CN112095345B - Hydrophilic oleophobic fabric and preparation method thereof - Google Patents
Hydrophilic oleophobic fabric and preparation method thereof Download PDFInfo
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- D06M2101/16—Synthetic fibres, other than mineral fibres
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- D06M2101/16—Synthetic fibres, other than mineral fibres
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Abstract
The invention discloses a hydrophilic oleophobic fabric and a preparation method thereof, wherein the fabric is pretreated by poly (diallyldimethylammonium chloride) polymer, and quaternary ammonium salt is coated on the surface of the fabric; then reacting with sodium perfluoropolyether carboxylate to obtain a hydrophilic-oleophobic fabric with the fiber surface coated with the ammonium fluorocarboxylate polymer, wherein the hydrophilic-oleophobic fabric can be subjected to hydration when contacting water, and the static contact angle of the fabric to water gradually decreases along with the prolonging of the contact time and is finally converted into hydrophilic; providing an oleophobic function when exposed to oil. According to the method, the surface of the fiber is coated with the quaternary ammonium salt, and then the perfluoropolyether carboxylic acid anions and the nitrogen cations are combined, the two steps of treatment are realized in the aqueous solution, the perfluoropolyether ammonium carboxylate is generated in situ on the surface of the fiber, the technical problem that the perfluoropolyether ammonium carboxylate is almost insoluble in all solvents and is difficult to spray or dip the fabric is solved, the method for obtaining the special wetting fabric and the oil-water separation fabric is simple in process, does not use an organic solvent, is mild in operation condition, and is suitable for process amplification and production.
Description
Technical Field
The invention relates to a hydrophilic oleophobic fabric and a preparation method thereof, which can be used for oil-water separation.
Background
In the research and use process of fluorine-containing materials, the extremely low surface energy characteristic and the stable surface conformation of long-carbon-chain perfluoroalkyl (namely, hydrogen atoms are completely replaced and carbon chains are more than or equal to 8) are utilized to achieve the purposes of water and oil resistance, pollution prevention, chemical corrosion resistance and other surface treatments, and the fluorine-containing materials are widely applied. However, the long-carbon-chain perfluoroalkyl group is oxidized and degraded in natural environment to generate corresponding perfluorocarboxylic Acid or carboxylate, and is difficult to degrade after environmental pollutants such as Perfluorooctane sulfonate (PFOS) and Perfluorooctanoic Acid (PFOA) are generated, and these decomposition products are the most difficult organic pollutants to degrade at present and have serious harm to human health. PFOS has a high long-lasting stability and is concentrated in the environment, human and animal tissues, so in 2001 the us EPA proposed to ban PFOS use, and countries of the european union etc. have stopped producing and using long fluorine chain products. PFOS was also listed as Persistent Organic Pollutant (POPs) controlled substance by stockholm convention 2009. Research shows that PFOS pollutants also exist in animals in south and north regions, which indicates that the series of pollutants have mobility. Worse still, research data show that PFOS concentrations in high-grade animals are higher than those in low-grade animals, indicating that bioamplification is in play. Aiming at the problems of biotoxicity, accumulation and PFOS (Perfluorooctane sulfonate) disablement of long-carbon-chain perfluoroalkyl, the research on PFOS substitutes with high surface activity but friendly environment becomes a research hotspot of current fluorine-containing materials.
Disclosure of Invention
The invention coats the perfluoropolyether ammonium carboxylate polymer on the surface of the fabric fiber, provides hydrophilicity by utilizing the intrinsic hydration and has an oleophobic function, thereby obtaining the hydrophilic-oleophobic fabric.
The method comprises the steps of generating a perfluoropolyether ammonium carboxylate polymer coating on the surface of a fiber in situ in the form of an aqueous solution, padding and finishing a fabric by using an ammonium chloride type polymer, and wrapping a quaternary ammonium salt polymer layer on the surface of the fiber; then replacing chloride anions in the quaternary ammonium salt polymer with perfluoropolyether carboxylate radicals, and coating the perfluoropolyether ammonium carboxylate on the surface of the fabric fiber through a two-step method; the problem of poor solubility commonly existing in perfluoropolyether type polymers is creatively solved.
The technical scheme for realizing the purpose of the invention is as follows:
a hydrophilic oleophobic fabric comprising a base fabric and an ammonium perfluoropolyether carboxylate coating having the following chemical structure:
the hydro-oleophobic fabric of the invention can be represented as follows:
wherein n = 10-1600; rf is as follows:
the invention discloses a preparation method of the hydrophilic oleophobic fabric, which comprises the following steps: padding the fabric into polydiallyl dimethyl ammonium chloride aqueous solution, drying, adding into perfluoropolyether sodium carboxylate aqueous solution, and reacting to obtain the hydrophilic oleophobic fabric.
In the invention, sodium hydroxide aqueous solution is dripped into perfluoropolyether carboxylic acid to react to obtain the perfluoropolyether carboxylic acid sodium aqueous solution.
In the present invention, the perfluoropolyether carboxylic acids are as follows:
in an open container, preparing a polydiallyldimethylammonium chloride aqueous solution with a certain concentration as an impregnation solution, adding a fabric according to a certain bath ratio (the mass ratio of the fabric to the impregnation solution in impregnation), rolling the fabric after impregnation, controlling the rolling rate, and drying;
preparing a stirrer in an open container, adding a certain amount of perfluoropolyether carboxylic acid, dropwise adding a sodium hydroxide aqueous solution under stirring, and continuously stirring to react for more than 1 hour after the addition is finished to obtain the perfluoropolyether carboxylic acid sodium aqueous solution, wherein the stirring is not limited and is a conventional method;
putting the dried fabric into the aqueous solution of sodium perfluoropolyether carboxylate, and reacting for a certain time in a conventional way, wherein the reaction time is preferably 10 minutes to 12 hours, and most preferably 20 minutes to 2 hours; obtaining the hydrophilic oleophobic fabric.
Further, after the reaction is finished, taking out the fabric, washing with water to remove unreacted raw materials and generated sodium chloride by-products, and drying to obtain the hydrophilic oleophobic fabric; the drying temperature of the fabric is 40-100 ℃, preferably 50-70 ℃; the drying time is 10 minutes to 5 hours, preferably 30 minutes to 2 hours.
In the invention, the fabric is single-spinning or blended fabric of terylene, acrylon, chinlon, polypropylene fiber and aramid fiber, and the fiber in the fabric is one or more of the terylene, the acrylon, the chinlon, the polypropylene fiber and the aramid fiber; the fiber surface of the hydrophilic oleophobic fabric contains a fluoropolyether ammonium carboxylate coating.
In the invention, the mass concentration of the poly diallyl dimethyl ammonium chloride aqueous solution is 1-50%, preferably 5-20%; when padding, the bath ratio is 1: 10-1: 200, preferably 1: 20-1: 50; the dipping time is 10 minutes to 6 hours, preferably 30 minutes to 1 hour; the mangle rolling rate is controlled to be 10-110%, preferably 20-80%; the drying temperature of the fabric is 40-100 ℃, preferably 50-70 ℃; the drying time is 10 minutes to 5 hours, preferably 30 minutes to 2 hours.
In the invention, the mass concentration of the sodium hydroxide aqueous solution is 1-20%, preferably 3-10%; the mass concentration of the aqueous solution of sodium perfluoropolyether carboxylate is 3-30%, preferably 8-12%.
In the present invention, the anion exchange reaction is as follows:
compared with the prior art, the technical scheme provided by the invention has the beneficial effects that:
1. the method coats the perfluoropolyether ammonium carboxylate on the fiber surface of the fabric for the first time, and can generate hydration when contacting water, so that the static contact angle of the fabric to water gradually decreases along with the prolonging of the contact time and is finally converted into hydrophilicity; providing an oleophobic function when exposed to oil. Thereby imparting a hydrophilic-oleophobic function to the fabric. The method has very important significance for developing oil-water separation of mixed components of light oil and water, the light oil floats on the upper layer of water, the lower layer of water contacts with the filter cloth firstly, and the water can be filtered due to the hydrophilicity of the filter cloth; the filter cloth is oleophobic, and light oil is trapped.
2. According to the method, the surface of the fiber is coated with the quaternary ammonium salt, and then the perfluoropolyether carboxylic acid anion is combined, so that the perfluoropolyether ammonium carboxylate is generated in situ on the surface of the fiber, and the technical problem that the fabric is difficult to spray or dip due to the fact that the ammonium perfluorocarboxylate polymer is almost insoluble in all solvents is solved.
3. The coating is formed on the surface of the fiber, and the coating is realized by a two-step method, the two-step treatment is realized in aqueous solution, and the production process is safe and environment-friendly; and the process for preparing the hydrophilic-oleophobic fabric is simple, the operating conditions are mild, and the method is suitable for process amplification and production.
Drawings
FIG. 1 is a schematic diagram of the chemical structure of ammonium polydiallyldimethylperfluoropolyether carboxylate of the present invention on the surface of a fiber;
FIG. 2 is a graph of the trend of tests on the decrease of water contact angle with time of the hydrophilic and oleophobic fabrics prepared in examples one to four, respectively; wherein, the treatment concentration of the poly diallyl dimethyl ammonium chloride is 5wt% in the example, 10wt% in the example, 15wt% in the example, and 20wt% in the example;
FIG. 3 is a graph of the trend of the tests on the decrease of the oil contact angle with time of the hydrophilic and oleophobic fabrics prepared in examples one to four, respectively; wherein, the treatment concentration of the poly diallyl dimethyl ammonium chloride is 5wt% in the example, 10wt% in the example, 15wt% in the example, and 20wt% in the example;
FIG. 4 is an attenuated total reflection infrared image of the surface of the treated fabric of example two; wherein, PDA is poly diallyl dimethyl ammonium chloride treated polyester fabric, and PDAF-2 is a surface infrared spectrogram of the hydrophilic oleophobic fabric after perfluoropolyether carboxylate anion exchange; PDAF-6 is a surface infrared spectrogram of the hydrophilic oleophobic fabric subjected to perfluoropolyether carboxylate anion exchange in the fourth embodiment;
FIG. 5 is an SEM image and an EDS element distribution diagram of the surface of a polyester fabric treated by polydiallyldimethylammonium chloride of an example, wherein the content of C element is 64.031%, the content of N element is 3.148%, and the content of O element is 32.821%, and the test result shows that polydiallyldimethylammonium chloride has been coated on the surface of the fiber because the polyester fabric does not contain N element;
FIG. 6 is an SEM image and EDS element distribution plot of the surface of an example ammonium polydiallyldimethylperfluoropolyether carboxylate treated polyester fabric, wherein the C element is 346.840%, the N element is 2.652%, the O element content is 15.550%, and the F element is 34.985%, and the results of the tests indicate that ammonium polydiallyldimethylperfluoropolyether carboxylate has been coated onto the surface of the fiber;
FIG. 7 is a graph showing the trend of the hydrophilic and oleophobic fabric for poly (ammonium diallyldimethylperfluorobutyrate) prepared in the first comparative example to decrease the water contact angle with time;
FIG. 8 is a graph showing the trend of the poly (diallyldimethyl perfluorooctanoic acid ammonium) hydrophilic oleophobic fabric prepared in the first comparative example to decrease the oil contact angle with time;
FIG. 9 is an appearance diagram of the ammonium polydiallyldimethylperfluoropolyether carboxylate product prepared in comparative example two;
FIG. 10 shows the oil-water separation of petroleum ether/water in a filter device by using the hydrophilic-oleophobic fabric prepared in the third embodiment of the invention as a filter cloth.
Detailed Description
The preparation method of the hydrophilic oleophobic fabric disclosed by the invention comprises the following steps:
(1) pretreatment of quaternary ammonium salt on the surface of the fiber: firstly, preparing a poly (diallyldimethylammonium chloride) aqueous solution, putting the poly (diallyldimethylammonium chloride) aqueous solution into a fabric, soaking, rolling the fabric, and drying the fabric;
(2) preparing a sodium perfluoropolyether carboxylate aqueous solution: dropwise adding a sodium hydroxide aqueous solution into the perfluoropolyether carboxylic acid, and carrying out neutralization reaction to obtain a perfluoropolyether carboxylic acid sodium aqueous solution;
(3) putting the dried quaternized fabric into a sodium perfluoropolyether carboxylate aqueous solution to perform an exchange reaction; and then taking out the fluorinated fabric, washing with water, and drying to obtain the hydrophilic and oleophobic fabric, wherein the chemical structure of the fiber surface coating in the fabric is schematically shown in figure 1.
The technical scheme of the invention is further described by combining the drawings and the embodiment; the fabric and the raw materials related to the invention are conventional substances sold in the market, and the fabric is not subjected to surface treatment and cannot be subjected to oil-water separation; the testing methods of contact angle and the like are conventional testing methods of fabrics, and the specific preparation method is also conventional technology. Compared with the prior art, the fabric treatment method has simple process and easy operation, and can obtain the hydrophilic-oleophobic coating on the surface of the fiber.
Taking 2g of polyester fabric as an example, 200g of petroleum ether/water (1: 1 volume) is separated after the surface treatment of the invention, and the separation efficiency is tested. Wherein 5 drops of red ink were added to the water. The method specifically comprises the steps of pouring petroleum ether/water on the surface of a hydrophilic oleophobic fabric, standing, allowing the water to be absorbed by the fabric and flow down through the fabric under the action of gravity without depending on external force, and finally collecting separated petroleum ether to finish oil-water separation. And drying the fabric subjected to oil-water separation, and performing oil-water separation test again to study the recycling performance.
Example one
Dissolving 25g of polydiallyldimethylammonium chloride (polydiallyldimethylammonium chloride purchased from Kunshan sanden bioscience and Technique Limited, Inc., model D1UL (molecular weight 23-25 ten thousand), as in the following example) in 475g of water to prepare 5.0wt% polydiallyldimethylammonium chloride aqueous solution; then 20g of polyester fabric is put into the container, after 30min of soaking, the polyester fabric is subjected to mangling, the mangling rate is controlled to be 50%, then the polyester fabric is dried for 1h at 50 ℃, the fabric is weighed, and the once weight gain rate of the fabric is measured to be 4.4%; the fabric can not be subjected to oil-water separation;
dissolving 0.4g of sodium hydroxide in 108g of water to prepare a sodium hydroxide aqueous solution with the mass concentration of 0.37%;
adding 12 g of K-type perfluoropolyether carboxylic acid with the number average molecular weight of 3000 into a 500mL beaker under conventional stirring, cooling to 5 ℃, dropwise adding the sodium hydroxide aqueous solution, and reacting at room temperature until the pH is = 7-8 after dropwise adding to obtain a perfluoropolyether carboxylic acid sodium aqueous solution with the solution concentration of 10.2 wt%; adding the dried fabric treated by quaternary ammonium, and oscillating for reaction for 30 min; and taking out the fabric, washing with water, and drying at 50 ℃ for 1h to obtain the hydrophilic oleophobic fabric.
Contact Angle testing
A DSA100 type full-automatic microscopic droplet wettability measuring instrument of Kruss company in Germany is adopted to test the wettability of the super-hydrophobic fabric before and after soaping, water is selected as a test droplet, the volume of the droplet is 5 mu L, and the average value is obtained by respectively testing for five times. The initial contact angle of the treated fabric surface to water was measured to be 135.9 ± 0.8 °, the contact angle dropped to 0 ° after 30 minutes of water contact, and the change in contact angle to water of the treated fabric over time is shown in fig. 2. The contact angle to oil is 90.9 + -3.4 deg., the contact angle decreases to 61.8 + -1.5 deg. after contacting with oil for 30 minutes, and the change of the contact angle to oil of the treated fabric with time is shown in FIG. 3.
Oil-water separation test
The hydrophilic oleophobic fabric prepared in this example was used as a filter cloth and loaded into the filtration apparatus of FIG. 10. The separation efficiency (η) of the oil-water mixture is calculated by collecting the separated oil volume (V1) and the oil volume (V0) in the initial oil-water mixture by the formula (1):
the hydrophilic-oleophobic fabric prepared by the embodiment is used for separating petroleum ether and water mixture (1: 1 volume) by formula (1), and the separation efficiency can reach 87.2% for 1 time. After the oil-water separation is finished, taking out the hydrophilic oleophobic fabric, drying for 1 hour at the temperature of 60 ℃, putting the fabric into a filtering device again, and testing the recycling performance; when the catalyst is recycled for 5 times, the separation efficiency of 200g of the petroleum ether-water mixture (1: 1 volume) is reduced to 76.9%.
Example two
50g of polydiallyldimethylammonium chloride is dissolved in 450g of water to prepareForming 10.0% polydiallyldimethylammonium chloride aqueous solution, then adding 20g of polyester fabric, soaking for 30min, carrying out mangling, controlling the mangling rate to be 50%, drying for 1h at 50 ℃, weighing the fabric, and measuring the once weight gain rate of the fabric to be 6.2%. The treated fabric is tested by infrared, the result is shown in a curve PDA of figure 4, and the surface of the visible fiber is 3500-3350 cm-1Strong and wide quaternary ammonium salt characteristic absorption peaks appear in the range. FIG. 5 is a SEM image and an EDS element distribution diagram of the surface of a treated polyester fabric, wherein the C element is 64.031%, the N element is 3.148%, and the O element content is 32.821%, and the test result shows that the poly (diallyldimethylammonium chloride) is coated on the surface of the fiber because the polyester fabric does not contain the N element;
dissolving 0.4g of sodium hydroxide in 108g of water to prepare an aqueous solution with the mass concentration of 0.37%;
adding 12 g of K-type perfluoropolyether carboxylic acid with the number average molecular weight of 3000 into a 500mL beaker under conventional stirring, cooling to 5 ℃, dropwise adding the sodium hydroxide aqueous solution, and reacting at room temperature until the pH is = 7-8 after dropwise adding to obtain a perfluoropolyether carboxylic acid sodium aqueous solution with the solution concentration of 10.2 wt%; adding the dried fabric treated by quaternary ammonium, and oscillating for reaction for 30 min; and taking out the fabric, washing with water, and drying at 50 ℃ for 1h to obtain the hydrophilic oleophobic fabric. The infrared results of the test of the treated fabric are shown in a curve PDAF-2 in figure 4, and the fact that the surface of the fiber has a strong and wide characteristic absorption peak of quaternary ammonium salt and newly appears 1690cm-1Is C = O stretching vibration absorption peak in fluorine-containing carboxylic acid anion, 1243 cm-1And 1157 cm-1The newly appeared absorption peak is the C-F stretching vibration absorption peak in the perfluoropolyether chain. Thus, the fiber surface absorbs fluorine-containing polyether carboxylate radicals through ionic bonds after the exchange of perfluoropolyether carboxylic acid anions. FIG. 6 further shows SEM images and EDS element distribution maps of the surface of the treated polyester fabric, wherein the content of C element 346.840%, N element 2.652%, O element 15.550% and F element 34.985%, and the test results show that ammonium polydiallyldimethylperfluoropolyether carboxylate has been coated on the surface of the fiber.
(3) Contact Angle testing
A DSA100 type full-automatic microscopic droplet wettability measuring instrument of Kruss company in Germany is adopted to test the wettability of the super-hydrophobic fabric before and after soaping, water is selected as a test droplet, the volume of the droplet is 5 mu L, and the average value is obtained by respectively testing for five times. The initial contact angle of the treated fabric surface to water was measured to be 148.2 + -0.2 deg., the contact angle dropped to 0 deg. after 30 minutes of water contact, and the change in contact angle to water of the treated fabric over time is shown in fig. 2. The contact angle to oil was 91.8 + -2.9 deg., the contact angle dropped to 81.2 + -3.1 deg. after 30 minutes of oil contact, and the change in contact angle to oil of the treated fabric with time is shown in FIG. 3.
(4) Oil-water separation test
The separation efficiency (η) of the oil-water mixture is calculated by collecting the separated oil volume (V1) and the oil volume (V0) in the initial oil-water mixture by the formula (1):
the hydrophilic-oleophobic fabric prepared by the embodiment is used for separating the petroleum ether and water mixture (1: 1 volume) by the formula (1), the separation efficiency can reach 91.1% 1 time, and when the hydrophilic-oleophobic fabric is recycled for 5 times, the separation efficiency of the petroleum ether and water mixture (1: 1 volume) is 86.9%.
EXAMPLE III
Dissolving 75g of poly (diallyldimethylammonium chloride) in 425g of water to prepare a poly (diallyldimethylammonium chloride) aqueous solution with the concentration of 15.0%, adding 20g of polyester fabric, soaking for 30min, rolling, controlling the rolling rate to be 50%, drying for 1h at 50 ℃, weighing the fabric, and measuring the once weight gain rate of the fabric to be 6.9%;
dissolving 0.4g of sodium hydroxide in 108g of water to prepare an aqueous solution with the mass concentration of 0.37%;
adding 12 g of K-type perfluoropolyether carboxylic acid with the number average molecular weight of 3000 into a 500mL beaker under conventional stirring, cooling to 5 ℃, dropwise adding the sodium hydroxide aqueous solution, and reacting at room temperature until the pH is = 7-8 after dropwise adding to obtain a perfluoropolyether carboxylic acid sodium aqueous solution with the solution concentration of 10.2 wt%; adding the dried fabric treated by quaternary ammonium, and oscillating for reaction for 30 min; and taking out the fabric, washing with water, and drying at 50 ℃ for 1h to obtain the hydrophilic oleophobic fabric.
(3) Contact Angle testing
A DSA100 type full-automatic microscopic droplet wettability measuring instrument of Kruss company in Germany is adopted to test the wettability of the super-hydrophobic fabric before and after soaping, water is selected as a test droplet, the volume of the droplet is 5 mu L, and the average value is obtained by respectively testing for five times. The initial contact angle of the treated fabric surface to water was measured to be 149.3 + -1.7 deg., the contact angle dropped to 18.2 + -0.2 deg. after 30 minutes of water contact, and the change in contact angle to water of the treated fabric over time is shown in FIG. 2. The contact angle to oil was 94.8 + -2.4 deg., the contact angle dropped to 92.0 + -2.2 deg. after 30 minutes of oil contact, and the change in contact angle to oil of the treated fabric with time is shown in FIG. 3.
(4) Oil-water separation test
The separation efficiency (η) of the oil-water mixture is calculated by collecting the separated oil volume (V1) and the oil volume (V0) in the initial oil-water mixture by the formula (1):
the hydrophilic-oleophobic fabric prepared by the embodiment is used for separating the petroleum ether and water mixture (1: 1 volume) by the formula (1), the separation efficiency can reach 96.8% 1 time, and when the fabric is recycled for 5 times, the separation efficiency on the petroleum ether and water mixture (1: 1 volume) is 93.7%, and when the fabric is recycled for 10 times, the separation efficiency on the petroleum ether and water mixture (1: 1 volume) is 90.9%. FIG. 10 is a diagram of an experiment of oil-water separation of petroleum ether/water in a filter device, in which the hydrophilic and oleophobic fabric is filter cloth.
Example four
Dissolving 100g of poly (diallyldimethylammonium chloride) in 400g of water to prepare a poly (diallyldimethylammonium chloride) aqueous solution with the concentration of 20.0%, adding 20g of polyester fabric, soaking for 30min, rolling, controlling the rolling rate to be 50%, drying for 1h at 50 ℃, weighing the fabric, and measuring the once weight gain rate of the fabric to be 10.1%;
dissolving 0.4g of sodium hydroxide in 108g of water to prepare an aqueous solution with the mass concentration of 0.37%;
adding 12 g of K-type perfluoropolyether carboxylic acid with the number average molecular weight of 3000 into a 500mL beaker under conventional stirring, cooling to 5 ℃, dropwise adding the sodium hydroxide aqueous solution, and reacting at room temperature until the pH is = 7-8 after dropwise adding to obtain a perfluoropolyether carboxylic acid sodium aqueous solution with the solution concentration of 10.2 wt%; adding the dried fabric treated by quaternary ammonium, and oscillating for reaction for 30 min; and taking out the fabric, washing with water, and drying at 50 ℃ for 1h to obtain the hydrophilic oleophobic fabric. The infrared results of the test of the treated fabric are shown in a curve PDAF-6 in figure 4, and the fact that the surface of the fiber has a strong and wide characteristic absorption peak of quaternary ammonium salt and newly appears 1690cm-1Is C = O stretching vibration absorption peak in fluorine-containing carboxylic acid anion, 1243 cm-1And 1157 cm-1The newly appeared absorption peak is the C-F stretching vibration absorption peak in the perfluoropolyether chain. Thus, the fiber surface absorbs fluorine-containing polyether carboxylate radicals through ionic bonds after the exchange of perfluoropolyether carboxylic acid anions.
(3) Contact Angle testing
A DSA100 type full-automatic microscopic droplet wettability measuring instrument of Kruss company in Germany is adopted to test the wettability of the super-hydrophobic fabric before and after soaping, water is selected as a test droplet, the volume of the droplet is 5 mu L, and the average value is obtained by respectively testing for five times. The initial contact angle of the treated fabric surface to water was measured to be 148.0 + -0.6 deg., and after 30 minutes of water contact the contact angle dropped to 43.2 + -1.1 deg., as the change in contact angle to water of the treated fabric over time is shown in FIG. 2. The contact angle to oil was 94.4 + -3.6 deg., the contact angle dropped to 92.2 + -2.4 deg. after 30 minutes of oil contact, and the change in contact angle to oil of the treated fabric over time is shown in FIG. 3.
(4) Oil-water separation test
The separation efficiency (η) of the oil-water mixture is calculated by collecting the separated oil volume (V1) and the oil volume (V0) in the initial oil-water mixture by the formula (1):
the hydrophilic-oleophobic fabric prepared by the embodiment is used for separating the petroleum ether and water mixture (1: 1 volume) by the formula (1), the separation efficiency can reach 97.6% 1 time, and when the fabric is recycled for 5 times, the separation efficiency on the petroleum ether and water mixture (1: 1 volume) is 94.3%, and when the fabric is recycled for 10 times, the separation efficiency on the petroleum ether and water mixture (1: 1 volume) is 91.8%.
Comparative example 1
Dissolving 75g of poly (diallyldimethylammonium chloride) in 425g of water to prepare a poly (diallyldimethylammonium chloride) aqueous solution with the concentration of 15.0%, adding 20g of polyester fabric, soaking for 30min, rolling, controlling the rolling rate to be 50%, drying for 1h at 50 ℃, weighing the fabric, and measuring the once weight gain rate of the fabric to be 6.9%;
dissolving 0.4g of sodium hydroxide in 108g of water to prepare an aqueous solution with the mass concentration of 0.37%;
under conventional stirring, adding 12 g of perfluorooctanoic acid into a 500mL beaker, cooling to 5 ℃, dropwise adding the sodium hydroxide aqueous solution, and reacting at room temperature until the pH is = 7-8 after dropwise adding to obtain a sodium perfluorooctanoate aqueous solution with the solution concentration of 10.0 wt%; adding the dried fabric treated by quaternary ammonium, and oscillating for reaction for 30 min; and taking out the fabric, washing with water, and drying at 50 ℃ for 1h to obtain the hydrophilic oleophobic fabric.
(3) Contact Angle testing
A DSA100 type full-automatic microscopic droplet wettability measuring instrument of Kruss company in Germany is adopted to test the wettability of the super-hydrophobic fabric before and after soaping, water is selected as a test droplet, the volume of the droplet is 5 mu L, and the average value is obtained by respectively testing for five times. The initial contact angle of the treated fabric surface to water was found to be 132.4 ± 3.0 °, the contact angle dropped to 0 ° after 30 minutes of water contact, and the change in contact angle to water of the treated fabric over time is shown in fig. 7. The contact angle to oil was 92.9 + -1.6 deg., the contact angle dropped to 92.2 + -2.1 deg. after 30 minutes of oil contact, and the change in contact angle to oil of the treated fabric with time is shown in FIG. 8.
(4) Oil-water separation test
The separation efficiency (η) of the oil-water mixture is calculated by collecting the separated oil volume (V1) and the oil volume (V0) in the initial oil-water mixture by the formula (1):
the hydrophilic-oleophobic fabric prepared in this example was used to separate a petroleum ether and water mixture (1: 1 volume) by equation (1) with a separation efficiency of 89.8% for 1 separation.
Comparative example two:
a250 mL three-necked flask was equipped with stirring, thermometer, and addition funnel. 7.2g of poly (diallyldimethylammonium chloride) and 72g of deionized water are added and stirred to be dissolved completely. 40.7 g of an aqueous solution of sodium perfluoropolyether carboxylate (concentration: 10% by weight) was added dropwise at room temperature, and a gelatinous solid was rapidly precipitated. The reaction was stirred at room temperature for 3 h. After the reaction was terminated, the solid product was sufficiently washed with water to obtain 27.5g of ammonium polydiallyldimethylperfluoropolyether carboxylate with a yield of 87.0%. The product appearance is as in figure 9. Since the ammonium perfluoropolyether carboxylate product is very low in polarity and insoluble in water, attempts have been made to dissolve the product in organic solvents (such as ethanol, acetone, isopropanol, and the like, almost all organic solvents) and completely dissolve it. Therefore, the ammonium polydiallyldimethylperfluoropolyether carboxylate cannot be prepared into a working solution for surface treatment of fabrics.
Comparative example No. three
Dissolving 0.4g of sodium hydroxide in 108g of water to prepare a sodium hydroxide aqueous solution with the mass concentration of 0.37%;
adding 12 g of K-type perfluoropolyether carboxylic acid with the number average molecular weight of 3000 into a 500mL beaker under conventional stirring, cooling to 5 ℃, dropwise adding the sodium hydroxide aqueous solution, and reacting at room temperature until the pH is = 7-8 after dropwise adding to obtain a perfluoropolyether carboxylic acid sodium aqueous solution with the solution concentration of 10.2 wt%; then adding the fabric without surface treatment, and oscillating for reaction for 30 min; and taking out the fabric, washing and drying at 50 ℃ for 1h, and finding that the surface of the obtained fabric has no C-F stretching vibration absorption peak by an infrared test.
The invention particularly relates to a method for treating a fabric by using a perfluoropolyether ammonium carboxylate polymer, a hydrophilic-oleophobic fabric prepared by treating the surface of a fiber, and application of the hydrophilic-oleophobic fabric in oil-water separation, belonging to the technical field of special functional textiles and preparation thereof. The perfluoropolyether is a special perfluoropolymer, only F, C, O elements exist in the molecule, the average molecular weight of the perfluoropolyether is 500-15000, and the viscosity of the perfluoropolyether is increased with the increase of the average molecular weight at room temperature. The molecular structure of perfluoropolyether is very similar to that of hydrocarbon polyethers, but the C-H bond is replaced by a C-F bond, i.e. a fluorine atom is used in place of a hydrogen atom in the molecule. The C-F bond in the perfluoropolyether molecule has a strong shielding effect on a main chain, and the fluoroether oil prepared by the fluoroether oil in the prior art can be applied to a harsh environment and is good special lubricating oil, but no report is provided for hydrophilic and oleophobic treatment of fabrics.
Claims (8)
1. A hydrophilic oleophobic fabric comprising a fabric and an ammonium perfluoropolyether carboxylate coating having the following chemical structure:
wherein n = 10-1600; rf is as follows:
the preparation method of the hydrophilic oleophobic fabric is characterized by comprising the following steps: padding the fabric into a polydiallyldimethylammonium chloride aqueous solution, drying, adding into a perfluoropolyether sodium carboxylate aqueous solution, and reacting to obtain a hydrophilic oleophobic fabric; the mass concentration of the polydiallyldimethylammonium chloride aqueous solution is 15% or 20%.
2. The hydrophilic oleophobic fabric of claim 1, wherein the fabric is a polyester, acrylic, nylon, polypropylene, aramid mono-spun or blended fabric.
3. A method of making a hydrophilic oleophobic fabric in accordance with claim 1, comprising the steps of: padding the fabric into a polydiallyldimethylammonium chloride aqueous solution, drying, adding into a perfluoropolyether sodium carboxylate aqueous solution, and reacting to obtain a hydrophilic oleophobic fabric; the mass concentration of the polydiallyldimethylammonium chloride aqueous solution is 15% or 20%.
4. The preparation method of the hydrophilic oleophobic fabric according to claim 3, characterized in that a sodium hydroxide aqueous solution is dripped into perfluoropolyether carboxylic acid to react to obtain a perfluoropolyether carboxylic acid sodium aqueous solution; the perfluoropolyether carboxylic acids are as follows:
m is 5 to 50.
5. The preparation method of the hydrophilic oleophobic fabric according to claim 3, characterized in that the fabric is taken out after the reaction is finished, washed with water and dried to obtain the hydrophilic oleophobic fabric.
6. The preparation method of the hydrophilic oleophobic fabric according to claim 3, characterized in that the drying temperature is 40-100 ℃ and the drying time is 10 minutes-5 hours.
7. Use of a hydrophilic oleophobic fabric of claim 1 in the preparation of an oil-water separation material.
8. Use of a hydrophilic oleophobic fabric according to claim 1 in the preparation of a water absorbent material.
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