CN113717589A - Waterproof self-cleaning fiber coating and preparation method thereof - Google Patents
Waterproof self-cleaning fiber coating and preparation method thereof Download PDFInfo
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
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- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
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Abstract
The invention discloses a waterproof self-cleaning fiber coating and a preparation method thereof, and relates to the technical field of new materials. The method comprises the steps of spinning ferroferric oxide coated by oleic acid and polyvinyl alcohol together to prepare modified polyvinyl alcohol fibers, mixing starch with the ferroferric oxide to prepare starch-based magnetic particles, adsorbing metal ions by the starch-based magnetic particles, inserting the metal ions into a niobate lamellar structure to prepare modified niobate, crushing the modified polyvinyl alcohol fibers, mixing the crushed modified polyvinyl alcohol fibers with the modified niobate, forming crosslinking under the action of polyphosphoric acid and maleic anhydride, and coating the fibers to form a film so as to prepare the waterproof self-cleaning fiber coating. The waterproof self-cleaning fiber coating prepared by the invention has excellent waterproofness and good self-cleaning performance on inorganic and organic pollutants.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to a waterproof self-cleaning fiber coating and a preparation method thereof.
Background
Polyvinyl alcohol: organic compounds, white flaky, flocculent or powdery solids, no odor. Is soluble in water (above 95 deg.C), slightly soluble in dimethyl sulfoxide, and insoluble in gasoline, kerosene, vegetable oil, benzene, toluene, dichloroethane, carbon tetrachloride, acetone, ethyl acetate, methanol, and ethylene glycol. Polyvinyl alcohol is an important chemical raw material, and is used for manufacturing polyvinyl acetal, gasoline-resistant pipelines, vinylon synthetic fibers, fabric treating agents, emulsifiers, paper coatings, adhesives, glue and the like.
When the polyvinyl alcohol is used for the fiber coating, the water resistance is poor due to the good hydrophilicity of the polyvinyl alcohol, and most fiber coatings on the market at present do not have the self-cleaning function, so the application of the fiber coating is limited.
Disclosure of Invention
The invention aims to provide a waterproof self-cleaning fiber coating and a preparation method thereof, and aims to solve the problems in the prior art.
The waterproof self-cleaning fiber coating is characterized by mainly comprising the following raw material components in parts by weight: 70-90 parts of modified polyvinyl alcohol fiber, 8-15 parts of maleic anhydride, 10-20 parts of modified niobate, 1-3 parts of polyphosphoric acid and 8-15 parts of crosslinking liquid;
the modified niobate comprises the following raw materials: niobate sol, ferroferric oxide, starch and metal salt.
As optimization, the modified polyvinyl alcohol fiber is prepared by carrying out electrostatic spinning on polyvinyl alcohol and modified ferroferric oxide; the modified ferroferric oxide is prepared from ferroferric oxide and oleic acid.
Preferably, the niobate sol is prepared by calcining niobium pentoxide and anhydrous potassium carbonate, and then acidifying by nitric acid and treating by tetrabutyl ammonium hydroxide.
Preferably, the metal salt is any one of lead nitrate or lead chloride.
As optimization, the waterproof self-cleaning fiber coating mainly comprises the following raw material components in parts by weight: 70 parts of modified polyvinyl alcohol fiber, 8 parts of maleic anhydride, 18 parts of modified niobate, 2 parts of polyphosphoric acid and 12 parts of crosslinking liquid.
As optimization, the preparation method of the waterproof self-cleaning fiber coating mainly comprises the following preparation steps:
(1) mixing an iron trichloride aqueous solution and a ferrous sulfate aqueous solution, dropwise adding ammonia water at a constant temperature and a constant speed under an inert gas atmosphere, adding oleic acid, stirring for reaction, adjusting the pH value to acidity, performing magnetic precipitation, removing waste liquid to obtain a modified ferroferric oxide blank, washing the modified ferroferric oxide blank with an acid solution, and performing vacuum drying to obtain modified ferroferric oxide;
(2) mixing polyvinyl alcohol with water, heating and stirring until the polyvinyl alcohol is completely dissolved to obtain a polyvinyl alcohol solution, mixing the polyvinyl alcohol solution with the modified ferroferric oxide obtained in the step (1), and then performing electrostatic spinning in an electrostatic spinning machine to obtain modified polyvinyl alcohol fibers;
(3) mixing starch with water, adding a ferrous sulfate heptahydrate solution, a ferric chloride hexahydrate solution and an alkali solution, stirring to react until the solution is black, carrying out magnetic separation, removing waste liquid to obtain modified starch, mixing the modified starch with a metal salt solution, adding niobate sol, adjusting the pH value to be acidic, filtering, and drying to obtain modified niobate;
(4) crushing modified polyvinyl alcohol fibers, mixing with water, adding modified niobate, stirring and mixing to obtain a mixed solution, mixing the mixed solution with maleic anhydride, adding polyphosphoric acid, stirring and reacting to obtain a film-forming solution, coating the film-forming solution on a substrate, drying to obtain a waterproof self-cleaning fiber coating blank, and fumigating the waterproof self-cleaning fiber coating blank with a crosslinking solution to obtain the waterproof self-cleaning fiber coating.
As optimization, the preparation method of the waterproof self-cleaning fiber coating mainly comprises the following preparation steps:
(1) mixing a ferric trichloride aqueous solution with the concentration of 0.4mol/L and a ferrous sulfate aqueous solution with the concentration of 0.4mol/L in a three-mouth flask according to the volume ratio of 14:9, introducing nitrogen into the three-mouth flask at the speed of 30-60 mL/min, removing oxygen in the three-mouth flask, raising the temperature of materials in the three-mouth flask to 55 ℃, adding ammonia water with the mass fraction of 25% into the three-mouth flask at the speed of 60-80 drops/min, stirring and reacting until the color of the materials in the three-mouth flask is black, stopping dropping, adding oleic acid with the volume of 0.02-0.03 time of that of the ferric trichloride aqueous solution into the three-mouth flask, stirring and reacting for 2 hours at the temperature of 80 ℃, adjusting the pH of the materials in the three-mouth flask to 4-6 by using acetic acid with the mass fraction of 8-10%, performing magnetic precipitation to remove waste liquid, obtaining a modified ferroferric oxide blank, washing the modified ferroferric oxide blank by using an acetic acid solution with the mass fraction of 5% for 2-3 times, vacuum drying at 50 deg.C for 12 hr to obtain modified ferroferric oxide;
(2) mixing polyvinyl alcohol and water according to a mass ratio of 3:20, stirring at a temperature of 95 ℃ until the polyvinyl alcohol and the water are completely dissolved to obtain a polyvinyl alcohol solution, mixing the polyvinyl alcohol solution and the modified ferroferric oxide obtained in the step (1) according to a mass ratio of 10: 1-10: 2, and performing electrostatic spinning in an electrostatic spinning machine to obtain modified polyvinyl alcohol fibers;
(3) mixing starch and water according to the mass ratio of 1: 10-1: 15 to obtain a starch solution, mixing the starch solution and a ferrous sulfate heptahydrate solution with the concentration of 0.056g/mL according to the volume ratio of 1:1 in a beaker, adding a ferric chloride hexahydrate solution with the concentration of 0.054g/mL and a sodium hydroxide solution with the concentration of 0.8-1.5 times of the volume of the starch solution which are 2 times of the volume of the starch solution in the beaker, stirring and reacting at the temperature of 100 ℃, performing magnetic separation to remove waste liquid to obtain modified starch, mixing the modified starch and a metal salt solution in the flask according to the mass ratio of 1: 15-1: 20, adding a niobate sol with the mass of 5-10 times of the modified starch in the flask, adjusting the pH of materials in the flask to 4-6 by using nitric acid with the concentration of 0.5mol/L, filtering, obtaining a filter cake, and drying the filter cake in vacuum for 2-4 h at the temperature of 80 ℃ to obtain the modified niobate;
(4) crushing the modified polyvinyl alcohol fiber obtained in the step (2), mixing the crushed modified polyvinyl alcohol fiber with water according to the mass ratio of 1: 8-1: 10, adding modified niobate with the mass of 0.28-0.30 time of that of the modified polyvinyl alcohol fiber into the stirring kettle, stirring and mixing the mixture for 30-60 min at the temperature of 30-50 ℃ and the rotating speed of 300-800 r/min to obtain a mixed solution, mixing the mixed solution with maleic anhydride according to the mass ratio of 990:8, adding polyphosphoric acid with the mass of 0.25 time of that of the maleic anhydride, stirring and reacting for 3-4 h at the temperature of 85-90 ℃ to obtain a film-forming solution, coating the film-forming solution on the surface of a substrate, controlling the coating thickness to be 200-420 mu m, drying the film-forming solution to constant weight at the temperature of 80 ℃ to obtain a waterproof self-cleaning fiber coating blank, fumigating the waterproof self cleaning fiber coating blank for 1-3 h by using a cross-linking solution with the mass of 0.1-0.2 time of the waterproof self cleaning fiber coating blank, obtaining the waterproof self-cleaning fiber coating.
And (3) optimizing, wherein the electrostatic spinning in the step (2) is carried out under the conditions that the spinning voltage is 18-30 kv and the receiving distance is 10-15 cm.
As optimization, the metal solution in the step (3) is any one of a lead nitrate solution with the mass fraction of 8% or a lead chloride solution with the mass fraction of 8%; the preparation method of the niobate sol comprises the steps of mixing and grinding potassium carbonate pentahydrate and niobium pentoxide according to a molar ratio of 2:3 to obtain mixed powder, mixing the mixed powder and water according to a mass ratio of 1: 2-1: 4, carrying out ultrasonic dispersion for 10-30 min under the condition of 45kHz, drying, roasting for 24h under the condition of 1100 ℃ to obtain potassium niobate, mixing the potassium niobate and nitric acid with a concentration of 6mol/L according to a mass ratio of 1:10, stirring and reacting for 5 days under the condition of 55 ℃, changing acid liquor every 24h, filtering, washing with deionized water until a washing liquid is neutral to obtain acidified niobate, mixing the acidified niobate and water according to a mass ratio of 1:200, adjusting the pH of the acidified niobate-water mixture to 9.5-10 by tetrabutylammonium hydroxide, oscillating for 30-80 h under the conditions of 60 ℃ and 20-30 kHz, obtaining the niobate sol.
As optimization, the substrate in the step (4) is any one of a quartz sheet or a metal sheet; the preparation method of the cross-linking liquid comprises the step of mixing 25% by mass of glutaraldehyde and 31% by mass of acetic acid according to the volume ratio of 1: 1-2: 1 to obtain the cross-linking liquid.
Compared with the prior art, the invention has the beneficial effects that:
the invention uses modified polyvinyl alcohol fiber and adds modified niobate when preparing waterproof self-cleaning fiber coating.
Firstly, modified polyvinyl alcohol fiber is used as a raw material, the modified polyvinyl alcohol fiber contains oleic acid-coated ferroferric oxide, the oleic acid-coated ferroferric oxide can effectively improve the strength of the polyvinyl alcohol fiber after being added into polyvinyl alcohol, and the modified niobate can be adsorbed on the surface of the modified polyvinyl alcohol fiber under the action of magnetism after the modified polyvinyl alcohol fiber and the modified niobate are mixed due to the existence of the ferroferric oxide, so that the waterproofness of the modified polyvinyl alcohol fiber is improved;
secondly, after the niobate is modified, starch-based magnetic particles are inserted into a niobate lamellar structure and adsorbed on the surface of polyvinyl alcohol under the magnetic action, and then the niobate lamellar structure can be crosslinked with the polyvinyl alcohol under the action of maleic anhydride and ammonium polyphosphate, so that the density of the product can be improved, and meanwhile, the modified niobate of the lamellar structure is firmly adsorbed on the surface of modified polyvinyl alcohol fibers, and further, the waterproof performance of the product is improved; moreover, due to the existence of the lamellar modified niobate, when the surface of the product contains more impurities, water vapor among lamellar structures cannot volatilize, so that the interlayer structure of the modified niobate in the product is in a wet state for a long time, a crosslinking network formed by starch, maleic anhydride and polyvinyl alcohol is promoted to degrade, and ferroferric oxide is rapidly oxidized to lose magnetism, so that the lamellar structure exposed to the outside in the modified niobate is unbound and falls off, and a self-cleaning effect is achieved; simultaneously, because the niobate has good catalytic activity, the product has good self-cleaning effect on organic and inorganic impurities.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to illustrate the method provided by the invention more clearly, the following examples are used for describing the method for testing each index of the waterproof self-cleaning fiber coating prepared in the following examples as follows:
water resistance: the water contact angle of the water repellent self-cleaning fibrous coating obtained in each example with the comparative product was measured.
Self-cleaning performance: placing the waterproof self-cleaning fiber coating obtained in each example and a comparative product outdoors, and measuring the weight change rate of the product after the product is placed for 30 days; the greater the weight, the poorer the self-cleaning performance.
Example 1
A waterproof self-cleaning fiber coating mainly comprises the following components in parts by weight: 70 parts of modified polyvinyl alcohol fiber, 8 parts of maleic anhydride, 18 parts of modified niobate, 2 parts of polyphosphoric acid and 12 parts of crosslinking liquid.
A preparation method of a waterproof self-cleaning fiber coating mainly comprises the following preparation steps:
(1) mixing a ferric trichloride aqueous solution with the concentration of 0.4mol/L and a ferrous sulfate aqueous solution with the concentration of 0.4mol/L in a three-mouth flask according to the volume ratio of 14:9, introducing nitrogen into the three-mouth flask at the speed of 50mL/min, removing oxygen in the three-mouth flask, raising the temperature of materials in the three-mouth flask to 55 ℃, adding ammonia water with the mass fraction of 25% into the three-mouth flask at the speed of 70 drops/min, stirring and reacting until the color of the materials in the three-mouth flask is black, stopping dropping, adding oleic acid with the volume of 0.024 times of that of the ferric trichloride aqueous solution into the three-mouth flask, stirring and reacting at the temperature of 80 ℃ for 2 hours, adjusting the pH of the materials in the three-mouth flask to 4.5 by using acetic acid with the mass fraction of 10%, carrying out ferromagnetic precipitation, removing waste liquid to obtain a modified ferroferric oxide blank, washing the modified ferroferric oxide blank by using an acetic acid solution with the mass fraction of 5% for 3 times, vacuum drying at 50 deg.C for 12 hr to obtain modified ferroferric oxide;
(2) mixing polyvinyl alcohol and water according to a mass ratio of 3:20, stirring the mixture at a temperature of 95 ℃ until the mixture is completely dissolved to obtain a polyvinyl alcohol solution, mixing the polyvinyl alcohol solution and the modified ferroferric oxide obtained in the step (1) according to a mass ratio of 10:1, and performing electrostatic spinning in an electrostatic spinning machine to obtain modified polyvinyl alcohol fibers;
(3) mixing starch and water according to the mass ratio of 1:12 to obtain a starch solution, mixing the starch solution and a ferrous sulfate heptahydrate solution with the concentration of 0.056g/mL according to the volume ratio of 1:1 in a beaker, adding a ferric trichloride hexahydrate solution with the concentration of 0.054g/mL, which is 2 times the volume of the starch solution, and a sodium hydroxide solution with the concentration of 0.04g/mL, which is 1 time the volume of the starch solution, into the beaker, stirring and reacting at the temperature of 100 ℃, performing magnetic separation to remove waste liquid to obtain modified starch, mixing the modified starch and a metal salt solution according to the mass ratio of 1:18 in the flask, adding niobate sol with the mass of 7 times that of the modified starch into the flask, adjusting the pH of the materials in the flask to 5 by using nitric acid with the concentration of 0.5mol/L, filtering to obtain a filter cake, performing vacuum drying on the filter cake for 3 hours at the temperature of 80 ℃, obtaining modified niobate;
(4) crushing the modified polyvinyl alcohol fiber obtained in the step (2), mixing the crushed modified polyvinyl alcohol fiber with water according to the mass ratio of 1:8 in a stirring kettle, adding the modified niobate obtained in the step (3) with the mass of 0.28 time of that of the modified polyvinyl alcohol fiber into the stirring kettle, stirring and mixing the mixture for 40min at the temperature of 45 ℃ and the rotating speed of 700r/min to obtain a mixed solution, mixing the mixed solution with maleic anhydride according to the mass ratio of 990:8, adding polyphosphoric acid with the mass of 0.25 time of that of the maleic anhydride, stirring and reacting the mixture for 3h at the temperature of 85 ℃ to obtain a film-forming solution, coating the film-forming solution on the surface of the matrix solution, controlling the coating thickness to be 350 mu m, drying the film-forming solution to constant weight at the temperature of 80 ℃ to obtain a waterproof self-cleaning fiber coating blank, fumigating the waterproof self-cleaning fiber coating blank for 2h by using a crosslinking solution with the mass of 0.12 time of the waterproof self-cleaning fiber coating blank, obtaining the waterproof self-cleaning fiber coating.
As optimization, the electrostatic spinning condition of the step (2) is a spinning voltage of 30kv, and the receiving distance is 15 cm.
As optimization, the metal solution in the step (3) is a lead nitrate solution with the mass fraction of 8%; the preparation method of the niobate sol comprises the steps of mixing and grinding potassium carbonate pentahydrate and niobium pentoxide according to the molar ratio of 2:3 to obtain mixed powder, mixing the mixed powder and water according to the mass ratio of 1: 2-1: 4, carrying out ultrasonic dispersion for 20min under the condition of the frequency of 45kHz, drying, roasting at 1100 deg.c for 24 hr to obtain potassium niobate, mixing potassium niobate with 6mol/L nitric acid in the mass ratio of 1 to 10, stirring at 55 deg.c for 5 days, replacing acid liquid every 24 hr, filtering, washing with deionized water to neutrality to obtain acidified niobate, mixing acidified niobate with water in the mass ratio of 1 to 200, and adjusting the pH value of the mixture of the acidified niobate and water to 9.5 by tetrabutylammonium hydroxide, and oscillating for 45 hours at the temperature of 60 ℃ and the frequency of 30kHz to obtain niobate sol.
As optimization, the substrate in the step (4) is a quartz plate; the preparation method of the cross-linking liquid comprises the step of mixing 25% by mass of glutaraldehyde and 31% by mass of acetic acid according to the volume ratio of 1:1 to obtain the cross-linking liquid.
Example 2
A waterproof self-cleaning fiber coating mainly comprises the following components in parts by weight: 70 parts of polyvinyl alcohol fiber, 8 parts of maleic anhydride, 18 parts of modified niobate, 2 parts of polyphosphoric acid and 12 parts of crosslinking liquid.
A preparation method of a waterproof self-cleaning fiber coating mainly comprises the following preparation steps:
(1) mixing polyvinyl alcohol and water according to a mass ratio of 3:20, stirring the mixture at a temperature of 95 ℃ until the mixture is completely dissolved to obtain a polyvinyl alcohol solution, and performing electrostatic spinning on the polyvinyl alcohol solution in an electrostatic spinning machine to obtain polyvinyl alcohol fibers;
(2) mixing starch and water according to the mass ratio of 1:12 to obtain a starch solution, mixing the starch solution and a ferrous sulfate heptahydrate solution with the concentration of 0.056g/mL according to the volume ratio of 1:1 in a beaker, adding a ferric trichloride hexahydrate solution with the concentration of 0.054g/mL, which is 2 times the volume of the starch solution, and a sodium hydroxide solution with the concentration of 0.04g/mL, which is 1 time the volume of the starch solution, into the beaker, stirring and reacting at the temperature of 100 ℃, performing magnetic separation to remove waste liquid to obtain modified starch, mixing the modified starch and a metal salt solution according to the mass ratio of 1:18 in the flask, adding niobate sol with the mass of 7 times that of the modified starch into the flask, adjusting the pH of the materials in the flask to 5 by using nitric acid with the concentration of 0.5mol/L, filtering to obtain a filter cake, performing vacuum drying on the filter cake for 3 hours at the temperature of 80 ℃, obtaining modified niobate;
(3) crushing the polyvinyl alcohol fiber obtained in the step (1), mixing the crushed polyvinyl alcohol fiber with water in a mass ratio of 1:8 in a stirring kettle, adding the modified niobate obtained in the step (2) with the mass of 0.28 time of that of the modified polyvinyl alcohol fiber into a stirring kettle, stirring and mixing for 40min at the temperature of 45 ℃ and the rotating speed of 700r/min to obtain a mixed solution, mixing the mixed solution with maleic anhydride according to the mass ratio 990:8, adding polyphosphoric acid with the mass of 0.25 time of that of the maleic anhydride, stirring and reacting for 3 hours at the temperature of 85 ℃, obtaining a film-forming solution, coating the film-forming solution on the surface of a substrate, controlling the coating thickness to be 350 mu m, drying the fiber coating blank to constant weight at 80 ℃ to obtain a waterproof self-cleaning fiber coating blank, and fumigating the waterproof self-cleaning fiber coating blank for 2 hours by using a cross-linking liquid with the mass of 0.12 time that of the waterproof self-cleaning fiber coating blank to obtain the waterproof self-cleaning fiber coating.
As optimization, the electrostatic spinning condition of the step (1) is a spinning voltage of 30kv, and a receiving distance of 15 cm.
As optimization, the metal solution in the step (2) is a lead nitrate solution with the mass fraction of 8%; the preparation method of the niobate sol comprises the steps of mixing and grinding potassium carbonate pentahydrate and niobium pentoxide according to the molar ratio of 2:3 to obtain mixed powder, mixing the mixed powder and water according to the mass ratio of 1: 2-1: 4, carrying out ultrasonic dispersion for 20min under the condition of the frequency of 45kHz, drying, roasting at 1100 deg.c for 24 hr to obtain potassium niobate, mixing potassium niobate with 6mol/L nitric acid in the mass ratio of 1 to 10, stirring at 55 deg.c for 5 days, replacing acid liquid every 24 hr, filtering, washing with deionized water to neutrality to obtain acidified niobate, mixing acidified niobate with water in the mass ratio of 1 to 200, and adjusting the pH value of the mixture of the acidified niobate and water to 9.5 by tetrabutylammonium hydroxide, and oscillating for 45 hours at the temperature of 60 ℃ and the frequency of 30kHz to obtain niobate sol.
As optimization, the substrate in the step (3) is a quartz plate; the preparation method of the cross-linking liquid comprises the step of mixing 25% by mass of glutaraldehyde and 31% by mass of acetic acid according to the volume ratio of 1:1 to obtain the cross-linking liquid.
Example 3
A waterproof self-cleaning fiber coating mainly comprises the following components in parts by weight: 70 parts of modified polyvinyl alcohol fiber, 8 parts of maleic anhydride, 18 parts of niobate, 2 parts of polyphosphoric acid and 12 parts of crosslinking liquid.
A preparation method of a waterproof self-cleaning fiber coating mainly comprises the following preparation steps:
(1) mixing a ferric trichloride aqueous solution with the concentration of 0.4mol/L and a ferrous sulfate aqueous solution with the concentration of 0.4mol/L in a three-mouth flask according to the volume ratio of 14:9, introducing nitrogen into the three-mouth flask at the speed of 50mL/min, removing oxygen in the three-mouth flask, raising the temperature of materials in the three-mouth flask to 55 ℃, adding ammonia water with the mass fraction of 25% into the three-mouth flask at the speed of 70 drops/min, stirring and reacting until the color of the materials in the three-mouth flask is black, stopping dropping, adding oleic acid with the volume of 0.024 times of that of the ferric trichloride aqueous solution into the three-mouth flask, stirring and reacting at the temperature of 80 ℃ for 2 hours, adjusting the pH of the materials in the three-mouth flask to 4.5 by using acetic acid with the mass fraction of 10%, carrying out ferromagnetic precipitation, removing waste liquid to obtain a modified ferroferric oxide blank, washing the modified ferroferric oxide blank by using an acetic acid solution with the mass fraction of 5% for 3 times, vacuum drying at 50 deg.C for 12 hr to obtain modified ferroferric oxide;
(2) mixing polyvinyl alcohol and water according to a mass ratio of 3:20, stirring the mixture at a temperature of 95 ℃ until the mixture is completely dissolved to obtain a polyvinyl alcohol solution, mixing the polyvinyl alcohol solution and the modified ferroferric oxide obtained in the step (1) according to a mass ratio of 10:1, and performing electrostatic spinning in an electrostatic spinning machine to obtain modified polyvinyl alcohol fibers;
(3) mixing a ferrous sulfate heptahydrate solution with the concentration of 0.056g/mL and a ferric chloride hexahydrate solution with the concentration of 0.054g/mL according to the volume ratio of 1:2, mixing the mixture in a beaker, adding a sodium hydroxide solution with the concentration of 0.04g/mL, the volume of which is 1 time of that of a ferrous sulfate heptahydrate solution, into the beaker, stirring the mixture at the temperature of 100 ℃ to react until the materials in the beaker are black, performing magnetic separation, removing waste liquid to obtain ferroferric oxide, mixing the ferroferric oxide and a metal salt solution in a mass ratio of 1:18 in the flask, adding niobate sol with the mass of 7 times of that of modified starch into the flask, adjusting the pH of the materials in the flask to 5 by using nitric acid with the concentration of 0.5mol/L, filtering the mixture to obtain a filter cake, and performing vacuum drying on the filter cake at the temperature of 80 ℃ for 3 hours to obtain niobate;
(4) crushing the modified polyvinyl alcohol fiber obtained in the step (2), mixing the crushed modified polyvinyl alcohol fiber with water in a mass ratio of 1:8 in a stirring kettle, adding the niobate obtained in the step (3) with the mass of 0.28 time of that of the modified polyvinyl alcohol fiber into a stirring kettle, stirring and mixing for 40min at the temperature of 45 ℃ and the rotating speed of 700r/min to obtain a mixed solution, mixing the mixed solution with maleic anhydride according to the mass ratio 990:8, adding polyphosphoric acid with the mass of 0.25 time of that of the maleic anhydride, stirring and reacting for 3 hours at the temperature of 85 ℃, obtaining a film-forming solution, coating the film-forming solution on the surface of a substrate, controlling the coating thickness to be 350 mu m, drying the fiber coating blank to constant weight at 80 ℃ to obtain a waterproof self-cleaning fiber coating blank, and fumigating the waterproof self-cleaning fiber coating blank for 2 hours by using a cross-linking liquid with the mass of 0.12 time that of the waterproof self-cleaning fiber coating blank to obtain the waterproof self-cleaning fiber coating.
As optimization, the electrostatic spinning condition of the step (2) is a spinning voltage of 30kv, and the receiving distance is 15 cm.
As optimization, the metal solution in the step (3) is a lead nitrate solution with the mass fraction of 8%; the preparation method of the niobate sol comprises the steps of mixing and grinding potassium carbonate pentahydrate and niobium pentoxide according to the molar ratio of 2:3 to obtain mixed powder, mixing the mixed powder and water according to the mass ratio of 1: 2-1: 4, carrying out ultrasonic dispersion for 20min under the condition of the frequency of 45kHz, drying, roasting at 1100 deg.c for 24 hr to obtain potassium niobate, mixing potassium niobate with 6mol/L nitric acid in the mass ratio of 1 to 10, stirring at 55 deg.c for 5 days, replacing acid liquid every 24 hr, filtering, washing with deionized water to neutrality to obtain acidified niobate, mixing acidified niobate with water in the mass ratio of 1 to 200, and adjusting the pH value of the mixture of the acidified niobate and water to 9.5 by tetrabutylammonium hydroxide, and oscillating for 45 hours at the temperature of 60 ℃ and the frequency of 30kHz to obtain niobate sol.
As optimization, the substrate in the step (4) is a quartz plate; the preparation method of the cross-linking liquid comprises the step of mixing 25% by mass of glutaraldehyde and 31% by mass of acetic acid according to the volume ratio of 1:1 to obtain the cross-linking liquid.
Comparative example
A waterproof self-cleaning fiber coating mainly comprises the following components in parts by weight: 70 parts of polyvinyl alcohol fiber, 8 parts of maleic anhydride, 18 parts of modified niobate, 2 parts of polyphosphoric acid and 12 parts of crosslinking liquid.
A preparation method of a waterproof self-cleaning fiber coating mainly comprises the following preparation steps:
(1) mixing polyvinyl alcohol and water according to a mass ratio of 3:20, stirring the mixture at a temperature of 95 ℃ until the mixture is completely dissolved to obtain a polyvinyl alcohol solution, and performing electrostatic spinning on the polyvinyl alcohol solution in an electrostatic spinning machine to obtain polyvinyl alcohol fibers;
(2) mixing a ferrous sulfate heptahydrate solution with the concentration of 0.056g/mL and a ferric chloride hexahydrate solution with the concentration of 0.054g/mL according to the volume ratio of 1:2, mixing the mixture in a beaker, adding a sodium hydroxide solution with the concentration of 0.04g/mL, the volume of which is 1 time of that of a ferrous sulfate heptahydrate solution, into the beaker, stirring the mixture at the temperature of 100 ℃ to react until the materials in the beaker are black, performing magnetic separation, removing waste liquid to obtain ferroferric oxide, mixing the ferroferric oxide and a metal salt solution in a mass ratio of 1:18 in the flask, adding niobate sol with the mass of 7 times of that of modified starch into the flask, adjusting the pH of the materials in the flask to 5 by using nitric acid with the concentration of 0.5mol/L, filtering the mixture to obtain a filter cake, and performing vacuum drying on the filter cake at the temperature of 80 ℃ for 3 hours to obtain niobate;
(3) crushing the polyvinyl alcohol fiber obtained in the step (1), mixing the crushed polyvinyl alcohol fiber with water in a mass ratio of 1:8 in a stirring kettle, adding the niobate obtained in the step (2) with the mass of 0.28 time of that of the modified polyvinyl alcohol fiber into a stirring kettle, stirring and mixing for 40min at the temperature of 45 ℃ and the rotating speed of 700r/min to obtain a mixed solution, mixing the mixed solution with maleic anhydride according to the mass ratio 990:8, adding polyphosphoric acid with the mass of 0.25 time of that of the maleic anhydride, stirring and reacting for 3 hours at the temperature of 85 ℃, obtaining a film-forming solution, coating the film-forming solution on the surface of a substrate, controlling the coating thickness to be 350 mu m, drying the fiber coating blank to constant weight at 80 ℃ to obtain a waterproof self-cleaning fiber coating blank, and fumigating the waterproof self-cleaning fiber coating blank for 2 hours by using a cross-linking liquid with the mass of 0.12 time that of the waterproof self-cleaning fiber coating blank to obtain the waterproof self-cleaning fiber coating.
As optimization, the electrostatic spinning condition of the step (1) is a spinning voltage of 30kv, and a receiving distance of 15 cm.
As optimization, the metal solution in the step (2) is a lead nitrate solution with the mass fraction of 8%; the preparation method of the niobate sol comprises the steps of mixing and grinding potassium carbonate pentahydrate and niobium pentoxide according to the molar ratio of 2:3 to obtain mixed powder, mixing the mixed powder and water according to the mass ratio of 1: 2-1: 4, carrying out ultrasonic dispersion for 20min under the condition of the frequency of 45kHz, drying, roasting at 1100 deg.c for 24 hr to obtain potassium niobate, mixing potassium niobate with 6mol/L nitric acid in the mass ratio of 1 to 10, stirring at 55 deg.c for 5 days, replacing acid liquid every 24 hr, filtering, washing with deionized water to neutrality to obtain acidified niobate, mixing acidified niobate with water in the mass ratio of 1 to 200, and adjusting the pH value of the mixture of the acidified niobate and water to 9.5 by tetrabutylammonium hydroxide, and oscillating for 45 hours at the temperature of 60 ℃ and the frequency of 30kHz to obtain niobate sol.
As optimization, the substrate in the step (3) is a quartz plate; the preparation method of the cross-linking liquid comprises the step of mixing 25% by mass of glutaraldehyde and 31% by mass of acetic acid according to the volume ratio of 1:1 to obtain the cross-linking liquid.
Examples of effects
Table 1 below gives the results of performance analysis of the waterproof self-cleaning fiber coatings using examples 1 to 3 of the present invention and comparative example.
TABLE 1
| Example 1 | Example 2 | Example 3 | Comparative example | |
| Water contact Angle (°) | 161 | 123 | 128 | 112 |
| Rate of change in weight (%) | -0.09 | +0.02 | +0.04 | +0.09 |
From the comparison of the experimental data of example 1 and the comparative example in table 1, it can be found that the use of the modified polyvinyl alcohol fiber and the modified niobate in the preparation of the waterproof self-cleaning fiber coating can effectively improve the waterproof property and the self-cleaning effect of the product; from the comparison of the experimental data of the embodiment 1 and the embodiment 2, it can be found that the modified niobate can not form good contact with the modified polyvinyl alcohol fiber without using the modified polyvinyl alcohol fiber when preparing the waterproof self-cleaning fiber coating, thereby reducing the performance of the product; from the comparison of the experimental data of example 1 and example 3, it can be found that when the modified niobate is not added in the preparation of the waterproof self-cleaning fiber coating, the bonding force between the niobate and the modified polyvinyl alcohol fiber is weakened, so that the niobate falls off in a large amount when the self-cleaning is realized for the first time, and the niobate does not have the self-cleaning effect in the later period, so that the weight of the product is increased.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
1. The waterproof self-cleaning fiber coating is characterized by mainly comprising the following raw material components in parts by weight: 70-90 parts of modified polyvinyl alcohol fiber, 8-15 parts of maleic anhydride, 10-20 parts of modified niobate, 1-3 parts of polyphosphoric acid and 8-15 parts of crosslinking liquid;
the modified niobate comprises the following raw materials: niobate sol, ferroferric oxide, starch and metal salt.
2. The waterproof self-cleaning fiber coating of claim 1, wherein the modified polyvinyl alcohol fiber is prepared by electrospinning polyvinyl alcohol and modified ferroferric oxide; the modified ferroferric oxide is prepared from ferroferric oxide and oleic acid.
3. The waterproof self-cleaning fiber coating of claim 2, wherein said niobate sol is prepared by calcining niobium pentoxide and anhydrous potassium carbonate, acidifying with nitric acid, and treating with tetrabutylammonium hydroxide.
4. A water-resistant self-cleaning fibre coating according to claim 3, characterised in that the metal salt is any one of lead nitrate or lead chloride.
5. The waterproof self-cleaning fiber coating of claim 4, which mainly comprises the following raw material components in parts by weight: 70 parts of modified polyvinyl alcohol fiber, 8 parts of maleic anhydride, 18 parts of modified niobate, 2 parts of polyphosphoric acid and 12 parts of crosslinking liquid.
6. A preparation method of a waterproof self-cleaning fiber coating is characterized by mainly comprising the following preparation steps:
(1) mixing an iron trichloride aqueous solution and a ferrous sulfate aqueous solution, dropwise adding ammonia water at a constant temperature and a constant speed under an inert gas atmosphere, adding oleic acid, stirring for reaction, adjusting the pH value to acidity, performing magnetic precipitation, removing waste liquid to obtain a modified ferroferric oxide blank, washing the modified ferroferric oxide blank with an acid solution, and performing vacuum drying to obtain modified ferroferric oxide;
(2) mixing polyvinyl alcohol with water, heating and stirring until the polyvinyl alcohol is completely dissolved to obtain a polyvinyl alcohol solution, mixing the polyvinyl alcohol solution with the modified ferroferric oxide obtained in the step (1), and then performing electrostatic spinning in an electrostatic spinning machine to obtain modified polyvinyl alcohol fibers;
(3) mixing starch with water, adding a ferrous sulfate heptahydrate solution, a ferric chloride hexahydrate solution and an alkali solution, stirring to react until the solution is black, carrying out magnetic separation, removing waste liquid to obtain modified starch, mixing the modified starch with a metal salt solution, adding niobate sol, adjusting the pH value to be acidic, filtering, and drying to obtain modified niobate;
(4) crushing modified polyvinyl alcohol fibers, mixing with water, adding modified niobate, stirring and mixing to obtain a mixed solution, mixing the mixed solution with maleic anhydride, adding polyphosphoric acid, stirring and reacting to obtain a film-forming solution, coating the film-forming solution on a substrate, drying to obtain a waterproof self-cleaning fiber coating blank, and fumigating the waterproof self-cleaning fiber coating blank with a crosslinking solution to obtain the waterproof self-cleaning fiber coating.
7. The preparation method of the waterproof self-cleaning fiber coating layer as claimed in claim 6, wherein the preparation method of the waterproof self-cleaning fiber coating layer mainly comprises the following preparation steps:
(1) mixing a ferric trichloride aqueous solution with the concentration of 0.4mol/L and a ferrous sulfate aqueous solution with the concentration of 0.4mol/L in a three-mouth flask according to the volume ratio of 14:9, introducing nitrogen into the three-mouth flask at the speed of 30-60 mL/min, removing oxygen in the three-mouth flask, raising the temperature of materials in the three-mouth flask to 55 ℃, adding ammonia water with the mass fraction of 25% into the three-mouth flask at the speed of 60-80 drops/min, stirring and reacting until the color of the materials in the three-mouth flask is black, adding oleic acid with the volume of 0.02-0.03 time of that of the ferric trichloride aqueous solution into the three-mouth flask, stirring and reacting at the temperature of 80 ℃ for 2 hours, adjusting the pH of the materials in the three-mouth flask to 4-6 by using acetic acid with the mass fraction of 8-10%, removing waste liquid by using ferromagnetic precipitation to obtain a modified ferroferric oxide blank, washing the modified ferroferric oxide blank by using acetic acid with the mass fraction of 5% for 2-3 times, vacuum drying at 50 deg.C for 12 hr to obtain modified ferroferric oxide;
(2) mixing polyvinyl alcohol and water according to a mass ratio of 3:20, stirring at a temperature of 95 ℃ until the polyvinyl alcohol and the water are completely dissolved to obtain a polyvinyl alcohol solution, mixing the polyvinyl alcohol solution and the modified ferroferric oxide obtained in the step (1) according to a mass ratio of 10: 1-10: 2, and performing electrostatic spinning in an electrostatic spinning machine to obtain modified polyvinyl alcohol fibers;
(3) mixing starch and water according to the mass ratio of 1: 10-1: 15 to obtain a starch solution, mixing the starch solution and a ferrous sulfate heptahydrate solution with the concentration of 0.056g/mL according to the volume ratio of 1:1 in a beaker, adding a ferric chloride hexahydrate solution with the concentration of 0.054g/mL and a sodium hydroxide solution with the concentration of 0.8-1.5 times of the volume of the starch solution which are 2 times of the volume of the starch solution in the beaker, stirring and reacting at the temperature of 100 ℃, performing magnetic separation to remove waste liquid to obtain modified starch, mixing the modified starch and a metal salt solution in the flask according to the mass ratio of 1: 15-1: 20, adding a niobate sol with the mass of 5-10 times of the modified starch in the flask, adjusting the pH of materials in the flask to 4-6 by using nitric acid with the concentration of 0.5mol/L, filtering, obtaining a filter cake, and drying the filter cake in vacuum for 2-4 h at the temperature of 80 ℃ to obtain the modified niobate;
(4) crushing the modified polyvinyl alcohol fiber obtained in the step (2), mixing the crushed modified polyvinyl alcohol fiber with water according to the mass ratio of 1: 8-1: 10, adding modified niobate with the mass of 0.28-0.30 time of that of the modified polyvinyl alcohol fiber into the stirring kettle, stirring and mixing the mixture for 30-60 min at the temperature of 30-50 ℃ and the rotating speed of 300-800 r/min to obtain a mixed solution, mixing the mixed solution with maleic anhydride according to the mass ratio of 990:8, adding polyphosphoric acid with the mass of 0.25 time of that of the maleic anhydride, stirring and reacting for 3-4 h at the temperature of 85-90 ℃ to obtain a film-forming solution, coating the film-forming solution on the surface of a substrate, controlling the coating thickness to be 200-420 mu m, drying the film-forming solution to constant weight at the temperature of 80 ℃ to obtain a waterproof self-cleaning fiber coating blank, fumigating the waterproof self cleaning fiber coating blank for 1-3 h by using a cross-linking solution with the mass of 0.1-0.2 time of the waterproof self cleaning fiber coating blank, obtaining the waterproof self-cleaning fiber coating.
8. The method for preparing a waterproof self-cleaning fiber coating layer according to claim 7, wherein the electrostatic spinning in the step (2) is performed under the condition of a spinning voltage of 18-30 kv and a receiving distance of 10-15 cm.
9. The method for preparing a waterproof self-cleaning fiber coating layer according to claim 7, wherein the metal solution in the step (3) and the step (3) is any one of a lead nitrate solution with a mass fraction of 8% or a lead chloride solution with a mass fraction of 8%; the preparation method of the niobate sol comprises the steps of mixing and grinding potassium carbonate pentahydrate and niobium pentoxide according to a molar ratio of 2:3 to obtain mixed powder, mixing the mixed powder and water according to a mass ratio of 1: 2-1: 4, carrying out ultrasonic dispersion for 10-30 min under the condition of 45kHz, drying, roasting for 24h under the condition of 1100 ℃ to obtain potassium niobate, mixing the potassium niobate and nitric acid with a concentration of 6mol/L according to a mass ratio of 1:10, stirring and reacting for 5 days under the condition of 55 ℃, changing acid liquor every 24h, filtering, washing with deionized water until a washing liquid is neutral to obtain acidified niobate, mixing the acidified niobate and water according to a mass ratio of 1:200, adjusting the pH of the acidified niobate-water mixture to 9.5-10 by tetrabutylammonium hydroxide, oscillating for 30-80 h under the conditions of 60 ℃ and 20-30 kHz, obtaining the niobate sol.
10. The method for preparing a waterproof self-cleaning fiber coating layer according to claim 7, wherein the substrate in the step (4) is one of a quartz sheet and a metal sheet; the preparation method of the cross-linking liquid comprises the step of mixing 25% by mass of glutaraldehyde and 31% by mass of acetic acid according to the volume ratio of 1: 1-2: 1 to obtain the cross-linking liquid.
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