CN109137102B - A kind of preparation method of imitating spider silk fiber structure with directional hydrophobicity - Google Patents

Abstract

The invention relates to a preparation method of a spider silk-like fiber structure with directional hydrophobicity, which is synthesized by an electrospinning machine. Oil-water separation can separate most of them under the action of gravity, but oil-water mixing at the oil-water interface is difficult to separate. In a dynamic flow environment, oil-water mixing will form water-in-oil or oil-in-water, imitating the water droplet orientation of the spider silk spindle The phenomenon of water collection caused by the flow, that is, the surface energy difference between the spindle fiber and the spindle node, which is a special structure like spider silk, causes the Laplace force to make the water droplets move and gather together, and then the oil and water are layered due to gravity. In industrial and domestic sewage, most of the oily sewage exists in the form of emulsified oil, which realizes the accumulation of oil and water and stratifies them, and then collects and processes them to achieve efficient, green, and environmentally friendly oil-water separation, and develop a new oil-water separation mechanical device.

Description

A kind of preparation method of imitating spider silk fiber structure with directional hydrophobicity

technical field

The invention relates to electrospinning technology, in particular to a separation water-in-oil polymer silk with a spider silk-like structure and a method for simply preparing the polymer silk.

Background technique

In recent years, various oil-water separation technologies and new materials have come out one after another. Although some general methods, such as gravity separation, centrifugation, chemical oxidation, biological aluminum treatment, electrocoalescence, and float method are widely used, due to the low separation efficiency, high operating cost, and the production of secondary pollutants, they cannot meet the needs of large-scale wastewater treatment. increasingly stringent requirements. Therefore, it is very necessary to develop efficient and green oil-water separation methods. The electrospinning method is simple and effective. Since the special surface wettability is controlled by surface chemistry and morphology, the methods for preparing superhydrophobic and superoleophilic surfaces can be divided into the following two categories: 1) Increasing surface roughness by forming micro/nanostructures on the substrate ; (2) Chemical modification of micro/nanostructured surfaces with materials with lower surface energy. Various approaches have been proposed to realize this special surface, including template synthesis, chemical etching, crystallization control, phase reversal, electrochemical deposition, self-assembly, electrospinning, chemical vapor deposition, one-step spraying, etc. Electrospinning is a simple and feasible method for the production of nanoscale to submicron-scale fibers in polymer solutions. Electrospun nanofibers with nanometer diameter, large specific surface area and small pore size have broad application prospects in the fields of protective clothing, biomaterials, tissue scaffolds, and nanomaterials.

Separation of water-in-oil, oil-water separation can separate most of them under the action of gravity, but it is difficult to separate oil-water mixing at the oil-water interface. In a dynamic flow environment, oil-water mixing will form water-in-oil or oil-in-water, imitating spider silk One of the effective methods for oil purification is the directional movement of water, which is caused by the directional flow of water droplets in the spindle, that is, the Laplace force caused by the surface energy difference between the nodes and points of the special structure like spider silk After making the water droplets move and gather together, the oil and water are then stratified by gravity. In industrial and domestic sewage, most of the oily sewage exists in the form of emulsified oil, which realizes oil-water accumulation and stratification, and then collects and treats to achieve efficient, green, and environmentally friendly oil-water separation, and develop a new oil-water separation mechanical device.

Electrospinning has been shown to be a simple and feasible method to produce fibers of polymer solutions with diameters ranging from nanometers to submicrometers. The nano-diameter, large specific surface area and small pore size of electrospun nanofibers have broad application prospects in the fields of protective clothing, biomaterials, tissue scaffolds, nanocomposites, sensors, and thin films. However, electrospun fibers are mostly produced in the form of randomly oriented nonwovens with relatively low mechanical strength and difficult to tailor fiber structures. Limiting their applications, therefore, the development of continuous yarns made from nanofibers has attracted considerable interest as an attractive method of stimulation. Electrospinning is a simple and feasible method of spinning one or more polymers into desired fibers. In addition to the control of the electrospinning machine, the structure of the fiber can also be changed by other external means. his material itself. Electrospun fibers are widely used in protective clothing, biomaterials, tissue scaffolds, nanocomposites, sensors, and filtration. Separating the water-in-oil, purifying the oil, overcoming the low water-collecting efficiency of the existing water-collecting method, cannot meet the water demand of people in the vast water-scarce areas, and also has the defects of high water-collecting cost and unfriendly environment. Based on the research on the water-collecting phenomenon of natural spider silk in nature, the periodic spindle knot structure of spider silk is imitated to provide a water-collecting polymer silk with high water-collecting efficiency, low cost and simple preparation of spider silk-like structure.

SUMMARY OF THE INVENTION

The purpose of the present invention is to form a needle structure of spider silk fibers, and to provide a method for preparing a spider silk-like fiber structure with directional hydrophobicity.

The object of the present invention is to realize through the following technical solutions:

A method for preparing a spider silk-like fiber structure with directional hydrophobicity. The fibers are divided into spindle filaments and spindle segments, the spindle filaments and the spindle segments are PMMA and PS respectively, gas-phase nano-SiO2 is added to the PS solution, and the solution of PS and gas-phase SiO2 is added. The solution of PMMA and PMMA is spun on a stainless steel mesh on a tin foil by electrospinning; it specifically includes the following steps:

A. Preparation of solution: PS (1-16%), fumed silica (0-2.67%) and PMMA (0.5-4%) were added to a 1:4 mixture of THF and DFM, and stirred magnetically for 12h After the drug is completely dissolved, it is sonicated for half an hour and then used for later use;

B. Coaxial needle production: Select the flat-headed needle with the appropriate inner and outer apertures, punch a hole in the large-diameter flat-headed needle, assemble the three flat-headed needles with a hot glue gun, and then connect a rubber tube to transmit the outer The solution of the diameter needle is assembled with a hot glue gun and cooled, after ultrasonic cleaning with acetone, ultrasonic cleaning with absolute ethanol, drying at room temperature and sealing for use;

C. Preparation of water-in-oil emulsion: take 50ml of oil, add 1ml of water to the oil, one cup without stirring, one cup with stirring, and one cup with stirring and add 1ml of Span 80 with a pipette, and there is no regurgitation phenomenon after standing for a day to spare;

D. Parameter setting of electrospinning machine: take the empty syringe and preset the final bolus stop distance of the bolus device, stick the tin foil paper on the cylindrical receiver, and then stick the stainless steel mesh on the tin foil paper. The solution is put into the syringe, installed on the injector, after connecting the voltage, set the positive and negative voltage difference, the speed of the outer injector, the speed of the inner injector, the receiving speed of the cylindrical receiver, the left and right movement speed, start Spinning, namely preparing the described spider silk-like fiber structure with directional hydrophobicity.

Step A, the MW of the PS is 104.14, the molecular weight of PMMA is 100.11, the fumed silica Degussa A200, the mass concentration of tetrahydrofuran is 0.88g/ml, and the mass concentration of N,N-dimethylformamide is 0.94g/ ml.

In step B, the stainless steel mesh is cleaned by acetone and absolute ethanol and then vacuum-dried.

In step C, the length of the flat-headed needle is 25 cm and 9 cm, and the diameter of the flat-headed needle is 0.4-2.0 mm.

In step D, the voltage of the electrospinning is 15KV.

In step E, the speed of the outer bolus injector is 0.5 mm/min, the speed of the inner bolus injector is 0.8 mm/min, and the receiving speed of the cylindrical receiver is 60 mm/min.

Step E, the temperature of the electrospinning machine is 25°C and the humidity is 5%.

Step E, the receiving distance is 15cm.

Step E, stainless steel mesh 150 mesh 0.06 mm.

The technical effect of the present invention is:

The invention provides a simple and convenient production method of imitating spider silk structure. The present invention is inspired by the phenomenon that spider silk is decorated by crystal water droplets in nature. By observing the microstructure of spider silk, the polymer solution is used to make silk through an electrospinning machine, and it is controlled by a coaxial needle as shown in Figure 1. The polymer solution can simply and directly form the polymer of the imitation spider silk, and the imitation spider silk fibers are coaxial, and the spindle nodes and the spindle fibers of the imitation spider silk fibers formed are of different components. Two kinds of spider silk fibers woven from PS and PMMA, which have a large difference in surface energy and are economical, are selected to have directional water transport, and the addition of fumed nano-silica increases its directional water transport and also increases its resistance to water. The driving force of water droplets. The previous spider silk-like fiber structure has insufficient driving force for the separation of water-in-oil. The addition of gas-phase nano-SiO2 to the spindle section increases the driving force between the spindle fiber and the spindle section, thereby preparing a cycle similar to spider silk. The spider silk-like structure of the sexually arranged spindle structure enables the separation of water-in-oil.

Description of drawings

Fig. 1 is the needle that the preparation method of the imitation spider silk fiber structure with directional hydrophobic energy separation water-in-oil emulsion adopts;

Fig. 2 is the needle connection adopted by the preparation method of the imitation spider silk fiber structure with directional hydrophobic energy separation water-in-oil emulsion;

Fig. 3 is the morphology of a spindle segment magnified 5000 times with directional hydrophobic spider silk fiber structure under the microscope;

Figure 4 shows the morphology of a spider silk fiber with directional hydrophobicity under a microscope magnified 5000 times;

Figure 5 is the morphology of a spindle segment with directional hydrophobic spider silk-like fiber structure under the scanning electron microscope.

Detailed ways

A method for preparing a spider silk-like fiber structure with directional hydrophobicity, the fibers are divided into spindle filaments and spindle segments, the spindle filaments and spindle segments are PMMA and PS respectively, PS is dissolved in THF and DMF solutions, and then added to the PS solution. Gas-phase nano-SiO2, PS and gas-phase SiO2 solution and PMMA solution were spun on a stainless steel mesh on tin foil by electrospinning.

Specifically include the following steps:

Step A, drying PS (MW=104.14) and PMMA (MW=100.11) at a temperature of 60°C for more than 6h, then weighing 0.193mg of PMMA, 0.386mg of PS and 0.064mg of gas-phase nano-silica;

Step B, THF (mass concentration of tetrahydrofuran 0.88g/ml) and DFM (mass concentration of N,N-dimethylformamide 0.94g/ml) get 5ml after mixing with 1:4 and add it to the PMMA beaker respectively and In PS (fumed nano-silica Degussa A200), the drug was completely dissolved after 12 hours of magnetic stirring, and then sonicated for half an hour to be uniform for later use;

Step C, coaxial needle production: the length of the flat-headed needle is 25cm and 9cm, the diameter of the flat-headed needle is 0.4-2.0mm, select the flat-headed needle with the appropriate inner and outer apertures, punch a hole in the large-aperture flat-headed needle, and insert the three flat-headed needles. The needles were assembled with a hot glue gun, and then a hose was connected to transfer the solution of the outer diameter needle, assembled with a hot glue gun, cooled, ultrasonically cleaned with acetone, then ultrasonically cleaned with absolute ethanol, dried at room temperature and sealed spare;

Step D. Preparation of water-in-oil emulsion: take 50ml of oil, add 1ml of water to the oil, one cup without stirring, one cup stirring, one cup stirring and adding 1ml Span 80 with a pipette, and no regurgitation occurs after standing for a day phenomenon for backup;

Step E. Parameter setting of the electrospinning machine: take the empty syringe and preset the last bolus stop distance of the bolus device, stick the tin foil on the cylindrical receiver, and then clean the vacuum-dried stainless steel mesh with acetone and anhydrous ethanol. 150 mesh 0.06 mm is glued on the tin foil paper, the receiving distance is 15 cm, the solution containing ultrasonic uniform is put into the syringe, and it is installed on the injector. After connecting the voltage, set the positive and negative voltage difference 15KV. The speed is 0.5mm/min, the speed of the inner injector is 0.8mm/min, the receiving speed of the cylindrical receiver is 60mm/min, the left and right moving speed, the temperature of the electrospinning machine is 25 ℃, the humidity is 5%, and the spinning is started. The described spider silk-like fiber structure with directional hydrophobicity.

Claims (9)

1. a kind of imitation spider silk fiber structure preparation method with directional hydrophobicity is characterized in that: The fibers are divided into spindle filaments and spindle segments. The spindle filaments and spindle segments are PMMA and PS, respectively. Gas-phase nano-SiO2 is added to the PS solution, and the PS and gas-phase SiO2 solution and PMMA solution are electrospinned on tin foil. Stainless steel mesh; specifically includes the following steps: A. Preparation of solution: 1-16% PS, 0-2.67% fumed silica and 0.5-4% PMMA are added to a 1:4 mixture of THF and DFM, and the drug is completely dissolved after magnetic stirring for 12 hours. Ultrasound for half an hour after uniformity; B. Coaxial needle production: punch a hole in a large-diameter flat-headed needle, assemble the three flat-headed needles with a hot glue gun, and then connect a rubber tube to transfer the solution of the outer diameter needle, and assemble them with a hot glue gun After cooling, ultrasonically clean with acetone, then ultrasonically clean with absolute ethanol, dry at room temperature and seal for later use; C. Preparation of water-in-oil emulsion: take 50ml of oil, add 1ml of water to the oil, one cup without stirring, one cup with stirring, and one cup with stirring and add 1ml of Span 80 with a pipette, and there is no regurgitation phenomenon after standing for a day to spare; D. Parameter setting of electrospinning machine: take the empty syringe and preset the final bolus stop distance of the bolus device, stick the tin foil paper on the cylindrical receiver, and then stick the stainless steel mesh on the tin foil paper. The solution is put into the syringe, installed on the injector, after connecting the voltage, set the positive and negative voltage difference, the speed of the outer injector, the speed of the inner injector, the receiving speed of the cylindrical receiver, the left and right movement speed, start Spinning, namely preparing the described spider silk-like fiber structure with directional hydrophobicity. 2. a kind of imitation spider silk fiber structure preparation method with directional hydrophobicity according to claim 1, is characterized in that: step A, the MW104.14 of described PS, the molecular weight 100.11 of PMMA, fumed silica Degu Sai A200, the mass concentration of tetrahydrofuran is 0.88g/ml, and the mass concentration of N,N-dimethylformamide is 0.94g/ml. 3. A kind of preparation method of imitation spider silk fiber structure with directional hydrophobicity according to claim 1, is characterized in that: in step B, described stainless steel mesh is vacuum-dried after cleaning by acetone and absolute ethanol. 4 . The method for preparing a spider silk-like fiber structure with directional hydrophobicity according to claim 1 , wherein in step C, the length of the flat-tipped needle is 25 cm and 9 cm, and the diameter of the flat-tipped needle is 0.4-2.0 mm. 5 . 5 . The method for preparing a spider silk-like fiber structure with directional hydrophobicity according to claim 1 , wherein in step D, the voltage of the electrospinning is 15KV. 6 . 6. a kind of imitation spider silk fiber structure preparation method with directional hydrophobicity according to claim 1, is characterized in that: in step E, the speed of the outer injector is 0.5mm/min, and the speed of the inner injector is 0.8mm/min. min, the receiving speed of the cylindrical receiver is 60mm/min. 7 . The method for preparing a spider silk-like fiber structure with directional hydrophobicity according to claim 1 , wherein in step E, the temperature of the electrospinning machine is 25° C. and the humidity is 5%. 8 . 8 . The method for preparing a spider silk-like fiber structure with directional hydrophobicity according to claim 1 , wherein in step E, the receiving distance is 15 cm. 9 . 9 . The method for preparing a spider silk-like fiber structure with directional hydrophobicity according to claim 1 , wherein in step E, the stainless steel mesh is 150 mesh 0.06 mm. 10 .

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