CN112899888A - Hydrophobic modified SiO2Method for preparing grafted polyvinyl alcohol super-hydrophobic fiber membrane - Google Patents
Hydrophobic modified SiO2Method for preparing grafted polyvinyl alcohol super-hydrophobic fiber membrane 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
- D01D5/247—Discontinuous hollow structure or microporous structure
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/96—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from other synthetic polymers
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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
- D04H1/4282—Addition polymers
- D04H1/4309—Polyvinyl alcohol
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Abstract
The invention relates to the technical field of super-hydrophobicity and discloses hydrophobically modified SiO2Grafting polyvinyl alcohol super-hydrophobic fiber membrane to prepare SiO2The surface hydroxyl of the substrate is reacted to be changed into hydrophobic and oleophilic SiO2Esterifying polyvinyl alcohol with mercaptoethylene to obtain polyvinyl alcohol containing a great deal of mercapto, and performing mercapto-alkene click reaction to hydrophobically modified SiO2Grafted in polyvinyl alcohol matrix to make it hydrophilicConversion of hydrophobic polyvinyl alcohol to a hydrophobic material, nano SiO2The grafting mode is introduced, so that the dispersibility is very good, a large number of micro-nano structured protrusions and microporous structures are better formed on the surface of the polyvinyl alcohol, when liquid drops contact with water, the micropores below the liquid drops seal air to form an air cushion, the composite fiber membrane has a bionic super-hydrophobic structure similar to lotus leaves, the contact angle between the water and the polyvinyl alcohol fiber membrane is increased, and the super-hydrophobic performance of the polyvinyl alcohol material is endowed.
Description
Technical Field
The invention relates to the technical field of super-hydrophobicity, in particular to hydrophobically modified SiO2A method for preparing a grafted polyvinyl alcohol super-hydrophobic fiber membrane.
Background
Along with the improvement of the quality of life, the demand of people on various functional substances is also increased, the demand is also increased, and the main functional modification direction at present is as follows: the super-hydrophobic material is also popular among researchers, due to the unique self-cleaning property and the excellent corrosion resistance, the super-hydrophobic material is even commonly applied to special fields such as weapon equipment surface coatings, electronic equipment lens protection, special protective clothing and the like and has very wide application prospects and values.
Polyvinyl alcohol is a common chemical raw material, and is widely applied to various functional film materials due to the advantages of excellent film-forming property, no toxicity, stable thermochemical property and the like, but a polyvinyl alcohol side chain contains a large amount of hydrophilic hydroxyl groups, so that the polyvinyl alcohol has very good hydrophilicity, the polyvinyl alcohol has the defects of high hygroscopicity, poor water resistance and the like, the application field of the polyvinyl alcohol is limited, the polyvinyl alcohol side chain is modified to roughen the surface, so that the polyvinyl alcohol side chain has good hydrophobic property, and the hydrophobically modified silicon dioxide is a good additive material.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a hydrophobically modified SiO2The preparation method of the grafted polyvinyl alcohol super-hydrophobic fiber membrane solves the problem that the polyvinyl alcohol does not have super-hydrophobicity.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: hydrophobic modified SiO2The preparation method of the grafted polyvinyl alcohol super-hydrophobic fiber membrane comprises the following steps:
(1) mixing SiO2Adding glycidyl methacrylate and N, N-dimethylformamide solvent, performing ultrasonic dispersion in an ultrasonic device, adding sulfuric acid solution, reacting at 90-110 deg.C for 8-12h in nitrogen atmosphere, filtering, washing, and vacuum drying to obtain hydrophobically modified alkenyl SiO2；
(2) Adding polyvinyl alcohol and thioglycollic acid into 4-6% sulfuric acid solution, reacting at 70-90 deg.C for 2-4h, dialyzing and purifying to obtain thiolated polyvinyl alcohol;
(3) the sulfhydrylation polyvinyl alcohol and the hydrophobic modified alkenyl SiO2Adding into absolute ethanol solution, ultrasonic dispersing, performing ultraviolet irradiation reaction, separating and washing to obtain polyvinyl alcohol grafted nanometer SiO2。
(4) And spinning in an electrostatic spinning machine at a spinning voltage of 20-25KV and a solution flow rate of 2-3mL/h and a receiving distance of 8-12cm to form a membrane, thus obtaining the hydrophobically modified SiO2 grafted polyvinyl alcohol superhydrophobic fiber membrane.
Preferably, SiO in the step (1)2The mass ratio of the monomer to the glycidyl methacrylate is 100: 200-300.
Preferably, the mass ratio of the polyvinyl alcohol to the thioglycolic acid in the step (2) is 100: 80-150.
Preferably, the thiolated polyvinyl alcohol and the hydrophobically modified alkenylated SiO in the step (3)2The mass ratio of (1) is 100: 120-200.
Preferably, the reaction temperature of the ultraviolet light irradiation in the step (3) is 30-40 ℃, and the ultraviolet light intensity is 45-65Mw/cm2The irradiation time is 30-45 min.
Preferably, the electrostatic spinning machine includes the control cabinet in step (4), the control cabinet openly is provided with display and control button, the control cabinet right side is provided with the heat dissipation window, control cabinet top fixedly connected with spinning storehouse, spinning storehouse swing joint has the quartz glass window, the spinning storehouse is provided with the magnetism door-inhale, fixedly connected with stock solution tank holder in the spinning storehouse, stock solution tank holder fixedly connected with liquid storage pot, the liquid storage pot has the electrostatic spinning needle through electric wire swing joint, the electrostatic spinning needle is provided with the spinning syringe needle, fixedly connected with electrostatic generator in the spinning storehouse, fixedly connected with receiving plate rail frame in the spinning storehouse.
(III) advantageous technical effects
Compared with the prior art, the invention has the following experimental principles and beneficial technical effects:
the hydrophobic modified SiO2Grafting a polyvinyl alcohol superhydrophobic fibrous membrane through SiO2Surface hydroxyl groups with methacrylic acidThe glycidyl ester generates nucleophilic substitution reaction under the acidic condition, the epoxy bond opens the ring and SiO2The surface hydroxyl group of the precursor reacts to obtain hydrophobic modified SiO2Rendering SiO hydrophilic2SiO converted into hydrophobic and oleophilic2Esterifying polyvinyl alcohol and mercaptoethylene under acidic condition to obtain mercaptolated polyvinyl alcohol containing a great amount of mercapto groups and reducing hydrophilicity of polyvinyl alcohol, and reacting via mercapto-alkene click reaction to obtain SiO2Grafting the product in polyvinyl alcohol matrix to obtain hydrophobically modified SiO2Grafting a polyvinyl alcohol super-hydrophobic fiber membrane, and grafting hydrophobically modified SiO on the surface of polyvinyl alcohol in a chemical grafting way2To convert hydrophilic polyvinyl alcohol into hydrophobic material, nano SiO2The grafting mode is introduced, so that the dispersibility is very good, a large number of micro-nano structured protrusions and microporous structures are better formed on the surface of the polyvinyl alcohol, when liquid drops contact with water, the micropores below the liquid drops seal air to form an air cushion, a solid-gas composite contact surface is formed, the composite fiber membrane has a bionic super-hydrophobic structure similar to lotus leaves, the contact angle between the water and the polyvinyl alcohol fiber membrane is increased, the super-hydrophobic performance of the polyvinyl alcohol material is endowed, and meanwhile, the coarse structure is more stably fixed on the surface of the polyvinyl alcohol fiber membrane by the chemical grafting mode, so that the cyclic service performance of the material is improved.
Drawings
FIG. 1 is a schematic front view of an electrospinning machine;
FIG. 2 is a schematic side view of an electrospinning machine.
1-a console; 2-a display; 3-a control button; 4-a heat dissipation window; 5-spinning chamber; 6-quartz glass windows; 7-magnetic door-inhale; 8-liquid storage tank rack; 9-a liquid storage tank; 10-an electrical wire; 11-an electrospinning needle; 12-a spinning needle head; 13-an electrostatic generator; 14-receiving the tray.
Detailed Description
In order to achieve the purpose, the invention provides the following technical scheme: the hydrophobic modified SiO2The preparation method of the grafted polyvinyl alcohol super-hydrophobic fiber membrane comprises the following steps:
(1) mixing SiO2With methyl propaneAdding glycidyl enoate into an N, N-dimethylformamide solvent with the mass ratio of 100:200-300, performing ultrasonic dispersion in an ultrasonic device, adding a sulfuric acid solution, reacting at 90-110 ℃ for 8-12h in a nitrogen atmosphere, filtering, washing and drying in vacuum to obtain the hydrophobically modified alkenyl SiO2；
(2) Adding polyvinyl alcohol and thioglycollic acid into a 4-6% sulfuric acid solution, reacting for 2-4h at 70-90 ℃ with the mass ratio of the two reactants being 100:80-150, dialyzing and purifying to obtain the thiolated polyvinyl alcohol;
(3) the sulfhydrylation polyvinyl alcohol and the hydrophobic modified alkenyl SiO2Adding into absolute ethanol solution with the mass ratio of two reactants of 100:120-200, ultrasonically dispersing at 30-40 deg.C under 45-65Mw/cm2Under the illumination intensity, ultraviolet irradiation reaction is carried out for 30-45min, and separation and washing are carried out to obtain the polyvinyl alcohol grafted nano SiO2。
(4) Then in the electrostatic spinning machine, the electrostatic spinning machine comprises a control console, a display and a control button are arranged on the front side of the control console, a heat dissipation window is arranged on the right side of the control console, a spinning bin is fixedly connected above the control console, the spinning bin is movably connected with a quartz glass window, a magnetic door stopper is arranged in the spinning bin, a liquid storage tank rack is fixedly connected in the spinning bin, a liquid storage tank is fixedly connected with the liquid storage tank rack, the liquid storage tank is movably connected with an electrostatic spinning needle through a wire, the electrostatic spinning needle is provided with a spinning needle head, an electrostatic generator is fixedly connected in the spinning bin, a receiving plate rack is fixedly connected in the spinning bin, the solution flow rate is 2-3mL/h under the spinning voltage of 20-25KV, the receiving distance is 82Grafting polyvinyl alcohol super-hydrophobic fiber membrane.
Example 1
(1) Mixing SiO2Adding glycidyl methacrylate and N, N-dimethylformamide solvent with the mass ratio of 100:200 into an ultrasonic device, ultrasonically dispersing, adding sulfuric acid solution, reacting at 90 ℃ for 8h in the nitrogen atmosphere, filtering, washing, and vacuum drying to obtain the hydrophobically modified alkenyl SiO2；
(2) Adding polyvinyl alcohol and thioglycollic acid into a 4% sulfuric acid solution, reacting for 2 hours at 70 ℃ with the mass ratio of the two reactants being 100:80, and dialyzing and purifying to obtain the thiolated polyvinyl alcohol;
(3) the sulfhydrylation polyvinyl alcohol and the hydrophobic modified alkenyl SiO2Adding into anhydrous ethanol solution at a mass ratio of 100:120, ultrasonic dispersing at 30 deg.C under 45Mw/cm2Under the illumination intensity, the reaction is carried out for 30min by ultraviolet irradiation, and the polyvinyl alcohol grafted nano SiO is obtained after separation and washing2。
(4) Then in the electrostatic spinning machine, the electrostatic spinning machine comprises a control console, a display and a control button are arranged on the front side of the control console, a heat dissipation window is arranged on the right side of the control console, a spinning bin is fixedly connected above the control console, the spinning bin is movably connected with a quartz glass window, a magnetic door stopper is arranged in the spinning bin, a liquid storage tank rack is fixedly connected in the spinning bin, a liquid storage tank is fixedly connected with the liquid storage tank rack, a liquid storage tank is movably connected with an electrostatic spinning needle through a wire, the electrostatic spinning needle is provided with a spinning needle head, an electrostatic generator is fixedly connected in the spinning bin, a receiving plate rack is fixedly connected in the spinning bin, the solution flow rate is 2mL/h under the spinning voltage of 20KV, the receiving distance2Grafting polyvinyl alcohol super-hydrophobic fiber membrane.
Example 2
(1) Mixing SiO2Adding glycidyl methacrylate and N, N-dimethylformamide solvent with the mass ratio of 100:240 into an ultrasonic device, ultrasonically dispersing in the ultrasonic device, adding sulfuric acid solution, reacting at 98 ℃ for 9h in the nitrogen atmosphere, filtering, washing, and vacuum drying to obtain the hydrophobically modified alkenyl SiO2；
(2) Adding polyvinyl alcohol and thioglycollic acid into a 5% sulfuric acid solution, reacting for 3 hours at 80 ℃ with the mass ratio of the two reactants being 100:120, and dialyzing and purifying to obtain the thiolated polyvinyl alcohol;
(3) the sulfhydrylation polyvinyl alcohol and the hydrophobic modified alkenyl SiO2Adding into anhydrous ethanol solution at a mass ratio of 100:140, ultrasonic dispersing at 35 deg.C and 50Mw/cm2Reacting for 35min under ultraviolet irradiation at illumination intensity, separating and washing to obtainPolyvinyl alcohol grafted nano SiO2。
(4) Then in the electrostatic spinning machine, the electrostatic spinning machine comprises a control console, a display and a control button are arranged on the front side of the control console, a heat dissipation window is arranged on the right side of the control console, a spinning bin is fixedly connected above the control console, the spinning bin is movably connected with a quartz glass window, a magnetic door stopper is arranged in the spinning bin, a liquid storage tank rack is fixedly connected in the spinning bin, a liquid storage tank is fixedly connected with the liquid storage tank rack, a liquid storage tank is movably connected with an electrostatic spinning needle through a wire, the electrostatic spinning needle is provided with a spinning needle head, an electrostatic generator is fixedly connected in the spinning bin, a receiving plate rack is fixedly connected in the spinning bin, the solution flow rate is 2mL/h under the spinning voltage of 22KV, the receiving distance2Grafting polyvinyl alcohol super-hydrophobic fiber membrane.
Example 3
(1) Mixing SiO2Adding glycidyl methacrylate and N, N-dimethylformamide solvent with the mass ratio of 100:260 into an ultrasonic device, ultrasonically dispersing, adding sulfuric acid solution, reacting at 105 ℃ for 10h in the nitrogen atmosphere, filtering, washing, and vacuum drying to obtain the hydrophobically modified alkenyl SiO2；
(2) Adding polyvinyl alcohol and thioglycollic acid into a 4-6% sulfuric acid solution, reacting for 3 hours at 80 ℃ with the mass ratio of the two reactants being 100:135, and dialyzing and purifying to obtain the thiolated polyvinyl alcohol;
(3) the sulfhydrylation polyvinyl alcohol and the hydrophobic modified alkenyl SiO2Adding into anhydrous ethanol solution at a mass ratio of 100:160, ultrasonic dispersing at 35 deg.C and 60Mw/cm2Under the illumination intensity, the ultraviolet irradiation reaction is carried out for 40min, and the polyvinyl alcohol grafted nano SiO is obtained after separation and washing2。
(4) Then in the electrostatic spinning machine, the electrostatic spinning machine includes the control cabinet, and the control cabinet openly is provided with display and control button, and the control cabinet right side is provided with the heat dissipation window, and fixedly connected with spinning storehouse in the control cabinet top, spinning storehouse swing joint have the quartz glass window, and the spinning storehouse is provided with the magnetism door-inhale, fixedly connected with stock solution tank holder in the spinning storehouse, and the stock solution tank holder is solidFixedly connected with a liquid storage tank, wherein the liquid storage tank is movably connected with an electrostatic spinning needle through a wire, the electrostatic spinning needle is provided with a spinning needle head, an electrostatic generator is fixedly connected in a spinning bin, a receiving plate frame is fixedly connected in the spinning bin, the solution flow rate is 3mL/h and the receiving distance is 10cm under the spinning voltage of 23KV, spinning is carried out to form a film, and the hydrophobic modified SiO is obtained2Grafting polyvinyl alcohol super-hydrophobic fiber membrane.
Example 4
(1) Mixing SiO2Adding glycidyl methacrylate and N, N-dimethylformamide solvent with the mass ratio of 100:300 into an ultrasonic device, ultrasonically dispersing, adding sulfuric acid solution, reacting at 110 ℃ for 12h in the nitrogen atmosphere, filtering, washing, and vacuum drying to obtain the hydrophobically modified alkenyl SiO2；
(2) Adding polyvinyl alcohol and thioglycollic acid into a 6% sulfuric acid solution, reacting for 4 hours at 90 ℃ with the mass ratio of the two reactants being 100:150, and dialyzing and purifying to obtain the thiolated polyvinyl alcohol;
(3) the sulfhydrylation polyvinyl alcohol and the hydrophobic modified alkenyl SiO2Adding into anhydrous ethanol solution at a mass ratio of 100:200, ultrasonic dispersing at 40 deg.C under 65Mw/cm2Under the illumination intensity, ultraviolet irradiation reaction is carried out for 45min, and separation and washing are carried out to obtain the polyvinyl alcohol grafted nano SiO2。
(4) Then in the electrostatic spinning machine, the electrostatic spinning machine comprises a control console, a display and a control button are arranged on the front side of the control console, a heat dissipation window is arranged on the right side of the control console, a spinning bin is fixedly connected above the control console, the spinning bin is movably connected with a quartz glass window, a magnetic door stopper is arranged in the spinning bin, a liquid storage tank rack is fixedly connected in the spinning bin, a liquid storage tank is fixedly connected with the liquid storage tank rack, a liquid storage tank is movably connected with an electrostatic spinning needle through a wire, the electrostatic spinning needle is provided with a spinning needle head, an electrostatic generator is fixedly connected in the spinning bin, a receiving plate rack is fixedly connected in the spinning bin, the solution flow velocity is 3mL/h under the spinning voltage of 25KV, the receiving distance2Grafting polyvinyl alcohol super-hydrophobic fiber membrane.
Comparative example 1
(1) Mixing SiO2Adding glycidyl methacrylate and N, N-dimethylformamide solvent with the mass ratio of 100:120 into an ultrasonic device, ultrasonically dispersing, adding sulfuric acid solution, reacting at 90 ℃ for 8h in the nitrogen atmosphere, filtering, washing, and vacuum drying to obtain the hydrophobically modified alkenyl SiO2；
(2) Adding polyvinyl alcohol and thioglycollic acid into a 4% sulfuric acid solution, reacting for 2 hours at 70 ℃ with the mass ratio of the two reactants being 100:40, and dialyzing and purifying to obtain the thiolated polyvinyl alcohol;
(3) the sulfhydrylation polyvinyl alcohol and the hydrophobic modified alkenyl SiO2Adding into anhydrous ethanol solution at a mass ratio of 100:60, ultrasonic dispersing at 30 deg.C under 45Mw/cm2Under the illumination intensity, the reaction is carried out for 30min by ultraviolet irradiation, and the polyvinyl alcohol grafted nano SiO is obtained after separation and washing2。
(4) Then in the electrostatic spinning machine, the electrostatic spinning machine comprises a control console, a display and a control button are arranged on the front side of the control console, a heat dissipation window is arranged on the right side of the control console, a spinning bin is fixedly connected above the control console, the spinning bin is movably connected with a quartz glass window, a magnetic door stopper is arranged in the spinning bin, a liquid storage tank rack is fixedly connected in the spinning bin, a liquid storage tank is fixedly connected with the liquid storage tank rack, a liquid storage tank is movably connected with an electrostatic spinning needle through a wire, the electrostatic spinning needle is provided with a spinning needle head, an electrostatic generator is fixedly connected in the spinning bin, a receiving plate rack is fixedly connected in the spinning bin, the solution flow rate is 2mL/h under the spinning voltage of 20KV, the receiving distance2Grafting polyvinyl alcohol super-hydrophobic fiber membrane.
The contact angles of the super-hydrophobic fiber membranes of the examples and the comparative examples and the super-hydrophobic fiber membranes placed in an air-draft kitchen for three months are measured by using a BDL-SDJY contact angle tester, and the test standard is GB/T24368-.
| Item | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 |
| Static contact angle | 152.51° | 153.73° | 156.24° | 151.09° | 102.70° |
| Standing time (moon) | 3 | 3 | 3 | 3 | 3 |
| Static contact angle | 149.76° | 151.14° | 152.40° | 146.73° | 82.59° |
Claims (6)
1. DredgingWater modified SiO2The grafted polyvinyl alcohol super-hydrophobic fiber membrane is characterized in that: the hydrophobic modified SiO2The preparation method of the grafted polyvinyl alcohol super-hydrophobic fiber membrane comprises the following steps:
(1) mixing SiO2Adding glycidyl methacrylate and N, N-dimethylformamide solvent, performing ultrasonic dispersion in an ultrasonic device, adding sulfuric acid solution, reacting at 90-110 deg.C for 8-12h in nitrogen atmosphere, filtering, washing, and vacuum drying to obtain hydrophobically modified alkenyl SiO2；
(2) Adding polyvinyl alcohol and thioglycollic acid into 4-6% sulfuric acid solution, reacting at 70-90 deg.C for 2-4h, dialyzing and purifying to obtain thiolated polyvinyl alcohol;
(3) the sulfhydrylation polyvinyl alcohol and the hydrophobic modified alkenyl SiO2Adding into absolute ethanol solution, ultrasonic dispersing, performing ultraviolet irradiation reaction, separating and washing to obtain polyvinyl alcohol grafted nanometer SiO2。
(4) Then spinning and forming a film in an electrostatic spinning machine at a spinning voltage of 20-25KV and a solution flow rate of 2-3mL/h and a receiving distance of 8-12cm to obtain the hydrophobically modified SiO2Grafting polyvinyl alcohol super-hydrophobic fiber membrane.
2. Hydrophobically modified SiO according to claim 12The grafted polyvinyl alcohol super-hydrophobic fiber membrane is characterized in that: SiO in the step (1)2The mass ratio of the monomer to the glycidyl methacrylate is 100: 200-300.
3. Hydrophobically modified SiO according to claim 12The grafted polyvinyl alcohol super-hydrophobic fiber membrane is characterized in that: the mass ratio of the polyvinyl alcohol to the thioglycolic acid in the step (2) is 100: 80-150.
4. Hydrophobically modified SiO according to claim 12The grafted polyvinyl alcohol super-hydrophobic fiber membrane is characterized in that: in the step (3), thiolated polyvinyl alcohol and hydrophobically modified alkenylated SiO2The mass ratio of (1) is 100: 120-200.
5. Hydrophobically modified SiO according to claim 12The grafted polyvinyl alcohol super-hydrophobic fiber membrane is characterized in that: in the step (3), the reaction temperature of ultraviolet irradiation is 30-40 ℃, and the ultraviolet intensity is 45-65Mw/cm2The irradiation time is 30-45 min.
6. Hydrophobically modified SiO according to claim 12The grafted polyvinyl alcohol super-hydrophobic fiber membrane is characterized in that: the electrostatic spinning machine comprises a control console in the step (4), a display and a control button are arranged on the front side of the control console, a heat dissipation window is arranged on the right side of the control console, a spinning bin is fixedly connected to the upper portion of the control console, the spinning bin is movably connected with a quartz glass window, a magnetic door stopper is arranged on the spinning bin, a liquid storage tank frame is fixedly connected to the inside of the spinning bin, a liquid storage tank is fixedly connected with a liquid storage tank, an electrostatic spinning needle is movably connected to the liquid storage tank through an electric wire, the electrostatic spinning needle is provided with a spinning needle head, an electrostatic generator is fixedly connected to the inside of the.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113668139A (en) * | 2021-09-17 | 2021-11-19 | 厦门大学 | Flexible high-temperature-resistant SiO2Preparation method of ceramic nanofiber membrane |
| CN117682499A (en) * | 2024-02-02 | 2024-03-12 | 四川易纳能新能源科技有限公司 | Super-hydrophobic modified ferric sodium pyrophosphate positive electrode material, and preparation method and application thereof |
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