CN114960036A - Super-hydrophobic composite membrane and preparation method thereof - Google Patents
Super-hydrophobic composite membrane and preparation method thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
- D04H1/43825—Composite fibres
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/02—Moisture-responsive characteristics
- D10B2401/021—Moisture-responsive characteristics hydrophobic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention discloses a super-hydrophobic composite membrane and a preparation method thereof, wherein phenyl trimethoxy silane and fluorine-containing trimethoxy silane are used as raw materials to prepare fluorine-containing polysiloxane; dissolving the fluorine-containing polysiloxane and the polyester into a solvent to prepare a spinning solution; spinning the spinning solution to obtain the super-hydrophobic composite membrane. The invention functionalizes the trapezoidal polysilsesquioxane by the fluorine-containing group, can effectively reduce the surface energy of the polymer material and improve the hydrophobic property of the polymer material, and the fluorine-containing chain segment has excellent amphiphobic property, is easy to generate microphase separation with other polymer chain segments, can be used for constructing a rough surface, and realizes the superhydrophobic property of a water contact angle of more than 160 degrees.
Description
Technical Field
The invention belongs to a hydrophobic material, and particularly relates to a super-hydrophobic composite membrane and a preparation method thereof.
Background
PCL is known for its advantages of good solubility, biocompatibility/degradability, spinnability and absorbability. It is easy to dissolve in polar solvents such as trichloromethane, toluene, carbon tetrachloride and the like, and is slightly soluble in organic solvents such as acetone, dimethylformamide and the like; as an inert material, has low reactivity with biological cells,no toxicity, no immunogenicity, no acid accumulation during degradation; PCLs of different molecular weights are degradable over a period of months to years, degradation under physiological conditions being affected by hydrolytic activity, amorphous regions and ester bonds in the affected regions being susceptible to degradation by enzymes to CO 2 And H 2 O, environmental protection and no pollution; hydrophobic and lipophilic, can be mixed and dissolved with a plurality of polymers, improves the performance of the composite material, and the like.
The electrostatic spinning equipment which takes a high-voltage power supply, an injection pump, an injector and a receiving device as main components is pushed by the injection pump to extrude the spinning solution loaded in the injector from the needle point. The liquid is exposed to a high voltage electric field and the presence of a potential difference between the needle tip and the receiving means causes the formation of a Tay cone (Tay 1f cone). The surface electrostatic field force then overcomes the tension and viscous drag, the liquid is further stretched while the solvent evaporates, forming a nanofibrous scaffold, which is collected on a receiving device. During the electrospinning process, the solution properties (viscosity, conductivity, surface tension), process parameters (applied voltage, liquid feeding rate, receiving distance), external environment (temperature, humidity) or other conditions can affect the morphology and diameter distribution of the formed nanofibers. At present, as a new and promising synthetic engineering material, the electrospun polymer nanofiber membrane has become an indispensable part of the filtration field (air filtration, seawater desalination, oil-water separation, and the like) due to its advantages of high porosity, permeation flux and selectivity, and excellent stability and adjustability.
Zheng et al [ Zheng S, Huang M, Sun S, et al. Synergistic effect of MIL-88A/g-C 3 N 4 and MoS 2 to construct a self-cleaning multifunctional electrospun membrane[J]. Chemical Engineering Journal, 2021, 421: 129621]Successfully prepares PSF @ MoS through electrostatic spinning technology 2 And PAN @ MIL-88A/g-C 3 N 4 A nanofiber functional layer, and a smooth and compact CS coating is coated on the surface of the fiber to prepare C-P @ MIL-P @ MoS 2 A multifunctional catalytic membrane. Co-catalyst MoS 2 Improves the photodegradability of the fiber filmMechanical strength. In PAN @ MIL-88A/g-C 3 N 4 Catalytic layer and PSF @ MoS 2 Under the synergistic action of the promoting layers, the multifunctional catalytic film has excellent removal effect on dye and Sb (III) in printing and dyeing wastewater. C-P @ MIL-P @ MoS within 20 min under the condition of adding hydrogen peroxide and illumination 2 The film may be completely degraded. When the composite material is used as a filtering membrane, the pure water flux can reach 431.2 LMH. The existence of-OH can effectively remove membrane pollution on the membrane surface and pores, recover water flux, oxidize Sb (III) into low-toxicity Sb (V) and remove the Sb (III), and show good antifouling, self-cleaning and recycling performances.
Membranes for oil-water separation generally have a particular wettability, such as hydrophilic-oleophobic or hydrophobic-oleophilic, when a mixture of oil and water comes into contact with the membrane, one liquid can penetrate through it, while the other liquid is blocked. In the prior art, a hydrophobic polycaprolactone film and a modified film thereof have certain hydrophobic property, but cannot achieve the super-hydrophobic effect.
Disclosure of Invention
The invention functionalizes the trapezoidal polysilsesquioxane by the fluorine-containing group, can effectively reduce the surface energy of the polymer material and improve the hydrophobic property of the polymer material, and the fluorine-containing chain segment has excellent amphiphobic property, is easy to generate microphase separation with other polymer chain segments, and can be used for constructing a rough surface.
The invention adopts the following technical scheme:
a preparation method of the super-hydrophobic composite membrane comprises the following steps:
(1) phenyl trimethoxy silane and fluorine-containing trimethoxy silane are used as raw materials to prepare fluorine-containing polysiloxane;
(2) dissolving the fluorine-containing polysiloxane and the polyester into a solvent to prepare a spinning solution;
(3) spinning the spinning solution to obtain the super-hydrophobic composite membrane.
In the invention, the polyester is Polycaprolactone (PCL), the existing hydrophobic polycaprolactone film has certain hydrophobic property but cannot reach 160 degrees of super-hydrophobic effect, and the fluorine-containing polysiloxane is creatively used for obtaining excellent hydrophobic property with a water contact angle of more than 160 degrees.
In the invention, the mass ratio of the fluorine-containing polysiloxane to the polyester is (0.2-1) to 1, and preferably, the mass ratio of the fluorine-containing polysiloxane to the polyester is (0.4-0.6) to 1; the ratio of the blended materials has an effect on the performance of the composite film.
In the invention, the concentration of the spinning solution is 5-15%, preferably, the concentration of the spinning solution is 8-12%; the mass concentration of the solute is taken as the concentration of the spinning solution, and the solute is fluorine-containing polysiloxane and polyester.
In the present invention, the solvent isN,N-a mixed solvent of dimethylformamide and chloroform, preferably,N,Nthe volume ratio of the dimethylformamide to the trichloromethane is 1 (4-8), and the more preferable range is,N,Nthe volume ratio of the dimethylformamide to the trichloromethane is 1 (5-7).
In the invention, phenyl trimethoxy silane and tridecafluorooctyl trimethoxy silane are mixed, hydrolyzed under alkaline condition and condensed to generate trapezoidal phenyl polysilsesquioxane with a fluorine-containing side chain, namely the fluorine-containing polysiloxane. Preferably, an inorganic base is used as the basic condition.
In the invention, the spinning solution is subjected to electrostatic spinning to obtain the super-hydrophobic composite membrane. The contact angle of the composite fiber membrane obtained by different blending ratios of polycaprolactone/fluorine-containing polysiloxane to water is higher than 150 degrees, wherein when the blending ratio is 1.0:0.4, the contact angle of the fiber membrane to water is as high as 164.8 +/-0.4 degrees.
The invention introduces partial fluorine-containing alkyl on the side group of the trapezoidal phenyl polysilsesquioxane to prepare the trapezoidal phenyl polysilsesquioxane (fluorine-containing polysiloxane) with the fluorine-containing side chain. And (3) blending the synthesized product and polycaprolactone to prepare the spinning solution. By electrostatic spinning, a uniform nanofiber membrane was prepared. The morphology and the surface performance of the trapezoid phenyl polysilsesquioxane nano-fiber modified by the fluoroalkyl group are researched, and some applications of the trapezoid phenyl polysilsesquioxane nano-fiber in the fields of self-cleaning and stain resistance are explored. Specifically, phenyl trimethoxy silane and tridecafluorooctyl trimethoxy silane are mixed, hydrolyzed under the condition of alkaline catalysis, and condensed to generate fluorine-containing polysiloxane. By usingN,N-dimethylformamide and trichloromethane (1: 6, V: V) as a mixed solvent, from polyhexamethyleneAnd (3) performing electrostatic spinning on the mixed solution of the lactone and the fluorine-containing polysiloxane to prepare the polycaprolactone/fluorine-containing polysiloxane composite fiber membrane. The contact angle of the composite fiber membrane obtained by different blending ratios of polycaprolactone/fluorine-containing polysiloxane to water is higher than 150 degrees, wherein when the blending ratio is 1.0:0.4, the contact angle of the fiber membrane to water is as high as 164.8 +/-0.4 degrees. The chemical composition of the composite fiber membrane surface was analyzed by ATR-IR, EDS and XPS. The thermal properties of the fiber membranes were characterized by TGA and found to have an initial degradation temperature of 360 ℃, a final degradation temperature of 445 ℃ and a carbon residue of 20.48%. Dynamic water repellency and water drop rolling tests show that the surface adhesion of the fiber film is low (90.144 mu N), and the fiber film shows excellent liquid repellency. Due to the introduction of the low-surface-energy fluorine-containing chain segment, the polycaprolactone/fluorine-containing polysiloxane fiber membrane has more excellent hydrophobic property and thermal stability, lower adhesion and better self-cleaning property compared with other fiber membranes.
Drawings
FIG. 1 is a scheme for the synthesis of a fluorine-containing polysiloxane.
FIG. 2 shows a silicon nuclear magnetic spectrum (a), an infrared spectrum (b) and a TGA curve (c) of the fluorine-containing polysiloxane.
FIG. 3 is a scanning electron microscope image of polycaprolactone/fluorine-containing polysiloxane composite fiber, the mass ratio is 1.0:0.2, and the scale is 5 μm.
FIG. 4 is a scanning electron microscope image of polycaprolactone/fluorine-containing polysiloxane composite fiber, with a mass ratio of 1.0:0.4 and a scale of 5 μm.
FIG. 5 is a scanning electron microscope image of polycaprolactone/fluorine-containing polysiloxane composite fiber, with a mass ratio of 1.0:0.6 and a scale of 5 μm.
FIG. 6 is a scanning electron microscope image of polycaprolactone/fluorine-containing polysiloxane composite fiber, with a mass ratio of 1.0:0.7 and a scale of 5 μm.
FIG. 7 is a scanning electron microscope image of polycaprolactone/fluorine-containing polysiloxane composite fiber, with a mass ratio of 1.0:1.0 and a scale of 5 μm.
FIG. 8 is a diagram of the dynamic water repellency process (a), a diagram of the water drop rolling process (b), a diagram of the adhesion force curve (c) and a diagram of the liquid repellency of the polycaprolactone/fluorine-containing polysiloxane composite fiber membrane (d).
FIG. 9 shows the self-cleaning process (a 1-a3, b1-b 3) and the stain-proofing process (c 1-c 3) of the polycaprolactone/fluorine-containing polysiloxane composite fiber film.
Detailed Description
Tridecafluorooctyltrimethoxysilane (high purity, not less than 97%) was purchased from Shanghai Tantake technology, Inc., potassium carbonate (high purity, not less than 99%) was purchased from Shanghai Bailingwei chemical technology, Inc., and tetrahydrofuran (high purity, not less than 99.5%) was purchased from Jiangsu argon krypton xenon materials technology, Inc. Phenyltrimethoxysilane (high purity, 98% or more) was purchased from Shanghai' an Ji-resistant chemical technology, Inc. Toluene, anhydrous methanol, hydrochloric acid, potassium hydroxide, trichloromethane,N,N-Dimethylformamide was purchased from Jiangsu Qiangsheng functional chemistry GmbH, and was of analytical pure (AR) specification. Polycaprolactone (PCL, M) n 80000 g/mol) from Shanghai Sigma Aldrich trade, Inc. Distilled water is self-made in a laboratory, and the reagents are directly used without further purification. Aluminum foil (30 cm. times.20 cm), polytetrafluoroethylene tube (18S, inner diameter 1.07 mm, outer diameter 1.87 mm), single-axis needle (18G, inner diameter 0.84 mm, outer diameter 1.27 mm) were purchased from Beijing Lanjie Koch, Shenzhen Ware nuclear materials, Inc. and Shanghai capacitor chemical technology, Inc., respectively.
Preparation examples
As shown in FIG. 1, phenyltrimethoxysilane and tridecafluorooctyltrimethoxysilane are used for cohydrolysis to generate silanol, and condensation polymerization is carried out to generate ladder-shaped phenyl polysilsesquioxane (fluorine-containing polysiloxane) with fluorine-containing side chains. Specifically, K is added into a 250 mL three-neck flask at room temperature 2 CO 3 (0.04 g), deionized water (4.8 g) and THF (16.0 g), stirred for 15 min, and then a mixture of phenyltrimethoxysilane (0.06 mol, 11.9 g) and tridecafluorooctyltrimethoxysilane (0.01 mol, 4.7 g) monomers was added dropwise to the reaction system over 30 min via a constant pressure addition funnel under a nitrogen atmosphere, and reacted for 5 days. After the reaction is finished, standing to take an emulsion layer, drying for 6 hours in a vacuum oven at the temperature of 50 ℃, then adding dichloromethane to dissolve the emulsion layer, and adding deionized water to perform extraction. Organic fraction CollectionThen, the mixture was dried over anhydrous magnesium sulfate, and then subjected to suction filtration and drying to obtain white fluorinated ladder-shaped phenylsilsesquioxane powder (fluorine-containing polysiloxane) having a number average molecular weight of 1500.
To a 500 mL three-necked flask equipped with electromagnetic stirring, 10 mL of phenyltrimethoxysilane and 60 mL of toluene were added under a nitrogen atmosphere, and the reaction system was placed in an ice bath at-10 ℃. The prepared diluted hydrochloric acid (20 mL, 0.1 mol/L) was added dropwise to the mixture over 30 min. After the end of the dropwise addition, the reaction was stirred for 24 h. After the hydrolysis reaction was completed, the reaction solution was allowed to stand in a separatory funnel, and the upper layer solution was taken and washed 5 times with 150 mL of deionized water to be neutral. The hydrolysate obtained in the previous step was transferred to a 250 mL three-neck flask equipped with a reflux condenser, and 3 mL of KOH solution (1 g/L) was added dropwise to the reaction solution through a syringe at room temperature under a nitrogen atmosphere. After the dropwise addition, the reaction temperature was set to 80 ℃ and the reaction was carried out under reflux for 24 hours. After the reaction is finished, 200 mL of deionized water is used for washing the reaction product to be neutral, and then the white solid product ph-LPSQ is obtained through rotary evaporation and vacuum drying.
FIG. 2 is a silicon nuclear magnetic spectrum, an infrared spectrum and a TGA chart of the fluorine-containing polysiloxane. In the silicon nuclear magnetic spectrum, the curve (a) shows two characteristic peaks, wherein the high peak at-79.292 ppm represents the chemical shift of the silicon atom on the trapezoidal skeleton, and the low peak at-69.985 ppm represents the chemical shift of the silicon atom at the terminal of the molecular chain. This shows that the phenyl polysilsesquioxane with fluorine-containing side chains prepared by adding the tridecafluorooctyl trimethoxysilane still has a trapezoidal structure. The infrared spectrum of the fluorine-containing polysiloxane is as shown in curve (b), and it is notable that it is 1243.71 cm in addition to the characteristic peaks of Si-OH, C-H, C-C and Si-C -1 The new peak appeared here is attributed to the stretching vibration of C-F, and the characteristic peak of Si-O-Si here appears as a double peak. In summary, fluorinated ladder-shaped phenyl polysilsesquioxanes have been successfully prepared. The initial and final degradation temperatures of the two ladder polymers are nearly identical, 435 ℃ and 665 ℃, respectively, as shown by the TGA curve (c) for ph-LPSQ and the fluorine-containing polysiloxane.
Example one
Mixing polycaprolactone withThe fluorine-containing polysiloxane was blended in a ratio (m: m) of 1: 0.2 toN,NA mixed solution (V: V, 1: 6) of dimethylformamide and chloroform as a solvent to prepare an electrospinning solution having a solute concentration of 10% (wt%). During electrostatic spinning, the receiving distance is 20 cm, the voltage is 12 kV, the flow rate is 1 mL/h, the humidity is 65 +/-5%, and the temperature is 29 +/-0.2 ℃. The resulting spun film is shown in FIG. 3, with a fiber diameter of 1.88. + -. 0.1. mu.m.
Example two
Blending polycaprolactone and fluorine-containing polysiloxane in a ratio (m: m) of 1: 0.4 to obtain a blendN,NA mixed solution (V: V, 1: 6) of dimethylformamide and chloroform as a solvent to prepare an electrospinning solution having a solute concentration of 10% (wt%). During electrostatic spinning, the receiving distance is 20 cm, the voltage is 12 kV, the flow rate is 1 mL/h, the humidity is 65 +/-5%, and the temperature is 29 +/-0.2 ℃. The obtained spinning membrane is shown in figure 4, the fiber diameter is 1.98 +/-0.23 mu m, the chemical components on the surface of the composite fiber membrane are characterized by ATR-IR, EDS and XPS, the EDS energy spectrum and element content analysis are carried out on the composite fiber membrane, and the polycaprolactone/fluorine-containing polysiloxane composite fiber membrane contains C, O, Si and F, wherein the percentage content of each element is 65.4%, 14.6%, 9.0% and 5.0%. 1160 cm in the infrared curve of polycaprolactone/fluorine-containing polysiloxane fiber membrane -1 The coincident characteristic peak can be attributed to the stretching vibration of C-F and O-C bonds. Besides, through XPS spectrum analysis of the fiber membrane, C, O, Si and F elements are found on the surface of the fiber membrane, which is consistent with the EDS energy spectrum result. Where the C1 s region can be decomposed into C-F (291.89 eV), C = O (289.03 eV), C-O (286.46 eV), and C-C (284.78 eV). The O1 s region consists of three peaks of Si-O-Si (534.59 eV), C = O (533.17 eV) and C-O (531.82 eV). The high resolution Si 2p spectrum consists of two peaks 103.48 eV and 102.12 eV, which correspond to Si-O-Si and Si-C, respectively. Notably, the presence of F-C (688.98 eV) was observed in the F1 s region. In conclusion, the fluorine-containing polysiloxane is successfully blended with PCL and is prepared into a composite fiber membrane through an electrostatic spinning method.
EXAMPLE III
Blending polycaprolactone and fluorine-containing polysiloxane in a ratio (m: m) of 1: 0.6 to obtain a blendN,NA mixed solution (V: V, 1: 6) of dimethylformamide and chloroform as a solvent to prepare an electrospinning solution having a solute concentration of 10% (wt%). During electrostatic spinning, the receiving distance is 20 cm, the voltage is 12 kV, the flow rate is 1 mL/h, the humidity is 65 +/-5%, and the temperature is 29 +/-0.2 ℃. The obtained spinning film is shown in FIG. 5, and the fiber diameter is 2.13. + -. 0.26. mu.m.
Example four
Blending polycaprolactone with a fluorine-containing polysiloxane in a ratio (m: m) of 1: 1 to obtain a blendN,NA mixed solution (V: V, 1: 6) of dimethylformamide and chloroform as a solvent to prepare an electrospinning solution having a solute concentration of 10% (wt%). During electrostatic spinning, the receiving distance is 20 cm, the voltage is 12 kV, the flow rate is 1 mL/h, the humidity is 65 +/-5%, and the temperature is 29 +/-0.2 ℃. The resulting spun film is shown in FIG. 6, with a fiber diameter of 2.28. + -. 0.29. mu.m.
EXAMPLE five
Blending polycaprolactone with a fluorine-containing polysiloxane in a ratio (m: m) of 1: 0.7 to obtain a blendN,NA mixed solution (V: V, 1: 6) of dimethylformamide and chloroform as a solvent to prepare an electrospinning solution having a solute concentration of 10% (wt%). During electrostatic spinning, the receiving distance is 20 cm, the voltage is 12 kV, the flow rate is 1 mL/h, the humidity is 65 +/-5%, and the temperature is 29 +/-0.2 ℃. The resulting spun film is shown in FIG. 7, with a fiber diameter of 2.57. + -. 0.29. mu.m.
When the mass blending ratio of the PCL to the fluorine-containing polysiloxane is increased from 1.0:0.2 to 1.0:1.0, the surface appearance of the fiber is not obviously changed and is a rough structure with protrusions and pits, but the diameter of the fiber is increased from 1.88 +/-0.10 mu m to 2.57 +/-0.29 mu m.
The rolling angle testing method comprises the following steps: fixing the nanofiber membrane on a glass slide through a double-sided adhesive tape, horizontally placing the glass slide on an objective table of a testing instrument, operating a program, slowly inclining the objective table from 0 degree, and when liquid drops just have the trend of relative movement, determining the included angle between the glass slide and the horizontal plane as a rolling angle. The wetting properties of the fiber membrane surface were characterized by a fully automated microscopic droplet wettability tester (OCA 40). The fiber membrane was fixed on a glass slide by double-sided tape, measured at any five points on the sample with 3 μ L of deionized water as the test drop, and averaged. The surface morphology and the three-dimensional structure of the fiber membrane were characterized by atomic force microscopy (VEECO Multimode 8). The interfacial tension of the fiber membrane surface was measured using a surface interfacial tension instrument (DCAT 11). The sample was glued to the slide using double sided tape and placed on the carrier. Subsequently, 4. mu.L of deionized water was aspirated by a pipette, transferred to a metal test ring above the sample, and the droplet was kept spherical. After the bearing platform is lifted to a proper height, the program is operated, the circular ring carrying the water drops approaches to the surface of the fiber membrane at the speed of 0.1 mm/s, and the maximum value of an acting force curve generated by the circular ring from the contact to the separation of the circular ring from the surface of the fiber membrane is the adhesion value of the sample.
EXAMPLE six
The static contact angle performance test is carried out on the composite fiber membranes prepared by different blending ratios, and when the blending ratios are measured to be 1.0:0.2, 1.0:0.4, 1.0:0.6, 1.0:0.8 and 1.0:1.0, the contact angles of the prepared fiber membranes to water are 154.7 +/-0.8 degrees, 164.8 +/-0.4 degrees, 162.4 +/-0.6 degrees, 157.9 +/-0.9 degrees and 157.0 +/-1.0 degrees respectively. Compared with the method of adding ph-LPSQ, the fiber membrane prepared by blending polycaprolactone and fluorine-containing polysiloxane and performing electrostatic spinning has more excellent hydrophobic property, the highest static contact angle to water can reach more than 165 degrees, and the fiber membrane has an obvious super-hydrophobic effect. Selecting the fiber membrane prepared by the technological parameters with the blending ratio of 1.0:0.4 for subsequent research.
Comparative example
PCL and ph-LPSQ were blended at a ratio (m: m) of 1: 0.4, and chloroform was used as a solvent to prepare an electrospinning solution having a solute concentration of 10% (wt%). During electrostatic spinning, the receiving distance is 20 cm, the voltage is 12 kV, the flow rate is 1 mL/h, the humidity is 65 +/-5%, and the temperature is 29 +/-0.2 ℃. The static contact angle of the prepared composite film is 157.2 +/-0.2 degrees.
EXAMPLE seven
The thermal performance (TGA) test is carried out on the fiber membranes obtained by blending and electrostatic spinning of polycaprolactone, ph-LPSQ and fluorine-containing polysiloxane, the initial degradation temperatures of the two fiber membranes are almost maintained at about 360 ℃, the final degradation temperatures are 445 and 495 ℃ respectively, and the corresponding carbon residue rates are 20.48% and 4.74%.
Example eight
Due to the existence of the surface rough structure and the addition of the low-surface-energy fluorine-containing substance, the prepared composite fiber film has higher contact angle and adhesion to water. The dynamic water repellency of the surface of the fiber membrane and the water drop sliding process are shown in fig. 8, and in the process that the sample surface is close to or far away from the water drop, even if the sample surface is squeezed or stretched, the water drop still maintains at the needle point, and no trace is left on the membrane surface. The sample stage was tilted at 4 °, a drop of water was dropped from above, the drop of water bounced up after contacting the surface of the fiber membrane, and rolled off rapidly. The polycaprolactone/fluoropolysiloxane was tested to have a lower surface adhesion of 90.144 μ N relative to the fluorine-free conjugate fiber film. Besides a higher contact angle to water, the composite fiber membrane also shows good liquid repellency to ink, coffee, 1M NaOH and 1M NaCl, and the contact angles of the fiber membrane to four liquids are 155.4 +/-0.7 degrees, 154.6 +/-0.6 degrees, 154.2 +/-0.5 degrees and 153.7 +/-0.4 degrees respectively.
Example nine
The composite fiber membrane has excellent super-hydrophobic performance and low adhesion, so that the composite fiber membrane has wide application prospect in the fields of self-cleaning and stain resistance. Methylene blue powder and chalk powder were used as test contaminants. When in test, the composite fiber membrane is fixed on the surface of a glass slide and is placed at an angle of 8 degrees. As shown in fig. 9 (a 1-a3, b1-b 3), the water droplets, after being extruded from the syringe, fall out of the air, after contacting the surface of the film, roll off quickly, dissolving and carrying away the contaminants distributed on the surface of the sample, and leaving no stains on the fiber film. In FIG. 9, (c 1-c 3) is a stain-proofing test chart of the sample film, water is stained with methylene blue powder, the sample film is immersed in the staining solution with tweezers, and after standing for a while, the sample film is taken out, and no stain trace is found on the surface. The results show that the polycaprolactone/fluorine-containing polysiloxane composite fiber film has good self-cleaning and anti-fouling properties.
The invention mixes phenyl trimethoxy silane and tridecafluorooctyl trimethoxy silane according to a certain molar ratio, adopts basic catalyst to fully hydrolyze the mixture into silanol, and generates trapezoidal phenyl polysilsesquioxane with a fluorine-containing side chain by polycondensation,by passing 29 Si-NMR, FT-IR and TGA. Blending polycaprolactone and fluorine-containing polysiloxane, and preparing the composite fiber membrane by a one-step electrostatic spinning method. The static contact angle tests of the fiber membranes prepared by different blending ratios show that the contact angles are higher than 150 degrees, and the fiber membranes have good super-hydrophobic performance, wherein when the blending ratio is 1.0:0.4, the contact angle of the obtained fiber membranes is the highest and can reach 164.8 +/-0.4 degrees, and the contact angle is superior to that of a PCL/ph-LPSQ composite fiber membrane (158 +/-0.1 degrees). The chemical components on the surface of the composite fiber membrane are analyzed through ATR-IR, EDS and XPS, and the F element and the C-F bond appear, so that the fluorine-containing polysiloxane is successfully mixed into the polycaprolactone fiber membrane. The thermal properties of the polycaprolactone/fluorine-containing polysiloxane fiber film (initial degradation temperature: 360 ℃, final degradation temperature: 495 ℃, carbon residue rate: 4.74%) and the PCL/ph-LPSQ fiber film (initial degradation temperature: 360 ℃, final degradation temperature: 445 ℃, carbon residue rate: 20.48%) were characterized by TGA test. And observing the rough structure on the surface of the composite fiber membrane by adopting SEM and AFM, and finding that the fiber surface has concave-convex wrinkle appearance. Through dynamic water repellency and water drop rolling tests, it is found that the liquid drops do not remain on the surface of the fiber film even if the liquid drops are pressed or stretched to be deformed on the surface of the fiber film, and the liquid drops can easily slide away from the surface of the fiber film at a very low inclination angle, showing very low adhesion (90.144 μ N). Various aqueous solutions can be maintained as spherical liquid drops on the surface of the fiber membrane, and the contact angles are all higher than 150 degrees. Compared with other composite fiber membranes, the polycaprolactone/fluorine-containing polysiloxane composite fiber membrane has better hydrophobic property, thermal property, self-cleaning property, anti-contamination property and lower adhesive force, and has good potential application prospect.
Claims (10)
1. A preparation method of a super-hydrophobic composite membrane is characterized by comprising the following steps:
(1) phenyl trimethoxy silane and fluorine-containing trimethoxy silane are used as raw materials to prepare fluorine-containing polysiloxane;
(2) dissolving the fluorine-containing polysiloxane and the polyester into a solvent to prepare a spinning solution;
(3) spinning the spinning solution to obtain the super-hydrophobic composite membrane.
2. The preparation method of the super-hydrophobic composite membrane according to claim 1, wherein the mass ratio of the fluorine-containing polysiloxane to the polyester is (0.2-1) to 1.
3. The preparation method of the super-hydrophobic composite membrane according to claim 2, wherein the mass ratio of the fluorine-containing polysiloxane to the polyester is (0.4-0.6) to 1.
4. The preparation method of the superhydrophobic composite membrane according to claim 1, wherein the concentration of the spinning solution is 5-15%.
5. The method for preparing the superhydrophobic composite membrane according to claim 1, wherein the solvent isN,N-a mixed solvent of dimethylformamide and chloroform.
6. The method for preparing the superhydrophobic composite membrane according to claim 1,N,Nthe volume ratio of the dimethylformamide to the trichloromethane is 1 (4-8).
7. The superhydrophobic composite membrane prepared by the method for preparing the superhydrophobic composite membrane according to claim 1.
8. Use of the superhydrophobic composite membrane of claim 7 in the preparation of a superhydrophobic material.
9. Use according to claim 8, wherein the superhydrophobic material has a water contact angle of greater than 150 °.
10. Use of the superhydrophobic composite membrane of claim 7 in the preparation of self-cleaning materials.
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