CN111494987B - Fluorine-free super-hydrophobic fabric and preparation method thereof - Google Patents
Fluorine-free super-hydrophobic fabric and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a fluorine-free super-hydrophobic fabric and a preparation method thereof. The super-hydrophobic fabric comprises a substrate and a coating layer arranged on the surface of the substrate; wherein the substrate is an alkalized polyester fabric; the coating is a water-based organic silicon polyurethane coating. The preparation method of the super-hydrophobic fabric comprises the steps of spraying the aqueous organic silicon polyurethane solution on the alkalized polyester fabric, curing and carrying out heat treatment to obtain the super-hydrophobic fabric. The invention synthesizes the water-based organic silicon polyurethane through molecular design, provides low surface energy for the preparation of the super-hydrophobic fabric, and skillfully utilizes alkali treatment to prepare the micro-nano structure required by the super-hydrophobic fabric on the polyester fabric. The method for preparing the super-hydrophobic fabric is simple, convenient, efficient, economical and environment-friendly, can effectively realize oil-water separation, is free of fluorine and particles, and is easier to industrialize.
Description
Technical Field
The invention relates to the technical field of fabrics, in particular to a fluorine-free super-hydrophobic fabric and a preparation method thereof.
Background
In recent years, the potential pollution of oily wastewater to the environment and the influence on human health have attracted attention from countries around the world due to the increasing amount of industrial oily wastewater and the frequent occurrence of oil spill accidents. However, the current oily water treatment technology has disadvantages in the aspects of universality, usability, adaptability and the like of oil-water separation due to low separation efficiency, poor reusability, high running cost, complex operation procedures and the like. Therefore, efficient separation of oily wastewater treatment has become an urgent global challenge. Recent studies have shown that superhydrophobic surfaces (SFS) are considered to be a simple and efficient method for oil-water separation.
A superhydrophobic surface can be defined as a surface having a Water Contact Angle (WCA) greater than 150 ° and a Water Sliding Angle (WSA) less than 10 °. Generally, the hierarchical roughness (including micro-and nanostructures) and low surface energy components are key to achieving superhydrophobic surfaces.
A common strategy to create the desired micro-nano topography is to add micro-or nanoparticles. However, the combination with high-cost nanoparticles may increase costs, and sometimes the nanoparticles may adversely affect the original physical properties of the substrate. In addition, these particles are easily exfoliated, resulting in poor superhydrophobicity and potential toxicity. Fluorine-containing compounds are widely used for surface modification or molecular fluorination of micro/nano-sized particles due to their low surface energy. The preparation of SFS by adopting fluorine-containing polymer and physically doped inorganic substances is the conventional preparation method at present, but the methods have the defects of long reaction time, complex and complicated process, poor environmental protection and the like. Fluorine compounds have been limited due to their harmful organisms and environment, and thus, there are many studies on silicon-free and particle-free materials.
Up to now, methods such as electrospinning, photolithography, chemical vapor deposition, phase separation, templating, layer-by-layer assembly, hydrothermal synthesis, electrochemical deposition, dip coating, spray coating, and sol-gel processes have been used to prepare superhydrophobic surfaces on various substrates, including metal meshes, textiles, filters, hydrogels, polymer films and porous sponges, to obtain oil-water separated superhydrophobic surfaces. Of all these techniques, dip coating and spray coating have found widespread use due to their simplicity, efficiency and cost effectiveness. The fabric is a material widely applied to daily life, has the obvious advantages of low cost, good flexibility, good chemical stability, strong absorption capacity and the like, and is considered as an ideal oil-water separation membrane.
At present, some methods for preparing fluorine-free and particle-free super-hydrophobic fabrics exist, but the general process is complex and difficult to industrialize.
Disclosure of Invention
In order to overcome the problems of the prior art in preparing the fluorine-free and particle-free super-hydrophobic fabric, the invention aims to provide the fluorine-free and particle-free super-hydrophobic fabric which is simple, convenient, efficient, economical and environment-friendly and can effectively realize oil-water separation, and the invention aims to provide the preparation method of the super-hydrophobic fabric.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a fluorine-free super-hydrophobic fabric, which comprises a substrate and a coating arranged on the surface of the substrate; wherein the substrate is an alkalized polyester fabric; the coating is a water-based organic silicon polyurethane coating.
Preferably, in the super-hydrophobic fabric, the alkalized polyester fabric is obtained by soaking polyester fibers in alkali liquor for treatment.
Preferably, in the alkalization treatment, the alkali in the alkali liquor is at least one selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate; further preferably, the alkali in the alkaline solution is at least one selected from sodium hydroxide and potassium hydroxide. In some preferred embodiments of the present invention, the alkaline solution is sodium hydroxide solution. The concentration of the sodium hydroxide solution is preferably 1mol/L to 5 mol/L.
Preferably, in the alkalization treatment, the treatment temperature is 50-90 ℃; the treatment time is 30 min-90 min.
Preferably, in the super-hydrophobic fabric, the preparation component of the aqueous organosilicon polyurethane comprises: dihydroxy polydimethylsiloxane, 3-methoxy-1, 2-propanediol, isophorone diisocyanate, dimethylol butyric acid and trihydroxy propane.
In the preparation components of the aqueous organosilicon polyurethane, dihydroxyl polydimethylsiloxane is used as a chain extender.
Preferably, the dihydroxypolydimethylsiloxane has the structural formula (I):
in the formula (I), m and n are respectively any positive integer.
More preferably, in the dihydroxy polydimethylsiloxane having the structure represented by formula (I), m is 1 to 13, and n is 1 to 54.
Preferably, the preparation component of the water-based organic silicon polyurethane also comprises an end-capping agent; more preferably, the end-capping agent is monohydroxy polydimethylsiloxane; still more preferably, the monohydroxypolydimethylsiloxane has the formula (II):
in the formula (II), x is any positive integer.
More preferably, in the monohydroxypolydimethylsiloxane having the structure represented by formula (ii), x is 3 to 4.
The invention also provides a preparation method of the super-hydrophobic fabric.
A preparation method of the fluorine-free super-hydrophobic fabric comprises the following steps: and spraying the aqueous organic silicon polyurethane solution on the alkalized polyester fabric, curing and carrying out heat treatment to obtain the super-hydrophobic fabric.
Preferably, in the preparation method of the super-hydrophobic fabric, the volume of the aqueous organic silicon polyurethane solution sprayed on each square meter of the alkalized polyester fabric is more than or equal to 100 mL; further preferably, the volume of the aqueous organic silicon polyurethane solution sprayed on each square meter of the alkalized polyester fabric is 100 mL-250 mL.
Preferably, in the preparation method of the super-hydrophobic fabric, the preparation method of the aqueous organosilicon polyurethane comprises the following steps:
1) mixing dihydroxy polydimethylsiloxane, 3-methoxy-1, 2-propanediol, isophorone diisocyanate and a solvent;
2) mixing the mixed solution obtained in the step 1) with dimethylolbutyric acid and trihydroxypropane;
3) adding a catalyst into the solution obtained in the step 2), heating for reaction, and adding amine for neutralization to obtain the water-based organic silicon polyurethane.
Preferably, in step 1) of the method for preparing the aqueous silicone polyurethane, the molar ratio of the bishydroxy polydimethylsiloxane, the 3-methoxy-1, 2-propanediol and the isophorone diisocyanate is 10: (0.3-8): (42.5-52.5).
Preferably, in step 1) of the aqueous silicone polyurethane preparation method, the solvent is at least one selected from the group consisting of N, N' -dimethylformamide, tetrahydrofuran, dimethyl sulfoxide, and acetone. The dosage of the solvent can be adjusted according to actual needs, so that the materials are completely dissolved.
Preferably, in step 2) of the preparation method of the aqueous organosilicon polyurethane, the addition amount of the dimethylolbutyric acid is 3.5-5.5% by mass of the total mass of the bishydroxy polydimethylsiloxane, the 3-methoxy-1, 2-propanediol and the isophorone diisocyanate.
Preferably, in step 2) of the preparation method of the aqueous organosilicon polyurethane, the addition amount of the trihydroxypropane is 0.25-1.25% by mass based on the total mass of the dihydroxy polydimethylsiloxane, the 3-methoxy-1, 2-propanediol and the isophorone diisocyanate.
Preferably, in step 3) of the preparation method of the aqueous organosilicon polyurethane, the catalyst is an organic tin catalyst, and may be at least one selected from dibutyltin dilaurate and stannous octoate.
Preferably, in the step 3) of the preparation method of the aqueous organosilicon polyurethane, the heating reaction is carried out for 4 to 10 hours at the temperature of between 40 and 90 ℃.
In step 3) of the preparation method of the water-based organic silicon polyurethane, a product obtained after heating reaction has a structural formula shown as a formula (III):
in the formula (III), x is any positive integer, R2Expressed as:
R1expressed as:
Preferably, in the compound having the structure represented by the formula (III), x is 3 to 4.
Preferably, in step 3) of the preparation method of the aqueous organosilicon polyurethane, a step of adding a blocking agent for blocking is further included after the heating reaction; more specifically, after the heating reaction is finished, the amount of the residual NCO groups of the system is measured, a blocking agent is added for blocking, and then amine is added for neutralization.
Preferably, in the step 3) of the preparation method of the water-based organic silicon polyurethane, the end-capping agent is monohydroxy polydimethylsiloxane, and the structural formula of the end-capping agent is shown as the formula (II). The molar ratio of blocking agent to the remaining NCO groups of the reaction system is preferably 1: 1.
Preferably, in step 3) of the preparation method of the aqueous organosilicon polyurethane, amine is added for neutralization and salt formation, and the reaction time is preferably 20min to 40 min.
Preferably, in step 3) of the method for preparing aqueous silicone polyurethane, the amine is at least one selected from triethylamine, ethylenediamine and dimethylethanolamine.
Preferably, step 3) of the preparation method of the aqueous organosilicon polyurethane is specifically: adding a catalyst at 45-55 ℃, uniformly mixing, heating to 75-85 ℃, reacting for 5-7 h, measuring the content of the residual NCO groups in the reaction system, adding monohydroxy polydimethylsiloxane with the same molar quantity as the NCO groups, finally adding amine for neutralization, finishing the reaction, and naturally cooling.
Preferably, in the preparation method of the super-hydrophobic fabric, the mass concentration of the aqueous organosilicon polyurethane solution is 8-15%.
Preferably, in the preparation method of the super-hydrophobic fabric, the curing is performed for 1 to 3 hours at the temperature of between 70 and 90 ℃; more preferably, the curing is at 75 ℃ to 85 ℃ for 1.5h to 2.5 h.
Preferably, in the preparation method of the super-hydrophobic fabric, the heat treatment is carried out for 10min to 60min at 160 ℃ to 180 ℃; more preferably, the heat treatment is carried out at 165 to 175 ℃ for 20 to 40 min.
The invention has the beneficial effects that:
the invention synthesizes the water-based organic silicon polyurethane through molecular design, provides low surface energy for the preparation of the super-hydrophobic fabric, and skillfully utilizes alkali treatment to prepare the micro-nano structure required by the super-hydrophobic fabric on the polyester fabric. The method for preparing the super-hydrophobic fabric is simple, convenient, efficient, economical and environment-friendly, can effectively realize oil-water separation, is free of fluorine and particles, and is easier to industrialize.
Drawings
FIG. 1 is a schematic of a synthetic scheme for an aqueous silicone polyurethane;
FIG. 2 is an infrared spectrum of an original polyester fabric (RT), an alkali-treated polyester fabric (AT) and a silicone polyurethane-sprayed polyester fabric (SiPuT);
FIG. 3 is an XPS spectrum of an original polyester fabric;
FIG. 4 is an XPS spectrum of an alkali treated polyester fabric;
FIG. 5 is an XPS spectrum of a spray coated silicone polyurethane polyester fabric;
FIG. 6 is an XPS spectrum of an original polyester fabric at a C1s signal band;
FIG. 7 is an XPS spectrum of an alkali treated polyester fabric at a C1s signal band;
FIG. 8 is an XPS spectrum of a spray silicone polyurethane polyester fabric in a C1s signal band;
FIG. 9 is an XPS spectrum of a Si 2p signal band of a spray coated silicone polyurethane polyester fabric;
FIG. 10 is an AFM diagram; (a) the method comprises the following steps of (a) obtaining a two-dimensional AFM image of an original polyester fabric, (b) obtaining a two-dimensional AFM image of the polyester fabric subjected to alkali treatment, (c) obtaining a two-dimensional AFM image of a sprayed organic silicon polyurethane polyester fabric, (d) obtaining a three-dimensional AFM image of the original polyester fabric, (e) obtaining a three-dimensional AFM image of the polyester fabric subjected to alkali treatment, and (f) obtaining a three-dimensional AFM image of the sprayed organic silicon polyurethane polyester fabric;
FIG. 11 is a scanning electron microscope image of an original polyester fabric (a), an alkali-treated polyester fabric (b), and a silicone polyurethane-sprayed polyester fabric (c);
FIG. 12 is a schematic view of an oil-water separation test;
FIG. 13 is a graph of the separation efficiency of superhydrophobic fabrics for different types of oil-water mixtures;
FIG. 14 is a graph of permeation flux of a superhydrophobic fabric for different types of oil-water mixtures;
FIG. 15 is a graph of separation efficiency for 50 oil-water separation tests of a superhydrophobic fabric cycle;
FIG. 16 is a graph of contact angle change for a superhydrophobic fabric cycling 50 oil water separation tests;
FIG. 17 is a graph of the effect of chemical durability of superhydrophobic fabrics in different solvents;
FIG. 18 is a schematic view of an underwater oil absorption test of a fabric;
FIG. 19 is a graph comparing the hydrophobic properties of fabrics; (a) the method comprises the following steps of (a) a schematic diagram of hydrophobic property test of an original fabric and a super-hydrophobic fabric, (b) an effect diagram of hydrophobic property test of the original fabric, and (c) an effect diagram of hydrophobic property test of the super-hydrophobic fabric.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials, reagents or equipment used in the examples are, unless otherwise specified, either conventionally commercially available or may be obtained by methods known in the art. Unless otherwise indicated, the testing or testing methods are conventional in the art.
The structural formulas of the bishydroxypolydimethylsiloxane and the monohydroxypolydimethylsiloxane used in the examples can be respectively shown in the above formulas (I) and (II).
Example 1
Preparation of aqueous organosilicon polyurethane
Referring to the schematic synthesis scheme of FIG. 1, the preparation of the aqueous silicone polyurethane dispersion is illustrated as follows:
(1) after mixing bishydroxy Polydimethylsiloxane (PDMS), 3-methoxy-1, 2-propanediol and isophorone diisocyanate (IPDI) in a molar ratio of 10:0.3:42.5, sufficient N, N' -Dimethylformamide (DMF) was added as a solvent.
(2) And (2) adding dimethylolbutyric acid (DMBA) and Trihydroxypropane (TMP) into the system in the step (1), wherein the adding amount of the dimethylolbutyric acid (DMBA) is 3.5 percent, and the adding amount of the Trihydroxypropane (TMP) is 0.25 percent.
(3) Under the stirring process of 50 ℃, dropwise adding enough dibutyltin dilaurate (DBTDL) into the system, uniformly mixing, raising the temperature of the reaction system to 80 ℃, reacting at constant temperature for 6 hours, measuring the residual NCO content in the reaction system, and adding equimolar monohydroxypolydimethylsiloxane. And naturally cooling after the reaction is finished, adding Triethylamine (TEA) into the reaction system for reacting for 30min when the temperature of the reaction system is reduced to 50 ℃, and neutralizing to form salt. Finally, under the condition of normal temperature and high speed stirring, adding a proper amount of distilled water to emulsify and disperse to obtain the organosilicone polyurethane (SiWPu) water dispersion.
Preparation method of super-hydrophobic fabric
The method comprises the following steps of putting the washed polyester fabric into a micro-nano roughness structure for constructing the super-hydrophobic polyester fabric: the concentration of NaOH is 5mol/L, the treatment temperature is 70 ℃, and the treatment time is 60 min. Then, the fabric is washed clean by deionized water until the pH value of the surface of the fabric is about 7, and is dried at 80 ℃. And finally, after drying, preparing the water-based organic silicon polyurethane into an organic silicon polyurethane aqueous solution with the mass concentration of 10%, putting a certain amount of the polyurethane aqueous solution into a clean spray gun, adjusting the speed of the spray gun, then spraying the polyurethane aqueous solution on the polyester fabric subjected to alkali treatment, wherein the volume of the polyurethane aqueous solution sprayed on each square meter of the polyester fabric subjected to alkali treatment is 100mL, and curing the polyurethane aqueous solution for 2 hours at the temperature of 80 ℃. Finally, the cured polyester fabric is subjected to heat treatment at 170 ℃ for 0.5h to obtain the environment-friendly super-hydrophobic fabric.
Example 2
Preparation of aqueous organosilicon polyurethane
Referring to the schematic synthesis scheme of FIG. 1, the preparation of the aqueous silicone polyurethane dispersion is illustrated as follows:
(1) mixing the components in a molar ratio of 10: 8: 52.5 Dihydroxypolydimethylsiloxanes (PDMS), 3-methoxy-1, 2-propanediol and isophorone diisocyanate (IPDI) were mixed and N, N' -Dimethylformamide (DMF) was added in sufficient quantity as a solvent.
(2) And (2) adding dimethylolbutyric acid (DMBA) and Trihydroxypropane (TMP) into the system in the step (1), wherein the adding amount of the dimethylolbutyric acid (DMBA) is 5.5 percent, and the adding amount of the Trihydroxypropane (TMP) is 1.25 percent.
(3) Under the stirring process of 50 ℃, dropwise adding enough dibutyltin dilaurate (DBTDL) into the system, uniformly mixing, raising the temperature of the reaction system to 80 ℃, reacting at constant temperature for 6 hours, measuring the residual NCO content in the reaction system, and adding equimolar monohydroxypolydimethylsiloxane. And naturally cooling after the reaction is finished, adding Triethylamine (TEA) into the reaction system for reacting for 30min when the temperature of the reaction system is reduced to 50 ℃, and neutralizing to form salt. Finally, under the condition of normal temperature and high speed stirring, adding a proper amount of distilled water to emulsify and disperse to obtain the organosilicone polyurethane (SiWPu) water dispersion.
Preparation method of super-hydrophobic fabric
The method comprises the following steps of putting the washed polyester fabric into a micro-nano roughness structure for constructing the super-hydrophobic polyester fabric: the concentration of NaOH is 1mol/L, the treatment temperature is 90 ℃, and the treatment time is 90 min. Then, the fabric is washed clean by deionized water until the pH value of the surface of the fabric is about 7, and is dried at 80 ℃. And finally, after drying, preparing the water-based organic silicon polyurethane into an organic silicon polyurethane aqueous solution with the mass concentration of 10%, putting a certain amount of the polyurethane aqueous solution into a clean spray gun, adjusting the speed of the spray gun, then spraying the polyurethane aqueous solution on the polyester fabric subjected to alkali treatment, wherein the volume of the polyurethane aqueous solution sprayed on each square meter of the polyester fabric subjected to alkali treatment is 150mL, and curing the polyurethane aqueous solution for 2 hours at the temperature of 80 ℃. Finally, the cured polyester fabric is subjected to heat treatment at 170 ℃ for 0.5h to obtain the environment-friendly super-hydrophobic fabric.
Example 3
Preparation of aqueous organosilicon polyurethane
Referring to the schematic synthesis scheme of FIG. 1, the preparation of the aqueous silicone polyurethane dispersion is illustrated as follows:
(1) mixing the components in a molar ratio of 10: 4: 47.5 Dihydroxypolydimethylsiloxanes (PDMS), 3-methoxy-1, 2-propanediol and isophorone diisocyanate (IPDI) were mixed and sufficient N, N' -Dimethylformamide (DMF) was added as solvent.
(2) And (2) adding dimethylolbutyric acid (DMBA) and Trihydroxypropane (TMP) into the system in the step (1), wherein the addition amount of the dimethylolbutyric acid (DMBA) is 4 percent, and the addition amount of the Trihydroxypropane (TMP) is 0.75 percent.
(3) Under the stirring process of 50 ℃, dropwise adding enough dibutyltin dilaurate (DBTDL) into the system, uniformly mixing, raising the temperature of the reaction system to 80 ℃, reacting at constant temperature for 6 hours, measuring the residual NCO content in the reaction system, and adding equimolar monohydroxypolydimethylsiloxane. And naturally cooling after the reaction is finished, adding Triethylamine (TEA) into the reaction system for reacting for 30min when the temperature of the reaction system is reduced to 50 ℃, and neutralizing to form salt. Finally, under the condition of normal temperature and high speed stirring, adding a proper amount of distilled water to emulsify and disperse to obtain the organosilicone polyurethane (SiWPu) water dispersion.
Preparation method of super-hydrophobic fabric
The method comprises the following steps of putting the washed polyester fabric into a micro-nano roughness structure for constructing the super-hydrophobic polyester fabric: the concentration of NaOH is 3mol/L, the treatment temperature is 60 ℃, and the treatment time is 60 min. Then, the fabric is washed clean by deionized water until the pH value of the surface of the fabric is about 7, and is dried at 80 ℃. And finally, after drying, preparing the water-based organic silicon polyurethane into an organic silicon polyurethane aqueous solution with the mass concentration of 10%, putting a certain amount of the polyurethane aqueous solution into a clean spray gun, adjusting the speed of the spray gun, then spraying the polyurethane aqueous solution on the polyester fabric subjected to alkali treatment, wherein the volume of the polyurethane aqueous solution sprayed on each square meter of the polyester fabric subjected to alkali treatment is 250mL, and curing the polyurethane aqueous solution for 2 hours at the temperature of 80 ℃. Finally, the cured polyester fabric is subjected to heat treatment at 170 ℃ for 0.5h to obtain the environment-friendly super-hydrophobic fabric.
Performance testing
First, structural characterization
The material from example 3 was tested for infrared, elemental composition, AFM and SEM.
1. Fourier infrared spectrogram analysis
FIG. 2 shows the IR spectra of RT (original polyester fabric), AT (alkali treated polyester fabric) and SiPuT (polyester fabric sprayed with silicone polyurethane). As can be seen from the comparison of the infrared images of RT and AT, the chemical bonds of the polyester fabric subjected to alkali treatment are not changed too much. While from the comparison of the infrared patterns of AT and SiPuT, it can be seen that 1240cm-1And 1713cm-1The peak is respectively the stretching vibration absorption peak of C-O bond and the stretching vibration absorption peak of C ═ O bond, but after the water-based organosilicon polyurethane is sprayed, the intensity of the peak is reduced, and the organosilicon polyurethane is proved to be successfully attached to the fiber surface of AT. In the infrared spectrogram of SiPuT, at 1086cm-1And 786cm-1And a stretching vibration absorption peak belonging to Si-O-Si and a stretching vibration absorption peak belonging to Si-C respectively appear. 2960cm of-1Belong to-CH3The symmetric stretching vibration peak of (a), which demonstrates the successful spray coating of aqueous silicone polyurethane on the fiber surface of AT. The infrared spectra of the materials prepared in examples 1-2 were the same as those of example 3.
2. Elemental composition analysis
FIGS. 3, 4, and 5 are XPS spectra of original polyester fabric (RT), alkali treated polyester fabric (AT), and silicone polyurethane coated polyester fabric (SiPuT) in sequence. Table 1 shows the XPS elemental analysis results.
TABLE 1 XPS elemental analysis results
The test result shows that the original polyester fabric is composed of C, O two elements, wherein 59.57% of C and 40.43% of O are contained. After alkaline hydrolysis treatment, the composition of the polyester fabric still consists of C, O two elements, and the polyester fabric contains 56.03% of C and 43.97% of O. Since hydroxyl anions in the sodium hydroxide aqueous solution attack carbonyl groups on the polyester fabric, the polyester fabric after alkali treatment contains less C elements and more O elements than the original fabric. Meanwhile, the method also shows that the element composition of the fabric is not changed in the alkaline hydrolysis process, and only the microstructure of the surface of the polyester fabric is changed. And after the surface of the fabric is sprayed with the waterborne organic silicon polyurethane, new Si signals of Si 2p and Si 2s are detected at 153.2eV and 102.2eV respectively, which shows that the surface of the polyester fiber has the cured waterborne organic silicon polyurethane.
For further exploration, high resolution spectral analysis was performed on C1s for RT, C1s for AT, C1s for SiPuT, and Si 2 p. FIGS. 6, 7, 8, and 9 are XPS spectra of RT AT C1s, AT AT C1s, SiPuT AT C1s, and SiPuT AT Si 2p, respectively. The C1s for AT can be curve fit to the typical characteristic peaks for C O, C-O and C-C with binding energies of 291eV, 287.2eV, 284.6 eV. When the aqueous silicone polyurethane was cured on the surface of the polyester fiber, the characteristic peak intensities of C-O, C ═ O, C-C were all reduced, consistent with the FT-IR spectra. Si 2p of SiPuT can be synthesized into typical characteristic peaks of Si-O-Si and Si-C, which indicates that the waterborne organic silicon polyurethane is successfully cured on the surface of polyester fiber.
3. AFM (atomic force microscope) analysis
The microscopic surface structures of RT, AT and SiPuT were further explored using atomic force microscopy. In the AFM chart of FIG. 10, (a) and (d) are a two-dimensional image and a three-dimensional image of RT, respectively; (b) and (e) two-dimensional images and three-dimensional images of the AT respectively; (c) and (f) are a two-dimensional image and a three-dimensional image of SiPuT respectively. From the AFM image, it can be seen that the surface of the original polyester fabric was relatively smooth, the average roughness thereof was 4.125nm, and the root mean Roughness (RMS) thereof was 5.755. The surface microstructure of the polyester fabric after alkali treatment is completely different from that of the original fabric, because a plurality of meteorite craters are formed on the surface of the fabric after the alkali treatment, the average roughness of the surface is improved from original 4.125nm to 37.967, and the root average roughness of the surface is increased to 50.6 nm. This demonstrates that the alkali treatment technique successfully builds micro-nano roughness on the surface of the dacron. Whereas the surface microstructure of SiPuT is much less "merle crater" than AT. That is, the water-based organic silicon polyurethane is attached to the surface of the fabric, and after heat treatment, the organic silicon polyurethane shrinks to form micro-spheres to be attached to the surface of the fabric, so that the surface roughness of the fabric is ensured to be enough to meet the condition of super-hydrophobicity, the average roughness of SiPuT is only reduced from 37.967nm to 31.167nm, and the root average roughness is reduced to 47.167 nm.
4. SEM analysis
Scanning electron microscopy analysis was performed on RT, AT and SiPuT as shown in FIG. 11. In FIG. 11, (a) is an SEM photograph of RT, (b) is an SEM photograph of AT, and (c) is an SEM photograph of SiPuT. As can be seen from the SEM image of FIG. 11, the surface of the original polyester fabric is very smooth with some inherent wrinkles, while the alkali-treated polyester fabric has many "merle craters" on the surface due to the etching of the sodium hydroxide aqueous solution. However, the surface of the polyester fabric coated with the organosilicone polyurethane was observed to have "merle pits" left by the alkali treatment, while the organosilicone polyurethane was observed to be uniformly coated on the surface of the fiber, and microspheres formed by shrinkage of the organosilicone polyurethane after the heat treatment were observed. The SEM patterns of the materials prepared in examples 1-2 were the same as those of example 3.
Second, super-hydrophobic fabric performance test
The superhydrophobic fabrics prepared in the examples were tested for contact angle, oil-water separation, chemical durability, and mechanical durability, as illustrated below:
1. contact Angle testing
The wettability of the sample was tested by using a model JC200A static contact angle tester from Dongguan Chengding precision instruments Ltd. The volume of the water drop taken during the test is 5 mu L, 5 different positions are selected on the surface of the same sample to be tested for measurement, and the test is carried out for 5 times in parallel.
2. Oil-water separation test
And (3) carrying out oil-water separation experiments by adopting a self-made oil-water separation device. The prepared organic silicon polyurethane polyester fabric is used as a filter membrane. Referring to the schematic diagram of fig. 12 (schematic diagram of fig. 12, from left to right, before, during and after the test), the two glass tubes are fixed by metal clips, and different kinds of oil/water mixtures, such as Diiodomethane (Diiodomethane)/water, Dichloromethane (DCM)/water, Chloroform (Chloroform)/water, N-hexane (N-hexane)/water, and Petroleum Ether (PE)/water, are selected, and the aqueous phase is dyed with methylene blue and the oil phase is dyed with oil red O, respectively. Then, 24mL of an oil/water mixture (oil phase: water phase: 1) was measured and poured into the self-made oil-water separator, and the oil-water separation process was recorded with a camera. The formula for calculating the oil-water separation efficiency of the super-hydrophobic fabric is shown as follows.
In the formula: m is0Mass of oil before separation, g; m is1Mass of oil after separation, g.
3. Chemical durability test
Respectively soaking the samples in hydrochloric acid (pH is 1-2), sodium hydroxide solution (pH is 12-13), water, normal hexane and ethanol for 24 hours, then cleaning the samples with deionized water, and drying the samples with a blower. Finally, the static contact angle of the sample was measured to evaluate the chemical durability of the superhydrophobic fabric.
4. Mechanical durability test
The mechanical durability of the superhydrophobic fabric was evaluated by measuring the static contact angle of the abraded sample after repeating abrasion cycles of moving the sample at the same speed in the same direction and the same 10cm cycle with 240-mesh sandpaper as an abrasion material and a weight of 200g as an abrasion pressure.
FIGS. 13 and 14 are respectively a graph of the separation efficiency and the permeation flux of the superhydrophobic fabric to different types of oil-water mixtures. As can be seen from FIGS. 13 and 14, the separation efficiency of the superhydrophobic fabric prepared by the invention on different types of oil-water mixtures is over 90%, and the permeation flux is 15000 L.m2·h-1Above, this indicates that the superhydrophobic fabric has good separation efficiency. Wherein the highest separation efficiency of Diiodomethane/water mixture is up to 95%, and the penetration flux is up to 20000 L.m2·h-1。
FIG. 15 is a graph of separation efficiency of a super-hydrophobic fabric in 50 oil-water separation tests, and FIG. 16 is a graph of contact angle change of the super-hydrophobic fabric in 50 oil-water separation tests. Through tests, the prepared super-hydrophobic fabric still maintains high separation efficiency even after separation for 50 cycles, and the WCA of the super-hydrophobic fabric is basically not changed obviously and is still over 150 degrees. This shows that the super-hydrophobic fabric prepared by the invention has good oil-water separation performance and recycling performance.
The chemical durability effect of the superhydrophobic fabric in different solvents can be seen in figure 17. Tests show that after the super-hydrophobic fabric is soaked in N-hexane (N-hexane), Ethanol (Ethanol), hydrochloric acid (HCl), deionized Water (Water) and sodium hydroxide (NaOH) solution for 24 hours, the contact angle values are respectively 156.3 degrees, 152.1 degrees, 156.6 degrees, 150.4 degrees and 156.9 degrees, and are all kept above 150 degrees.
The mechanical stability of the superhydrophobic fabrics was evaluated by abrasion tests and the contact angle remained above 150 ° after 400 cycles.
FIG. 18 is a schematic representation of the underwater oil absorption test of a fabric. As explained below in connection with fig. 18, due to its hydrophobic properties, the superhydrophobic fabric can absorb oil (dyed with oil red O) under water (dyed with methyl blue) without leaving a trace. Therefore, only the oil-absorbed portion of the superhydrophobic fabric showed a color change. The original fabric absorbs water while absorbing oil due to its hydrophilic property. Thus, the original fabric exhibited the phenomenon of "half red, half blue". Figure 19 is a graph comparing the hydrophobic properties of fabrics. Fig. 19a is a schematic view of hydrophobic property test of an original fabric and a super-hydrophobic fabric, fig. 19b is a graph of hydrophobic property test effect of the original fabric, and fig. 19c is a graph of hydrophobic property test effect of the super-hydrophobic fabric. As can be seen from fig. 19, the original fabric sinks into the water bottom very quickly because of its hydrophilic properties. However, the super-hydrophobic fabric prepared by the invention can float on the water surface due to the hydrophobic property of the super-hydrophobic fabric. When the super-hydrophobic fabric is immersed in water, a layer of solid-liquid-gas interface is formed on the surface of the fabric due to the hydrophobic property of the super-hydrophobic fabric, so that the phenomenon of silver mirror can be observed. It was found through experiments that the superhydrophobic fabric of the present invention exhibited excellent hydrophobic properties for Water (Water), Dyed Water (Dyed Water), Ink (Ink), Coffee (Coffee), Tea (Tea), Milk (Milk), etc., relative to the original fabric.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A fluorine-free superhydrophobic fabric, comprising: the super-hydrophobic fabric comprises a substrate and a coating arranged on the surface of the substrate; the substrate is an alkalized polyester fabric; the coating is a water-based organic silicon polyurethane coating;
the preparation components of the water-based organic silicon polyurethane comprise: dihydroxy polydimethylsiloxane, 3-methoxy-1, 2-propanediol, isophorone diisocyanate, dimethylol butyric acid, trihydroxy propane and a blocking agent;
the structural formula of the dihydroxyl polydimethylsiloxane is shown as the formula (I):
in the formula (I), m and n are respectively any positive integer;
the end-capping agent is monohydroxy polydimethylsiloxane, and the structural formula of the monohydroxy polydimethylsiloxane is shown in a formula (II):
in the formula (II), x is any positive integer.
2. The superhydrophobic fabric of claim 1, wherein: the alkalized polyester fabric is obtained by soaking polyester fibers in alkali liquor for treatment.
3. The superhydrophobic fabric of claim 2, wherein: the alkali in the alkali liquor is selected from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate; the treatment temperature is 50-90 ℃; the treatment time is 30-90 min.
4. A method for preparing a fluorine-free superhydrophobic fabric according to any one of claims 1 to 3, characterized in that: the method comprises the following steps: and spraying the aqueous organic silicon polyurethane solution on the alkalized polyester fabric, curing and carrying out heat treatment to obtain the super-hydrophobic fabric.
5. The method of claim 4, wherein: the preparation method of the water-based organic silicon polyurethane comprises the following steps:
1) mixing dihydroxy polydimethylsiloxane, 3-methoxy-1, 2-propanediol, isophorone diisocyanate and a solvent;
2) mixing the mixed solution obtained in the step 1) with dimethylolbutyric acid and trihydroxypropane;
3) adding a catalyst into the solution obtained in the step 2), heating for reaction, and adding amine for neutralization to obtain the water-based organic silicon polyurethane.
6. The method of claim 5, wherein: in step 1) of the preparation method of the aqueous organosilicon polyurethane, the molar ratio of the dihydroxy polydimethylsiloxane, the 3-methoxy-1, 2-propanediol and the isophorone diisocyanate is 10: (0.3-8): (42.5-52.5).
7. The method of claim 5, wherein: in the step 2) of the preparation method of the water-based organic silicon polyurethane, the addition amount of the dimethylolbutyric acid accounts for 3.5-5.5 percent of the total mass of the dihydroxy polydimethylsiloxane, the 3-methoxy-1, 2-propylene glycol and the isophorone diisocyanate; the adding amount of the trihydroxy propane is 0.25 to 1.25 percent.
8. The method of claim 5, wherein: in the step 3) of the preparation method of the water-based organic silicon polyurethane, the heating reaction is carried out for 4 to 10 hours at the temperature of between 40 and 90 ℃; the heating reaction also comprises a step of adding an end-capping agent for end capping.
9. The method of claim 4, wherein: the curing is carried out for 1 to 3 hours at the temperature of between 70 and 90 ℃; the heat treatment is carried out for 10min to 60min at 160 ℃ to 180 ℃.
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