomenon occurs to obtain PAA; adding lwt per mill of cetyltrimethylammonium bromide into PAA before electrostatic spinning, preparing the PAA into a PAA nanofiber membrane through electrostatic spinning, placing the PAA nanofiber membrane in a tube furnace, gradually heating to 350 ℃ for imidization to obtain a PI membrane, wherein the electrostatic spinning conditions comprise spinning in a 15kV high-voltage electrostatic field, the propelling speed of an injector is 1.0mL/h, the spinning distance is 10cm, and the rotating speed of a roller is 1500 rpm;
immersing the PI film in FeCl3In solution, obtaining positively charged Fe3+a/PI membrane; removing excessive FeCl on the surface of the fiber membrane by using distilled water3Solution of positively charged Fe3+Soaking the PI film in phytic acid to obtain PA-Fe with negative charge3+a/PI membrane, which is thoroughly rinsed with distilled water to remove excess phytic acid, completing one self-assembly cycle, and the process is repeated to obtain self-assembly on the PI nanofiber membrane 5 times, in a vacuum oven, curing and drying; the FeCl3The concentration is 0.01mol/L, and the concentration of the phytic acid is 0.013 mol/L;
drying to obtain PA-Fe3+And immersing the PI membrane into an ethyl acetate solution of 2 wt% PDMS prepolymer for curing, and drying in a vacuum drying oven to obtain the super-hydrophobic nanofiber membrane.
2. The superhydrophobic nanofiber membrane prepared by the preparation method of the superhydrophobic nanofiber membrane of claim 1, wherein: the separation flow rate of the super-hydrophobic nanofiber membrane is higher than 7935 L.m-2h-1The separation efficiency reaches more than 99 percent, and the drainage angle reaches more than 150 degrees.
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| CN111207299B (en) * | 2020-01-08 | 2021-08-06 | 中国石油大学(北京) | Surface modification method for oil field gathering and transportation pipeline |
| CN111362351B (en) * | 2020-02-19 | 2022-04-05 | 华东师范大学 | Oil-water separation device and method based on hydrophilic metal net and hydrophobic metal net |
| CN114504954B (en) * | 2020-11-16 | 2023-03-28 | 中国石油化工股份有限公司 | Multilayer super-hydrophobic composite membrane and preparation method thereof |
| CN113117671B (en) * | 2021-03-31 | 2022-08-19 | 四川大学 | Hydrogen peroxide catalyst, preparation method and application |
| CN114635230B (en) * | 2022-04-02 | 2024-03-26 | 天津工业大学 | Bulk super-hydrophobic nanofiber membrane for membrane distillation and preparation method thereof |
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| CN116043416B (en) * | 2022-10-20 | 2024-07-16 | 陕西地建土地工程技术研究院有限责任公司 | Electrostatic spinning super-hydrophobic membrane for oil-water separation and preparation method thereof |
| CN115572941A (en) * | 2022-11-08 | 2023-01-06 | 东莞瑞彩光学薄膜有限公司 | Processing technology of high-brightness composite board |
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