CN112048910A - Water-repellent fabric and preparation method thereof - Google Patents
Water-repellent fabric and preparation method thereof Download PDFInfo
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- CN112048910A CN112048910A CN202010936730.8A CN202010936730A CN112048910A CN 112048910 A CN112048910 A CN 112048910A CN 202010936730 A CN202010936730 A CN 202010936730A CN 112048910 A CN112048910 A CN 112048910A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
Abstract
The invention discloses a water-repellent fabric and a preparation method thereof. Using short-carbon-chain fluoroalkyl alcohols with different fluorine atom numbers as an initiator, firstly processing the short-carbon-chain fluoroalkyl bromoacetate by using an acylation reagent, and then synthesizing a short-carbon-chain fluoroalkyl diazo acetate monomer with N, N' -bis (p-toluenesulfonyl) hydrazine; respectively processing the fabric by an acylation reagent and N, N' -xylene sulfonyl hydrazide to prepare a diazotized fabric with a grafting site on the surface; finally, grafting the fluorine-containing polymer with the single carbon repeating unit to the surface of the fabric through covalent bonds by carbene polymerization to prepare the modified fabric with hydrophobicity. The whole reaction is carried out at low temperature/room temperature, the operation is simple, and the process is environment-friendly. Based on the characteristics of single carbon repetition and three-dimensional regularity of the carbene polymer, fluoropolymer roughened structures with different geometric appearances and sizes are constructed on the surface of the fabric in one step by inducing the carbene polymer to crystallize and driving the carbene polymer to self-assemble under different conditions, and uniform appearance and controllable size are achieved to a certain extent.
Description
Technical Field
The invention relates to a water-repellent fabric and a preparation method thereof, in particular to a carbene polymerization covalent grafting fluorine-containing polymer, a low surface energy roughening structure with geometric morphology is constructed on the surface of a fiber, and belongs to the technical field of special functional textiles and preparation thereof.
Background
With the continuous development of composite materials, although the functional textile materials in China are still in the initial stage of development, the development space is large and the added value is high, so that the functional textile materials become a hot spot of material development in recent years. The fabric fiber is a material with a large specific surface, and the surface modification of the fiber material becomes a main method for preparing the functional materials, particularly in the field of preparation of waterproof and oil-repellent textiles. At present, the main methods for preparing the water repellent fabric comprise a dip coating method, a spraying method, a sol-gel method, a gas/liquid phase deposition method and the like, but the surface hydrophobic effect of the modified fabric prepared by the methods is easily weakened or lost.
Covalent grafting is a relatively fast and effective method of chemical modification in recent years. Because lower surface energy and certain roughness are necessary conditions for obtaining a water repellent surface, covalent grafting generally comprises constructing an active site on the fiber surface, or grafting a low surface energy polymer to a fabric through a covalent bond by utilizing a functional group of the fiber, or carrying out a polymerization reaction on a monomer containing a low surface energy element directly at a grafting site on the fiber surface to generate the low surface energy polymer. But due to the conventional carbene polymers (C)2Polymer) molecular chain compliance, such that it tends to form a film rather than a topographically uniform roughened structure after grafting onto the fabric surface.
Disclosure of Invention
The invention discloses a method for preparing a water-repellent fabric by covalent grafting of carbene polymerization, aiming at the defects that the water-repellent functional fabric prepared by a dip coating method has poor fastness, generates certain damage to fibers and mostly needs multistep organic-inorganic hybridization, and the problem that a traditional carbene polymerization covalent grafting method is adopted to graft a low-surface-energy polymer on the surface of the fabric and cannot generate a roughened structure with a geometric shape. The characteristic of single carbon repetition of the carbene polymer is utilized, namely, when the covalent grafting is carried out on the surface of the fabric, the polymer of a monomer only providing one carbon unit is grown in each chain growth link, so that the grafted short fluorine chain fluoroalkyl chain segment has a good shielding effect on the main chain of the polymer. Under the induction of the fiber surface, the carbene fluoropolymer grafted on the fabric surface generates a low-surface-roughness structure with geometric morphology, and the water repellency of the fabric is effectively improved.
The invention constructs a low-surface-energy roughened structure with a geometric shape on the surface of the fabric by covalent grafting through carbene polymerization so as to produce the water-repellent fabric, wherein the chemical structural formula of the water-repellent fabric is shown as follows:
r is H or R', m and n represent a repeating unit and are represented by a conventional expression; the surface of the fiber grafted by covalent carbene polymerization has a micro/nano-scale low-surface-energy polymer crystal roughening structure with uniform appearance and controllable size.
The technical scheme for realizing the purpose of the invention is as follows:
a water repellent fabric, which comprises a fabric and a covalently grafted fluoropolymer through carbene polymerization on the surface of the fabric; the structural formula of the carbene polymerization covalent grafting fluorine-containing polymer is as follows:
Rfis fluoroalkyl; preferably, the number of fluorine atoms in the fluoroalkyl group is 3 to 15.
The invention discloses application of the water-repellent fabric in preparing a waterproof material.
The preparation method of the water repellent fabric comprises the following steps: under the action of a catalyst, placing fluoroalkyl diazo acetate and an active fabric in an organic solvent, and covalently grafting a fluorine-containing polymer on the fiber surface of the fabric through carbene polymerization reaction to obtain a water-repellent fabric; the active fabric is a fabric containing grafting sites.
In the invention, the fluorine atom number in the fluoroalkyl diazo acetate is 3-15; the grafting site is diazo; the catalyst is palladium salt; the organic solvent is one or more of tetrahydrofuran, dichloromethane and ethanol; the carbene polymerization reaction is carried out under shaking or stirring.
According to the preparation method, fluoroalkyl alcohol and bromoacetyl bromide react to obtain fluoroalkyl bromoacetate, and then the fluoroalkyl bromoacetate reacts with N, N' -xylene sulfonyl hydrazide to obtain fluoroalkyl diazoacetate; acylating the fabric, and then reacting the fabric with N, N' -xylene sulfonyl hydrazide to prepare an active fabric; wherein the reaction of the fluoroalkyl alcohol with bromoacetyl bromide is carried out in the presence of a base; the reaction of the fluoroalkyl bromoacetate and the N, N' -xylene sulfonyl hydrazide is carried out in the presence of an organic acid-binding agent; the fluoroalkyl alcohol has 3 to 15 fluorine atoms.
The preparation method of the water repellent fabric specifically comprises the following steps:
(1) preparing bromoacetate: fluoroalkyl alcohol is used as an initiator, anhydrous tetrahydrofuran is used as a reaction medium, and the fluoroalkyl bromoacetate is generated by substitution reaction with bromoacetyl bromide under the action of sodium bicarbonate;
(2) preparing a diazonium salt: dissolving fluoroalkyl bromoacetate and diazo precursor N, N' -xylene sulfonyl hydrazide in an anhydrous tetrahydrofuran solvent, and performing catalytic reaction under 1, 8-diazabicycloundec-7-ene to generate fluoroalkyl diazoacetate;
(3) preparing a fiber surface grafting site: tetrahydrofuran is used as a solvent, under the action of an acid-binding agent, fiber surface groups of the fabric are firstly acylated by an acylation reagent and then react with a diazo precursor N, N' -xylene sulfonyl hydrazide at room temperature to prepare an active fabric containing grafting sites;
(4) carbene polymerization covalent grafting reaction: under the action of a catalyst, fluoroalkyl diazo acetate and active fabric are placed in an organic solvent, and a polymer crystal roughening structure with geometric appearance and size is prepared on the surface of the fiber through carbene polymerization reaction under different conditions.
In the step (1) of the preparation method of the water repellent fabric, the fluoroalkyl alcohol is 3, 3, 3-trifluoropropan-1-ol, perfluorobutyl ethanol, perfluorohexyl ethanol and the like; the temperature of the substitution reaction is-5 ℃, and preferably 0-5 ℃; the reaction time of the substitution reaction is 3-5 h.
In the step (2) of the preparation method of the water repellent fabric, the temperature of catalytic reaction is-5 ℃, preferably-5-0 ℃; the reaction time of the catalytic reaction is 3-5 h.
In the step (3) of the preparation method of the water repellent fabric, the acid-binding agent is any one of sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate. The reaction time of the room temperature reaction is 12-24 h.
In the step (4) of the preparation method of the water repellent fabric, the catalyst is any one of palladium chloride, palladium acetate, allyl palladium (II) chloride dimer or bis (acetonitrile) palladium (II) chloride; the organic solvent is any one or more mixed solvents of anhydrous tetrahydrofuran, anhydrous dichloromethane, ethanol and the like; the carbene polymerization reaction is carried out under the conditions of oscillation, stirring and the like, preferably oscillation; the temperature of the carbene polymerization reaction is 25-35 ℃, preferably 28-32 ℃; the reaction time of the carbene polymerization reaction is 12-24 h. Oscillation generally refers to the movement of the fabric along with the erlenmeyer flask; agitation generally refers to movement of the fabric, while the erlenmeyer flask is stationary.
Compared with the prior art, the technical scheme provided by the invention has the beneficial effects that:
1. chemical modification method by covalent grafting: the hydrophilic polar groups such as hydroxyl on the surface of the fiber are taken as active grafting sites, and the surface modifier and the active groups are subjected to chemical grafting reaction, so that the hydrophilic groups on the surface of the fiber are reduced, and the low-surface-energy functional polymer is introduced. Compared with the traditional method, the chemical covalent grafting method at normal temperature not only ensures that the modified fabric has effective and durable water repellency, but also can reduce the original performance of the fabric material to the minimum.
2. The carbene polymerization is a brand new single-carbon repeated polymerization mode, so that the fluorine-containing side chains on the grafted polymer main chain are closely stacked, and a small amount of short-carbon-chain fluoroalkyl monomers are used, so that a good shielding effect on the polymer main chain can be generated. The whole course of the polymerization reaction is carried out at normal temperature, so that the potential danger caused by heating in the material preparation and treatment process is avoided. And the polymerization byproduct is nitrogen, so that tail gas treatment is not needed and the method is relatively environment-friendly.
3. By utilizing the characteristics of single carbon repetition and stereo regularity of the carbene polymer, a polymer roughened structure with low surface energy is constructed on the surface of the fabric in one step, so that the complexity of traditional organic-inorganic hybrid multi-step modification is overcome. The modification mode of Bottom-up (Bottom-up) can achieve the required geometric coarsened morphology structure by designing the molecular structure of the precursor and changing the process, and can achieve uniform morphology and controllable size, thereby overcoming the defect of single coarsened morphology of the inorganic micro/nano particles.
Drawings
FIG. 1 is a surface micro-topography of a fabric grafted by carbene polymerization prepared in accordance with example one;
FIG. 2 is a surface microtopography of a fabric grafted by carbene polymerization prepared in example two (12 hours);
FIG. 3 is a surface micro-topography of the fabric after carbene polymerization grafting prepared in example two (24 hours);
FIG. 4 is a surface micro-topography of the fabric after carbene polymerization grafting prepared in example three;
FIG. 5 is a surface microtopography of the fabric after carbene polymerization grafting prepared in example four;
FIG. 6 is a surface micro-topography of the fabric after carbene polymerization grafting prepared in example five;
FIG. 7 is a surface micro-topography of the fabric after carbene polymerization grafting of example six preparation (12 hours);
FIG. 8 is a surface microtopography of the fabric after carbene polymerization grafting of example six preparation (24 hours);
FIG. 9 is a surface microtopography of a fabric grafted with carbene polymerizations prepared in example seven (12 hours);
FIG. 10 is a surface microtopography of a fabric grafted with carbene polymerizations prepared in example seven (24 hours);
FIG. 11 is a surface microtopography of a fabric grafted with carbene polymerizations prepared in example eight (12 hours);
FIG. 12 is a surface microtopography of the fabric after carbene polymerization grafting prepared in example eight (24 hours);
FIG. 13 is the surface element content and distribution of the fabric after grafting by carbene polymerization prepared in example two (12 hours);
FIG. 14 is the fabric adhesion and hydrophobicity after grafting of the carbene polymer prepared in example two (12 hours);
FIG. 15 shows the surface element content and distribution of the fabric grafted by carbene polymerization prepared in example seven (12 hours).
Detailed Description
The invention discloses a water repellent fabric formed by covalently grafting a fluorine-containing polymer on the surface of a fabric through carbene polymerization.
The preparation method of the water repellent fabric comprises the following steps:
(1) preparing bromoacetate: taking short-carbon-chain fluoroalkyl alcohol containing a certain fluorine atom number as an initiator, taking anhydrous tetrahydrofuran as a reaction medium, and carrying out substitution reaction with bromoacetyl bromide under the action of sodium bicarbonate to generate short-carbon-chain fluoroalkyl bromoacetate;
(2) preparing a diazonium salt: dissolving short-carbon-chain fluoroalkyl bromoacetate and diazo precursor N, N' -xylene sulfonyl hydrazide in an anhydrous tetrahydrofuran solvent, and reacting under the catalysis of 1, 8-diazabicycloundec-7-ene as an acid binding agent to generate short-carbon-chain fluoroalkyl diazoacetate;
(3) preparing a fiber surface grafting site: tetrahydrofuran is used as a solvent, and under the action of an acid-binding agent, hydroxyl on the surface of the fiber is firstly acylated by an acylation reagent and then reacts with a diazo precursor N, N' -xylene sulfonyl hydrazide to prepare active fiber containing a grafting site;
(4) carbene polymerization covalent grafting reaction: under the action of a catalyst, placing short-carbon-chain fluoroalkyl diazo acetate and active fibers in an organic solvent, and preparing polymer crystal roughening structures with different shapes and sizes on the surfaces of the fibers through carbene polymerization reaction under different conditions.
The method comprises the following specific steps:
(1) synthesizing short carbon chain fluoroalkyl bromoacetate:
under the protection of nitrogen, tetrahydrofuran is taken as a reaction medium. Short-carbon-chain fluoroalkyl alcohol and sodium bicarbonate are added into a three-neck flask, bromoacetyl bromide is slowly added into the mixed solution drop by drop at a low temperature (the three are added according to the mol ratio of 1:1.5: 3) for reaction. After the reaction is finished, quenching the reaction by deionized water, then adding saturated sodium bicarbonate solution, extracting by dichloromethane, drying by anhydrous magnesium sulfate, filtering, and removing the low-boiling-point solvent by rotary evaporation to obtain a product;
(2) synthesizing short carbon chain fluoroalkyl diazo acetate:
taking dehydrated tetrahydrofuran as a reaction medium, adding short-carbon-chain fluoroalkyl bromoacetate and N, N' -bis (p-toluenesulfonyl) hydrazine into a three-neck flask under the protection of nitrogen, and dropwise adding 1, 8-diazabicycloundecen-7-ene (DBU) into the mixed solution at low temperature to react for a certain time at constant temperature (the three are added according to the proportion of 1:2:5 mol). After the reaction is finished, quenching the reaction by deionized water, then adding saturated sodium bicarbonate solution, extracting by trichloromethane, drying by anhydrous magnesium sulfate, filtering, and removing the low-boiling-point solvent by rotary evaporation to obtain a product;
(3) fiber surface grafting site generation:
under the protection of nitrogen, adding sodium bicarbonate and cotton fabric into a conical flask by taking dewatered tetrahydrofuran as a reaction medium, dropwise adding bromoacetyl bromide at low temperature, and then placing at normal temperature for reaction. After the reaction is stopped, the fabric is cleaned by tetrahydrofuran and deionized water respectively, and dried at low temperature. And then putting the dried fabric and N, N' -bis (p-toluenesulfonyl) hydrazine into a reactor, and dropwise adding 1, 8-diazabicycloundec-7-ene (DBU) into the mixed solution at low temperature for constant-temperature reaction. After the reaction is finished, respectively cleaning the fabric with tetrahydrofuran and deionized water, and drying at a low temperature for later use;
(4) covalent grafting of a fluoropolymer to a carbene on the surface of a fiber:
under the protection of nitrogen, the reaction media are respectively dehydrated tetrahydrofuran, dichloromethane, toluene, a mixed solution of the dehydrated tetrahydrofuran and absolute ethyl alcohol, and the like. The monomer, the reactive fiber and NaBPh are mixed at room temperature4Placing in a conical flask containing reaction medium, adding (pi-allylPdCl) at low temperature2Then the reaction is carried out at constant temperature in a stable power mode. And after the reaction is finished, respectively cleaning the cotton fabric with tetrahydrofuran and deionized water, and drying at a low temperature to obtain the water-repellent fabric.
The related raw materials are conventional products sold in the market, and the fabric is conventional cotton fabric and is subjected to conventional alkalization treatment; the specific operation method and the test method are conventional techniques. The technical solution of the present invention is further described with reference to the accompanying drawings and examples. Cotton fabric pretreatment: at room temperature, the conventional cotton fabric is immersed into a sodium hydroxide solution with the mass fraction of 20% for treatment for 25 min, washed with distilled water for three times, then immersed in 5% glacial acetic acid for 30min, then washed with deionized water to be neutral, and dried to obtain the alkalized cotton fabric which is used in the embodiment of the invention.
Example one
(1) Synthesis of trifluoropropyl diazoacetic acid ester
50mL of anhydrous tetrahydrofuran, 0.57g of 3, 3, 3-trifluoropropan-1-ol and 1.26g of sodium bicarbonate are added into a three-neck flask, the temperature is reduced to 0 ℃, 1.54g of bromoacetyl bromide is dropwise added under the condition of nitrogen, the reaction is carried out for 3h at constant temperature, after the reaction is finished, deionized water is used for quenching reaction, then saturated sodium bicarbonate solution is added, dichloromethane is used for extraction, anhydrous magnesium sulfate is used for drying, the product is obtained by suction filtration and rotary evaporation to remove the low-boiling point solvent, and 1.17g of intermediate trifluoropropyl bromoacetate is prepared, wherein the yield is 89%. The prepared intermediate is put into a three-neck flask containing 60mL of anhydrous tetrahydrofuran, then 3.41g N, N' -bis (p-toluenesulfonyl) hydrazine is added, the temperature is reduced to 0 ℃, and 3.82g of 1, 8-diazabicycloundecene-7-ene is added into the mixed solution dropwise under the nitrogen condition for reaction for 3 hours. After the reaction is finished, the mixture is quenched by deionized water, then saturated sodium bicarbonate solution is added, dichloromethane is used for extraction for 3 times, anhydrous magnesium sulfate is used for drying, and the product with the low boiling point is obtained by suction filtration and rotary evaporation, wherein the yield is 75%.
(2) Creation of graft sites on the fiber surface:
putting 0.815g of cotton fabric into a conical flask filled with 50mL of anhydrous tetrahydrofuran and 1.68g of sodium bicarbonate, cooling to 0 ℃, dropwise adding 1.68g of bromoacetyl bromide under nitrogen gas, reacting at constant temperature for 30min, then placing the mixture into a water bath shaking pot, naturally heating to 30 ℃, reacting at constant temperature for 15 h, then respectively washing with tetrahydrofuran and deionized water, and drying to obtain the brominated fabric. Immersing the brominated fabric into a conical flask filled with anhydrous tetrahydrofuran, adding 5.11g N, N' -bis (p-toluenesulfonyl) hydrazine, cooling to 0 ℃, dropwise adding 4.57g of 1, 8-diazabicycloundecen-7-ene under nitrogen, reacting at 0 ℃ for 30min, finally placing in a water bath shaking pot, naturally heating to 30 ℃, and carrying out constant-temperature oscillation reaction for 20 hours. And (4) after the reaction is finished, cleaning the fabric with the grafting sites by using tetrahydrofuran and deionized water respectively, and drying for the step (3).
(3) Preparing a hydrophobic fabric:
adding 5mmol of the synthesized trifluoropropyldiazoacetate into an erlenmeyer flask containing 60mL of anhydrous tetrahydrofuran, immersing the fabric with grafting sites into the erlenmeyer flask, and adding 9.15mg (Pi-allylPdCl)2Then the temperature is reduced to minus 10 ℃, 32.5mg NaBPh is added4. The conical flask is moved into a water bath shaking pot at 0 ℃ for oscillation reaction for 1h, then the temperature is sequentially increased to 10 ℃ for reaction for 1h, the temperature is increased to 20 ℃ for reaction for 1h, and finally the reaction is carried out at 30 ℃ for 24 h. After the reaction is finished, the fabric grafted with the polymer is respectively cleaned by ethanol and deionized water, and dried at 50 ℃ to obtain the water-repellent fabric.
And adjusting the last reaction time at 30 ℃ for 24 hours to the last reaction time at 30 ℃ for 12 hours, and keeping the rest unchanged to obtain the water-repellent fabric.
(4) Contact Angle testing
The grafted functional fabric is subjected to a wetting performance test by adopting an OCAH200 type microscopic droplet wetting tester of Dataphysics company, USA, 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 five times.
Example two
(1) Synthesis of nonafluorohexyl diazoacetate
50mL of anhydrous tetrahydrofuran, 1.32g of perfluorobutyl alcohol and 1.26g of sodium bicarbonate are added into a three-neck flask, the temperature is reduced to 0 ℃, 1.54g of bromoacetyl bromide is dropwise added under the condition of nitrogen, and the mixture reacts at constant temperature for 3 hours to purify and obtain 1.75g of intermediate nonafluorohexyl bromoacetate. Then putting the prepared intermediate into a three-neck flask containing 60mL of anhydrous tetrahydrofuran, adding 3.41g N, N' -bis (p-toluenesulfonyl) hydrazine, cooling to 0 ℃, dropwise adding 3.82g of 1, 8-diazabicycloundecene-7-ene into the mixed solution under the nitrogen condition, and reacting for 3 hours. After the reaction is finished, the solution is quenched by deionized water, extracted by dichloromethane for 3 times, dried by anhydrous magnesium sulfate, filtered by suction, and subjected to rotary evaporation to remove the low-boiling-point solvent, so that 1.29g of product, 78%, is obtained.
(2) Creating grafting sites on the surface of the fibers
Consistent with the embodiments.
(3) Preparing a hydrophobic fabric:
adding 5mmol of nonafluorohexyldiazoacetic acid ester synthesized in (1) into a conical flask containing 60mL of anhydrous tetrahydrofuran, immersing the fabric having the graft site in the flask, and adding 9.15mg (π -allylPdCl)2Then placing the mixture into a low-temperature reaction kettle, cooling the mixture to-10 ℃, and adding 32.5mg of NaBPh4. The conical flask is moved into a water bath shaking pot at 0 ℃ to be slowly shaken for 1h, and then the reaction is carried out for 1h at 10 ℃, 1h at 20 ℃ and finally 24h at 30 ℃. After the reaction is finished, the fabric of the grafted polymer is respectively cleaned by ethanol and deionized water and dried at 50 ℃.
And adjusting the last reaction time at 30 ℃ for 24 hours to the last reaction time at 30 ℃ for 12 hours, and keeping the rest unchanged to obtain the water-repellent fabric.
(4) Contact Angle testing
The grafted functional fabric is subjected to a wetting performance test by adopting an OCAH200 type microscopic droplet wetting tester of Dataphysics company, USA, 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 five times.
Example three:
(1) synthesis of nonafluorohexyl diazoacetate
In accordance with example two.
(2) Creating grafting sites on the surface of the fibers
Consistent with the embodiments.
(3) Preparing a hydrophobic fabric:
adding 5mmol of nonafluorohexyldiazoacetic acid ester synthesized in (1) into a round-bottomed flask containing 60mL of anhydrous tetrahydrofuran, fixing the fabric having the grafting site at the bottom end of a stirring paddle, immersing in a bottle, and adding 9.15mg of (. pi. -allylPdCl)2Then placing the mixture into a low-temperature reaction kettle, cooling the mixture to-10 ℃, and adding 32.5mg of NaBPh4(ii) a The reaction is carried out for 1h under the stirring dynamic condition (fabric rotation, strength similar to that of the second example) at 0 ℃, then the reaction is carried out for 1h at 10 ℃, for 1h at 20 ℃ and finally for 12h at 30 ℃. After the reaction is finished, the fabric of the grafted polymer is respectively cleaned by ethanol and deionized water and dried at 50 ℃.
(4) Contact Angle testing
The grafted functional fabric is subjected to a wetting performance test by adopting an OCAH200 type microscopic droplet wetting tester of Dataphysics company, USA, 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 five times.
Example four:
(1) synthesis of nonafluorohexyl diazoacetate
In accordance with example two.
(2) Creating grafting sites on the surface of the fibers
Consistent with the embodiments.
(3) Preparing a hydrophobic fabric:
adding 5mmol of nonafluorohexyldiazoacetate synthesized in (1) into a conical flask containing 60mL of anhydrous toluene, dipping the fabric having the graft site into the flask, and adding 9.15mg (π -allylPdCl)2Then placing the mixture into a low-temperature reaction kettle, cooling the mixture to-10 ℃, and adding 32.5mg of NaBPh4. The conical flask is moved into a water bath shaking pot at 0 ℃ to be slowly shaken for 1h, and then the reaction is carried out for 1h at 10 ℃, 1h at 20 ℃ and finally 24h at 30 ℃. After the reaction is finished, the fabric of the grafted polymer is respectively cleaned by ethanol and deionized water and dried at 50 ℃.
And adjusting the last reaction time at 30 ℃ for 24 hours to the last reaction time at 30 ℃ for 12 hours, and keeping the rest unchanged to obtain the water-repellent fabric.
(4) Contact Angle testing
The grafted functional fabric is subjected to a wetting performance test by adopting an OCAH200 type microscopic droplet wetting tester of Dataphysics company, USA, 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 five times.
Example five:
(1) synthesis of nonafluorohexyl diazoacetate
In accordance with example two.
(2) Creating grafting sites on the surface of the fibers
Consistent with the embodiments.
(3) Preparing a hydrophobic fabric:
adding 5mmol of nonafluorohexyldiazoacetate synthesized in (1) into a conical flask containing 60mL of anhydrous dichloromethane, dipping the fabric having the graft site into the flask, and adding 9.15mg (π -allylPdCl)2Then placing the mixture into a low-temperature reaction kettle, cooling the mixture to-10 ℃, and adding 32.5mg of NaBPh4. The conical flask is moved into a water bath shaking pot at 0 ℃ to be slowly shaken for 1h, and then the reaction is carried out for 1h at 10 ℃, 1h at 20 ℃ and finally 24h at 30 ℃. After the reaction is finished, the fabric of the grafted polymer is respectively cleaned by ethanol and deionized water and dried at 50 ℃.
And adjusting the last reaction time at 30 ℃ for 24 hours to the last reaction time at 30 ℃ for 12 hours, and keeping the rest unchanged to obtain the water-repellent fabric.
(4) Contact Angle testing
The grafted functional fabric is subjected to a wetting performance test by adopting an OCAH200 type microscopic droplet wetting tester of Dataphysics company, USA, 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 five times.
Example six:
(1) synthesis of nonafluorohexyl diazoacetate
In accordance with example two.
(2) Creating grafting sites on the surface of the fibers
Consistent with the embodiments.
(3) Preparing a hydrophobic fabric:
adding 5mmol of nonafluorohexyl diazoacetate synthesized in (1) into a conical flask filled with a mixed solution of 50mL of anhydrous tetrahydrofuran and 10mL of anhydrous ethanol, immersing the fabric with grafting sites into the flask, and adding 9.15mg (Pi-allylPdCl)2Placing the mixture in a low-temperature reaction kettle, cooling the mixture to-10 ℃, and adding 32.5mg of NaBPh4. The conical flask is moved into a water bath shaking pot at 0 ℃ to be slowly shaken for 1h, and then the reaction is carried out for 1h at 10 ℃, 1h at 20 ℃ and finally 24h at 30 ℃. After the reaction is finished, the fabric of the grafted polymer is respectively cleaned by ethanol and deionized water and dried at 50 ℃.
And adjusting the last reaction time at 30 ℃ for 24 hours to the last reaction time at 30 ℃ for 12 hours, and keeping the rest unchanged to obtain the water-repellent fabric.
(4) Contact Angle testing
The grafted functional fabric is subjected to a wetting performance test by adopting an OCAH200 type microscopic droplet wetting tester of Dataphysics company, USA, 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 five times.
EXAMPLE seven
(1) Synthesis of tridecafluorooctyl diazoacetate:
50mL of anhydrous tetrahydrofuran, 1.82g of perfluorohexylethanol and 1.26g of sodium bicarbonate are added into a three-neck flask, the temperature is reduced to 0 ℃, 1.54g of bromoacetyl bromide is dropwise added under the condition of nitrogen, and the mixture reacts for 3 hours at constant temperature to prepare 2.09g of intermediate tridecafluorooctyl bromoacetate. The prepared intermediate is put into a three-neck flask filled with 60mL of anhydrous tetrahydrofuran, then 3.41g N, N' -bis (p-toluenesulfonyl) hydrazine is added, the temperature is reduced to 0 ℃, and 3.82g of 1, 8-diazabicycloundecen-7-ene is added under the nitrogen condition for reaction for 3 hours. After the reaction is finished, the product is quenched by deionized water, extracted by dichloromethane for 3 times, dried by anhydrous magnesium sulfate, filtered by suction, and subjected to rotary evaporation to remove the low-boiling-point solvent, so that 1.64g of product is obtained, and the yield is 76%.
(2) Creation of graft sites on the fiber surface:
consistent with the embodiments.
(3) Preparing a hydrophobic fabric:
adding 5mmol of the tridecafluorooctyl diazoacetate synthesized in (1) into an Erlenmeyer flask containing 60mL of anhydrous tetrahydrofuran, immersing the fabric having the grafting sites in the flask, and adding 9.15mg (pi-allylPdCl)2Cooling to-10 deg.C, adding 32.5mg NaBPh4. The conical flask is moved into a water bath shaking pot at 0 ℃ to be slowly shaken for 1h, and then the reaction is carried out for 1h at 10 ℃ and 1h at 20 ℃ in sequence, and finally the reaction is carried out for 24h at 30 ℃. After the reaction is finished, the fabric of the grafted polymer is respectively cleaned by ethanol and deionized water and dried at 50 ℃.
And adjusting the last reaction time at 30 ℃ for 24 hours to the last reaction time at 30 ℃ for 12 hours, and keeping the rest unchanged to obtain the water-repellent fabric.
(4) Contact Angle testing
The grafted functional fabric is subjected to a wetting performance test by adopting an OCAH200 type microscopic droplet wetting tester of Dataphysics company, USA, 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 five times.
Example eight:
(1) synthesis of Octadrifluorooctyl diazoacetate
The same as the embodiment.
(2) Creation of graft sites on the fiber surface:
consistent with the embodiments.
(3) Preparing a hydrophobic fabric:
the tridecafluorooctyl radical synthesized in (1)Diazoacetate 5mmol is added to a conical flask containing 50mL of a mixture of anhydrous tetrahydrofuran and 10mL of anhydrous ethanol, the fabric bearing the grafting sites is immersed in the flask, and 9.15mg (π -allylPdCl) is added2Placing the mixture in a low-temperature reaction kettle, cooling the mixture to-10 ℃, and adding 32.5mg of NaBPh4. The conical flask is moved into a water bath shaking pot at 0 ℃ to be slowly shaken for 1h, and then the reaction is carried out for 1h at 10 ℃, 1h at 20 ℃ and finally 24h at 30 ℃. After the reaction is finished, the Polymer-cotton fabric of the grafted Polymer is cleaned by ethanol and deionized water respectively, and is dried at 50 ℃.
And adjusting the last reaction time at 30 ℃ for 24 hours to the last reaction time at 30 ℃ for 12 hours, and keeping the rest unchanged to obtain the water-repellent fabric.
(4) Contact Angle testing
The grafted functional fabric is subjected to a wetting performance test by adopting an OCAH200 type microscopic droplet wetting tester of Dataphysics company, USA, 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 five times.
FIG. 1 is a surface micro-topography of a fabric grafted by carbene polymerization prepared in example one, and the generated rod-like roughened structure evolves to a local hollow tubular structure with time, and the contact angle to water is less than 100 degrees.
FIG. 2 is a microstructure of the fabric surface after grafting by carbene polymerization prepared in example two (12 hours), and the generated micron-sized rod-shaped roughened structure has uniform coverage, higher grafting rate and a contact angle of 146 degrees with water.
FIG. 3 is a microstructure of the fabric surface after grafting by carbene polymerization prepared in example two (24 hours), and the generated micron-sized tubular roughened structure has uniform coverage, higher grafting ratio and a contact angle to water of 152 degrees.
FIG. 4 is a topographical view of the surface of the fabric grafted with carbene polymers prepared in example three, resulting in a micron-scale ball/hemisphere-shaped roughened structure with a contact angle of 125 ° with water.
FIG. 5 is a microstructure of the surface of the fabric grafted by carbene polymerization prepared in example four, which has stronger structural regularity, a cross section of a micron-sized rod-shaped roughened structure with obvious rectangular shape, and contact angles to water of 132 ° (12 hours) and 135 ° (24 hours), respectively.
FIG. 6 is a surface micro-topography of the fabric grafted by the carbene polymer prepared in example five, and the resulting rod-like roughened structures will eventually cross-link with each other to form sheet-like structures with contact angles to water of 135 ° (12 hours) and 138 ° (24 hours), respectively.
FIG. 7 is a surface micro-topography of the fabric grafted by carbene polymerization prepared in example six (12 hours), and the generated uniformly dispersed nano-scale particles gradually aggregate into micro-scale roughened particles, and the contact angle to water is 153 degrees.
FIG. 8 is a surface micro-topography of the fabric grafted by carbene polymerization prepared in example six (24 hours), and the generated uniformly dispersed nano-particles gradually aggregate into micro-scale coarse particles and further change into loose sheet shapes, and the contact angle to water is 148 degrees.
FIG. 9 is a microstructure of the fabric surface after grafting by carbene polymerization prepared in example seven (12 hours), and the resulting rod-like roughened structure with uniform coverage and high grafting ratio is not transformed into a tubular structure, and the contact angles to water are respectively 145 degrees.
FIG. 10 is a microscopic topography of the surface of the fabric grafted by carbene polymerization prepared in example seven (24 hours), resulting in a rod-like roughened structure with uniform coverage and high grafting yield, and clearly showing that the fiber surface is covered with a layer of rod-like crystal structure with uniform morphology and size, and the contact angles to water are respectively 151 deg..
FIG. 11 is a surface microtopography of the fabric grafted by carbene polymerization prepared in example eight (12 hours), the generated nanoscale particles converge to form a coarsened structure of the microscale particles, and finally evolve to larger aggregate particles with a contact angle to water of 152 °.
Fig. 12 is a surface microtopography of fabric grafted by carbene polymerization prepared in example eight (24 hours), generated nano-scale particles converge to form a coarse structure of micro-scale particles, and finally change to larger aggregative particles, and new nanoparticles grow on the accumulated large-scale micro-surface twice, and the contact angle to water is 154 °.
FIG. 13 shows the surface element content and distribution of the fabric after grafting by carbene polymerization prepared in example two (12 hours).
FIG. 14 is a graph of the adhesion of the fabric after grafting by carbene polymerization and its hydrophobicity as prepared in example two (12 hours).
The adhesion between the solid surface and the liquid drop is one of the important parameters for measuring the anti-wetting functional fabric, the chemical composition of the solid surface not only influences the size of the static contact angle, but also has a considerable influence on the size of the dynamic adhesion, and the adhesion of the surface to water is different regardless of the high-hydrophobicity or super-hydrophobicity surface. The adhesion curve shows that the water adhesion of the surface of the raw cotton fabric is above 140 uN, while FIG. 14 shows that the water adhesion of the fabric is 64 uN after grafting by carbene polymerization of nonafluorohexyldiazoacetate.
FIG. 15 shows the surface element content and distribution of the fabric grafted by carbene polymerization prepared in example seven (12 hours).
The invention discloses a water-repellent fabric, and develops application research of carbene polymerization in the field of functional material preparation. Based on the single-carbon repetition and stereo-regularity characteristics of the carbene polymer, a roughened structure with low surface energy can be constructed on the surface of the fabric in one step through novel carbene polymerization covalent grafting, the traditional organic-inorganic hybridization and multi-step reaction processes are not needed, and a relatively durable hydrophobic effect is obtained. Novel carbene polymerizations (C)1Polymerization) can graft a low surface energy polymer based on a single carbon repeating unit onto cotton fabric, and by utilizing the molecular chain rigidity of dense stacking of the single carbon units, carbene polymer crystallization can be expected to be induced on the surface of the fiber, and self-assembly is driven by the crystallization to form a polymer crystal structure with a roughened appearance on the surface of the fabric, thereby obtaining the required protective physical structure. The carbene polymerization grafting process is carried out at low/room temperature, the fiber is damaged to the minimum extent compared with other modification methods which need to be carried out under a high-temperature/high-pressure process or a strong acid/alkali or strong oxidant condition, and a by-product generated in the polymerization process is nitrogen, so that the carbene polymerization grafting process is relatively environment-friendly.
Claims (10)
1. The water-repellent fabric is characterized by comprising a fabric and a covalently grafted fluoropolymer through carbene polymerization on the surface of the fabric.
2. The water repellent fabric according to claim 1, wherein said carbene-polymerized covalently grafted fluoropolymer has the following structural formula:
Rfis a fluoroalkyl group.
3. The water-repellent fabric according to claim 2, wherein the number of fluorine atoms in the fluoroalkyl group is 3 to 15.
4. Use of the water repellent fabric of claim 1 in the manufacture of a water repellent material.
5. A method of producing a water repellent fabric according to claim 1, comprising the steps of: under the action of a catalyst, placing fluoroalkyl diazo acetate and an active fabric in an organic solvent, and covalently grafting a fluorine-containing polymer on the fiber surface of the fabric through carbene polymerization reaction to obtain a water-repellent fabric; the active fabric is a fabric containing grafting sites.
6. The method for preparing the water-repellent fabric according to claim 5, wherein the fluoroalkyl diazo acetate has 3 to 15 fluorine atoms; the grafting site is diazo.
7. The method for producing a water repellent fabric according to claim 5, wherein the catalyst is a palladium salt; the organic solvent is one or more of tetrahydrofuran, dichloromethane and ethanol; the carbene polymerization reaction is carried out under shaking or stirring.
8. The method for preparing the water repellent fabric according to claim 5, characterized in that fluoroalkyl alcohol is reacted with bromoacetyl bromide to obtain fluoroalkyl bromoacetate, and then the fluoroalkyl bromoacetate is reacted with N, N' -xylene sulfonyl hydrazide to obtain fluoroalkyl diazoacetate; and acylating the fabric, and then reacting with N, N' -xylene sulfonyl hydrazide to prepare the active fabric.
9. The method for producing a water repellent fabric according to claim 8, wherein the reaction of a fluoroalkyl alcohol with bromoacetyl bromide is carried out in the presence of an alkali; the reaction of the fluoroalkyl bromoacetate and the N, N' -xylene sulfonyl hydrazide is carried out in the presence of an organic acid-binding agent.
10. The method for producing a water repellent fabric according to claim 8, wherein the number of fluorine atoms in the fluoroalkyl alcohol is 3 to 15.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112878053A (en) * | 2021-02-05 | 2021-06-01 | 苏州大学 | Micro-nano structure based super-hydrophobic fabric and preparation method thereof |
| WO2022051953A1 (en) * | 2020-09-09 | 2022-03-17 | 苏州大学 | Water-repellent fabric and preparation method therefor |
| CN114481608A (en) * | 2022-02-15 | 2022-05-13 | 苏州大学 | Carbene co-grafted modified fabric and preparation method and application thereof |
| WO2022165777A1 (en) * | 2021-02-05 | 2022-08-11 | 苏州大学 | Micro-nano structure-based super-hydrophobic fabric and preparation method therefor |
| WO2023155308A1 (en) * | 2022-02-15 | 2023-08-24 | 苏州大学 | Fluorine-free carbon chain hydrophobic fabric, and preparation method therefor and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106988120A (en) * | 2017-04-26 | 2017-07-28 | 苏州大学 | Intelligent real silk fabric of a kind of hydrophilic and hydrophobic and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106988120A (en) * | 2017-04-26 | 2017-07-28 | 苏州大学 | Intelligent real silk fabric of a kind of hydrophilic and hydrophobic and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022051953A1 (en) * | 2020-09-09 | 2022-03-17 | 苏州大学 | Water-repellent fabric and preparation method therefor |
| CN112878053A (en) * | 2021-02-05 | 2021-06-01 | 苏州大学 | Micro-nano structure based super-hydrophobic fabric and preparation method thereof |
| CN112878053B (en) * | 2021-02-05 | 2022-03-15 | 苏州大学 | Micro-nano structure based super-hydrophobic fabric and preparation method thereof |
| WO2022165777A1 (en) * | 2021-02-05 | 2022-08-11 | 苏州大学 | Micro-nano structure-based super-hydrophobic fabric and preparation method therefor |
| CN114481608A (en) * | 2022-02-15 | 2022-05-13 | 苏州大学 | Carbene co-grafted modified fabric and preparation method and application thereof |
| CN114481608B (en) * | 2022-02-15 | 2022-12-30 | 苏州大学 | Carbene co-grafting modified fabric and preparation method and application thereof |
| WO2023155368A1 (en) * | 2022-02-15 | 2023-08-24 | 苏州大学 | Carbene co-grafted modified fabric, preparation method therefor, and application thereof |
| WO2023155308A1 (en) * | 2022-02-15 | 2023-08-24 | 苏州大学 | Fluorine-free carbon chain hydrophobic fabric, and preparation method therefor and use thereof |
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