CN114990885A - Anti-ultraviolet super-hydrophobic fabric and preparation method thereof - Google Patents
Anti-ultraviolet super-hydrophobic fabric and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an anti-ultraviolet super-hydrophobic fabric and a preparation method thereof, wherein the anti-ultraviolet super-hydrophobic fabric comprises a fabric and a nano porous metal organic framework structure growing on the surface of the fabric in situ; the nano-porous metal organic framework structure is formed by coordination and assembly of metal ions and organic ligands. Carrying out diazo free radical polymerization reaction on carboxyl-containing aromatic free radicals on the surface of the fiber to generate a carboxyl-containing aromatic polymer chain; then growing an MOF structure crystal coating on the surface of the fiber in situ by a layer-by-layer self-assembly strategy, and obtaining the super-hydrophobic MOF @ fabric by hydrophobization and post-finishing. Based on the excellent characteristics of the MOF structure, such as porous performance, large specific surface area and the like, the MOF crystal is connected with the fiber surface by covalent bonds, so that the MOF @ fabric is endowed with excellent ultraviolet resistance and super-hydrophobic performance, and the application of the MOF @ fabric in the fields of pollution resistance, self-cleaning and the like is expanded. The finishing process of the fabric is completed at room temperature, the production and preparation process is simple, the reaction condition is mild, the operation is safe, and the expanded production is easy.
Description
Technical Field
The invention relates to an MOF @ fabric with ultraviolet-proof and super-hydrophobic functions and a preparation method thereof, belonging to the technical field of special functional textiles and preparation thereof.
Background
The prior art has developed a number of MOF materials with different organic ligands and metal ions, and has rapidly developed in the fields of filtration, gas storage, separation, antibacterial, energy storage, catalysis, water collection, and drug-coated sustained release. However, previous studies on MOF materials have been mostly performed in powder form, which greatly limits their practical application fields. The textile has wide and important application background in the fields of actual production life, industrial development and the like, such as clothing, household textiles, industrial textiles, medical textiles and the like, due to natural advantages of flexibility, wearability, air permeability, easy processing and the like. With the rapid development of modern society, the demands for textiles are increasing day by day, especially for personalized and multifunctional textiles, so that the textiles with single function can not meet the development needs of society. Conventional fabrics are not satisfactory when exposed to harsh conditions, such as intense ultraviolet light, toxic chemicals, or bacteria. Therefore, it is generally necessary to modify the fibers with functional materials to improve the protective properties of ordinary fabrics and to increase their application functions.
Fabrics provide an ideal flexible platform for the loading of MOFs, and methods for incorporating MOFs into fibrous substrate materials by dip coating, mixing, etc. have been reported to achieve enhanced functionality and ideal specific applications with large specific surface areas. However, the MOF-fibre composites prepared by the above method have poor and unstable interaction between MOF and fibre. Therefore, the resulting final product cannot achieve the intended application effect. Furthermore, hydrolytic instability is also one of the major drawbacks of existing MOF materials.
Disclosure of Invention
The invention discloses a functionalized MOF @ fabric and a preparation method thereof, wherein diazo free radical covalent grafting polymerization is used for surface modification of a cellulose fiber material, and the unique advantages of an MOF material are combined. During preparation, aromatic free radicals containing carboxyl are grafted and polymerized on the surface of the fiber to form a carboxyl polymerization chain brush; and then, growing the MOF crystal coating in situ by a treatment process on the premise of ensuring that the strength, the air permeability, the hand feeling, the wearability and the like of the fabric are not influenced, thereby obtaining the functionalized MOF @ fabric. Aiming at the problems of unsatisfactory fastness, single function, uneven crystal growth and the like of MOF loaded on the fiber surface at present, the invention utilizes carboxyl aromatic free radical to graft the fiber to form a carboxyl-containing polymer chain brush on the fiber surface, so as to provide enough active sites for the growth of MOF crystals, thereby improving the MOF loading rate and the durability fastness and endowing the fabric with multiple functions.
The technical scheme for realizing the purpose of the invention is as follows:
an anti-ultraviolet super-hydrophobic fabric comprises a fabric, carboxyl aromatic polymer chains grafted on the surface of the fabric, an MOF crystal structure and a hydrophobic coating; the MOF crystal structure is formed by coordination assembly of metal ions with organic ligands.
Adding the fabric into aromatic diazonium salt solution containing carboxyl, adding a chemical reducing agent, and carrying out polymerization reaction to obtain the fabric with the surface grafted with the carboxyl aromatic polymer chain; then, the fabric with the surface grafted with the carboxyl aromatic polymer chain is subjected to layer-by-layer self-assembly in a metal ion-containing solution and an organic ligand solution to obtain the MOF @ fabric, and then the hydrophobic coating of the MOF @ fabric is finished to obtain the anti-ultraviolet super-hydrophobic fabric.
In the invention, the fabric is cotton fabric and/or linen fabric; the MOF is CuBTC.
In the invention, aromatic amine containing carboxyl is diazotized in acid solution of sodium nitrite to obtain aromatic diazonium salt solution containing carboxyl.
Specifically, the preparation method of the ultraviolet-proof super-hydrophobic fabric comprises the following steps:
(1) diazotizing aromatic amine containing carboxyl in an acid solution of sodium nitrite to obtain a diazonium salt solution, wherein the acid is dilute hydrochloric acid or dilute sulfuric acid;
(2) adding a fabric into the diazonium salt solution, then adding a reducing agent, reducing carboxyl-containing aromatic diazonium salt into carboxyl-containing aromatic free radicals at room temperature, and carrying out free radical covalent grafting polymerization reaction on carboxyl-containing aromatic free radical monomers on the surface of the fiber to obtain carboxyl aromatic polymer chains;
(3) dissolving metal salt in N, N-dimethylacetamide, ethanol and water to prepare a metal ion solution A; dissolving an organic ligand in N, N-dimethylacetamide, ethanol and water to prepare an organic ligand solution B;
(4) and (3) sequentially adding the carboxylated fabric prepared in the step (2) into the metal ion solution A and the organic ligand solution B prepared in the step (3), carrying out circulating layer-by-layer self-assembly growth to form an MOF coating structure, and reacting for a certain time to obtain the MOF @ fabric.
(5) Soaking the MOF @ fabric prepared in the step (4) in ethanol solution of siloxane, such as n-octyltriethoxysilane or n-hexyltriethoxysilane, for a certain time, and baking to obtain the functionalized MOF @ fabric.
In the invention, the carboxyl-containing aromatic amine is preferably carboxyl-containing aniline, and the chemical structural formula of the carboxyl-containing aromatic amine is as follows:
the carboxyl-containing aromatic free radical has the following chemical structure:
in the above structural formula of the present invention, R 1 Hydrogen or carboxyl. Preferably, the carboxyl group is-COOH, -CH 2 COOH or-C 2 H 4 COOH。
In the present invention, the polymerization time is 6 to 72 hours, preferably 36 to 48 hours.
In the invention, a carboxylated fabric (namely, a fabric with a surface grafted with a carboxyl aromatic polymer chain) is sequentially added into a metal ion solution and an organic ligand solution for circulating self-assembly, and the primary dipping reaction time is 3-60 min, preferably 10-20 min; the number of self-assembly cycles is 3 to 30, preferably 10 to 15.
In the invention, the finishing agent for the hydrophobic coating is siloxane containing hydrophobic chain segments, and is preferably n-octyl triethoxysilane or n-hexyl triethoxysilane. The invention adopts the non-fluorine-containing finishing agent to realize the super-hydrophobic property of the fabric and meet the super-hydrophobic requirement that the water contact angle is more than 150 degrees.
The anti-ultraviolet super-hydrophobic functionalized MOF @ fabric is a modified fiber, the surface of the modified fiber is provided with a regular crystal structure coating, and the crystal coating gradually grows into micron-sized particles from the nano-sized particles along with the increase of the cycle times.
In the above technical scheme, in the step (1), the molar concentration of the acid solution is 0.2-3M, preferably 0.8-1.5M; the diazotization is carried out at a low temperature, wherein the temperature is-15-25 ℃, and preferably-5 ℃; the diazotization reaction time is 0.1-12 h, preferably 0.5-3 h.
In the above technical scheme, the reducing agent is Vitamin C (VC).
The invention utilizes single electron free radical covalent graft polymerization between carboxyl-containing aromatic radical free radical monomers and natural fibers to prepare a carboxylated fabric, utilizes the coordination between metal ions and organic ligands to produce a MOF @ fabric with a roughened surface, and obtains a functionalized MOF @ fabric through hydrophobic coating finishing.
The invention relates to a method for graft polymerization of aromatic amine containing carboxyl through diazo free radical covalent bond, forming a polymer chain brush containing carboxyl on the surface of fiber; then growing a metal organic framework structure on the surface of the carboxylated fiber in situ by a layer-by-layer self-assembly strategy; and finally, finishing the fiber surface by a hydrophobic coating to obtain the functionalized MOF @ fabric. Compared with the prior art, the technical scheme provided by the invention has the beneficial effects that:
1. the invention carries out carboxylation grafting modification and finishing on the surface of the fiber by a covalent grafting polymerization method of aromatic diazo free radicals, forms a carboxyl polymer molecular chain brush on the surface of the fiber, provides a carboxyl active site, and provides necessary conditions for anchoring metal ions and growth of MOF crystals. This is of great importance for the in situ growth of MOF materials on fiber surfaces to produce a new generation of functionalized MOF fabrics.
2. The combination between the carboxylated fiber and the MOF crystal is stable, thereby endowing the MOF and the fabric with excellent fastness, and solving the problem of poor fastness of the conventional MOF @ fabric due to fixation through physical mixing adsorption. This is of great importance for the development of a durable MOF @ fabric.
3. The prepared MOF @ fabric combines the unique advantages of softness, wearability, air permeability and adjustable specific surface area, porosity and structural performance of the MOF material, and has very important significance for improving the wearability, multifunctionality and additional value of the fabric and expanding the application prospect of the MOF material.
4. The preparation method of the MOF @ fabric is simple, mild in reaction condition, easy to operate, capable of realizing large-scale production and easy to popularize.
Drawings
FIG. 1 is a schematic diagram of the reaction of the present invention.
FIG. 2 is a schematic of the chemical structure of the fiber surface of the modified fabric.
FIG. 3 is a Scanning Electron Microscope (SEM) image of cotton fabric having wrinkles on the surface, shown as A, as a raw material in example; example one Scanning Electron Microscope (SEM) image of the resultant carboxyl group-containing radical graft polymerization finished fabric, the fiber surface having a nano-scale particle structure formed by carboxyl group-containing aromatic polymer chains, B; example one Scanning Electron Microscope (SEM) image of the resulting MOF @ fabric with a regular micron regular octahedral crystal structure MOF coating on the fiber surface, C, in the image.
FIG. 4 is an infrared and X-ray diffraction pattern of the functionalized MOF @ fabric prepared in the first example.
FIG. 5 is a graph showing the UV transmittance absorption curves of an unmodified cotton fabric, a carboxylated modified cotton fabric, a MOF @ fabric and a super-hydrophobic MOF @ fabric of examples, and the UPF values of the fabrics are 20.9 +/-3.2, 45.9 +/-6.6, 199.5 +/-14.7 and 192.2 +/-13.2 respectively.
FIG. 6 is a contact angle test chart of cotton fabric of an unmodified material of example, and the contact angles of the surfaces of the fabrics are respectively measured to be 0 degrees, and the chart A is shown; example a contact angle test chart of a carboxylated modified cotton fabric, the measured surface contact angles of the fabric are 0 ° respectively, and the chart B; example a MOF @ fabric contact angle test chart, measuring the surface contact angles of the fabric as 0 °, panel C; example contact angle test patterns for a hydrophobized MOF @ fabric, the fabric surface contact angles were measured to be 168.4 ± 1.6 °, panel D, respectively.
FIG. 7 is a Scanning Electron Microscope (SEM) image of a MOF @ fabric prepared according to example two, with the fiber surface coated with a MOF coating containing a micro-scale octahedral crystal structure.
FIG. 8 is a Scanning Electron Microscope (SEM) image of a MOF @ fabric prepared according to example three, with the fiber surface coated with a MOF coating containing a micro-scale octahedral crystal structure.
FIG. 9 is a Scanning Electron Microscope (SEM) image of a long MOF prepared in comparative example one, without the carboxylated modified fabric, with a sparse population of irregular micro-nano scale crystal structure particles distributed on the surface of the fiber.
Detailed Description
Fabrics provide an ideal flexible platform for the loading of MOFs, and methods for incorporating MOFs into fibrous base materials by dip coating, mixing, etc. have been reported to achieve enhanced functionality and the specific application of ideally large specific surface area. However, in the MOF-fiber composites prepared by the above method, the interaction force between MOF and fiber is poor and unstable. Therefore, the resulting final product cannot achieve the intended application effect. Furthermore, hydrolytic instability is also one of the major drawbacks of existing MOF materials. To address these problems, the present invention provides a viable solution for future MOF @ fabric development by integrating MOF materials into fibers via a new approach.
The invention discloses a preparation method of the MOF @ fabric by taking carboxyl-containing aniline as an example, which comprises the following steps:
(1) diazotizing aniline containing carboxyl in dilute acid solution of sodium nitrite to form diazonium salt;
(2) the carboxyl-containing benzene diazonium salt is converted into carboxyl-containing benzene free radical under the action of a reducing agent; carrying out single-electron free radical covalent grafting polymerization reaction on the carboxyl-containing benzene free radical monomer and oxygen radicals on natural fibers in situ;
(3) the metal ions are anchored on the surface of the fiber through coordination with carboxyl, and then self-assembly with the metal ion solution A, ethanol and the organic ligand solution B is sequentially carried out layer by layer, so that an MOF coating structure is formed on the surface of the fiber through in-situ growth.
(4) The MOF @ fabric is subjected to coating finishing by using a hydrophobic substance to obtain the functionalized MOF @ fabric.
The reactions involved are shown in FIG. 1. Adding sodium nitrite into dilute acid solution at low temperature, stirring and dissolving to form sodium nitrite acid solution, adding aniline containing carboxyl into the sodium nitrite acid solution, stirring and carrying out diazotization reaction to generate diazo salt containing carboxyl benzene; adding a reducing agent into the diazonium salt solution, heating the reaction temperature to room temperature, reducing the carboxyl-containing benzene diazonium salt into a carboxyl-containing benzene free radical monomer, and releasing nitrogen; firstly, in a reaction solution of a carboxyl-containing benzene free radical monomer, the carboxyl-containing benzene free radical monomer performs single-electron free radical initiation on hydroxyl on cellulose fiber to generate oxygen free radicals, and after VC is added, other carboxyl-containing benzene free radical monomers and the oxygen free radicals on the cellulose fiber perform covalent graft polymerization reaction for a certain time through in-situ free radicals to form a carboxyl aromatic polymer chain on the surface of the fiber; firstly, adding a carboxylated fabric into a metal ion solution A for a certain time, then putting the fabric into an ethanol solution for cleaning for 10 seconds, then adding the fabric into an organic ligand solution B, and then putting the fabric into the ethanol solution for cleaning for 10 seconds, wherein the process is a cycle; and (4) continuously circulating the operation process, and finally forming a dense MOF crystal coating on the surface of the fiber. And then soaking the MOF @ fabric in an ethanol solution of a hydrophobic substance for a certain time, and baking and finishing to obtain the functionalized MOF @ fabric.
The invention carries out graft copolymerization on cellulose-based fibers of cotton, hemp and other fabrics, and utilizes the carboxyl active sites on the surfaces of the fibers, namely Cu 2+ The coordination with organic ligand grows on the fiber surface in situ to construct MOF crystal structure and modify the chemistry of the fiber surface of the fabricThe structure is shown in figure 2, wherein n = 3-100, is the structure of fabric cellulose and is common knowledge; m = 1~ 50.
The technical scheme of the invention is further described by combining the attached drawings and the embodiment, the related raw materials are conventional commodities, and the raw material cotton fabric is hydrophilic fabric with the size of 5cm multiplied by 8 cm; the specific preparation operations and tests were carried out by conventional techniques, and the experiments were carried out in air unless otherwise specified.
Example one
(1) Generation of m-aminobenzoic acid diazonium salt
The round bottom flask was equipped with a thermometer and equipped with magnetic stirring. Adding 60 ml of 1M hydrochloric acid solution, cooling to 15 ℃ in a cold bath, adding 3.3 mmol of sodium nitrite, cooling to-5 ℃ in the cold bath, and stirring to dissolve to form sodium nitrite solution. Then adding 3 mmol of m-aminobenzoic acid, preserving heat and diazotizing for 1h to generate m-carboxybenzoic acid diazonium salt solution.
(2) Formation of the m-carboxyphenyl radical
Adding a piece of cotton fabric into the diazonium salt solution, then adding 53mg of a reducing agent VC, heating the temperature of the reaction solution to room temperature, keeping the temperature for 36 hours, reducing the m-carboxybenzoic acid diazonium salt into a m-carboxybenzene free radical monomer, and releasing nitrogen; the m-carboxyl benzene free radical monomer initiates the homolytic cleavage of hydroxyl on the cotton fiber to generate oxygen free radicals, and simultaneously other m-carboxyl benzene free radical monomers continue to generate in-situ free radical covalent grafting polymerization with the oxygen free radicals on the cotton fiber to form the carboxyl aromatic polymer chain brush, which is called as carboxylated cotton fabric.
(3) 3.8g of Cu (NO) 3 ) 2 ·3H 2 Dissolving O in 48 mL of mixed solvent of N, N-dimethylacetamide, ethanol and water in a ratio of 1:1:1 to prepare a metal ion-containing solution A; 1.35g of 1,3, 5-benzenetricarboxylic acid was dissolved in 48 mL of a mixed solvent of N, N-dimethylacetamide, ethanol and water in a ratio of 1:1:1 to prepare an organic ligand solution B.
(4) Soaking a piece of carboxylated cotton fabric of 5cm × 8cm in the solution A containing metal ions for 15min, taking out, washing in ethanol solution for 10s, taking out, washing in the solution B containing organic ligands for 15min, taking out, and washing in ethanol solution for 10 s; the above operation steps are a cycle process, and then the process is operated circularly 10 times. Finally the samples were taken out and washed by shaking in 50mL of fresh absolute ethanol solution, repeated 5 times to remove the remaining unbound metal ions and organic ligands, and finally dried in an oven at 50 ℃ for 3 hours to obtain MOF @ fabric.
(5) And (3) immersing the MOF @ fabric obtained in the step (4) in 20mL of n-octyltriethoxysilane methanol solution for 1h, and then taking out the fabric and baking the fabric at 140 ℃ for 1h to obtain the hydrophobic MOF @ fabric.
(6) Ultraviolet resistance test
UV-2000F fabric sun protection index analyzer of blue-phenanthrene optics (Labsphere) Inc. is adopted to test the UPF value of the uvioresistant performance before and after the fabric modification according to GB/T18830. Each single fabric sample was tested five times respectively and averaged. UPF values of the unmodified raw material cotton fabric, the carboxylated modified cotton fabric, the MOF @ fabric and the super-hydrophobic MOF @ fabric are respectively 20.9 +/-3.2, 45.9 +/-6.6, 199.5 +/-14.7 and 192.2 +/-13.2. The MOF @ fabric after modification shows very excellent ultraviolet resistance.
(7) Contact Angle testing
The wetting performance of the MOF @ fabric before and after modification is tested by adopting a DSA100 type full-automatic microscopic liquid drop wetting instrument of Kruss company in Germany, deionized water is selected as a test liquid drop, the volume of the liquid drop is 5 mu L, and the average value is obtained by respectively testing for five times. The surface contact angles of the unmodified cotton fabric, the carboxylated modified cotton fabric, the MOF fabric and the hydrophobized MOF fabric are respectively 0 degree, 0 degree and 168.4 +/-1.6 degrees, which shows that the unmodified cotton fabric, the carboxylated modified cotton fabric and the MOF @ fabric have super-hydrophilic performance, and the MOF @ fabric after the hydrophobization modification shows super-hydrophobic performance.
FIG. 3 is a Scanning Electron Microscope (SEM) image of cotton fabric having wrinkles on the surface, shown as A, as a raw material in example; example one Scanning Electron Microscope (SEM) image of the resultant carboxyl group-containing radical graft polymerization-finished fabric, in which the fiber surface is of a nano-scale particle structure formed by carboxyl group-containing aromatic polymer chains, B; example one Scanning Electron Microscope (SEM) image of the resulting MOF @ fabric with a regular micron regular octahedral crystal structure MOF coating on the fiber surface, C, in the image.
FIG. 4 is an infrared spectrum and an X-ray diffraction spectrum of the functionalized MOF @ fabric prepared in the first example.
FIG. 5 is a graph showing the UV transmittance absorption curves of an unmodified cotton fabric, a carboxylated modified cotton fabric, a MOF @ fabric and a super-hydrophobic MOF @ fabric of examples, and the UPF values of the fabrics are 20.9 +/-3.2, 45.9 +/-6.6, 199.5 +/-14.7 and 192.2 +/-13.2 respectively.
FIG. 6 is a contact angle test chart of cotton fabric of an unmodified material of example, and the contact angles of the surfaces of the fabrics are respectively measured to be 0 degrees, and the chart A is shown; example a contact angle test chart of a carboxylated modified cotton fabric, the measured surface contact angles of the fabric are respectively 0 degrees, and the chart B; example a MOF @ fabric contact angle test chart, measuring the surface contact angles of the fabric as 0 °, panel C; example contact angle test of a hydrophobized MOF @ fabric, the surface contact angles of the fabric were measured to be 168.4 ± 1.6 °, panel D, respectively.
If the above-mentioned Cu (NO) is added 3 ) 2 ·3H 2 Substitution of O for Co (NO) 3 ) 2 ·6H 2 O, the remainder being unchanged, the resulting MOF @ fabric had a UPF value of 91.9. + -. 10.2.
Example two
(1) Generation of m-aminobenzoic acid diazonium salt
The round bottom flask was equipped with a thermometer and equipped with magnetic stirring. Adding 60 ml of 1M hydrochloric acid solution, cooling to 15 ℃ in a cold bath, adding 3.3 mmol of sodium nitrite, cooling to-5 ℃ in the cold bath, and stirring to dissolve to form sodium nitrite solution. Then 3 mmol of triaminobenzoic acid is added for heat preservation and diazotization for 1h, and the m-carboxybenzoic acid diazonium salt solution is generated.
(2) Formation of the m-carboxybenzene radical
Adding a piece of cotton fabric into the diazonium salt solution, then adding 53mg of a reducing agent VC, heating the temperature of the reaction solution to room temperature, keeping the temperature for 36 hours, reducing the m-carboxybenzoic acid diazonium salt into a m-carboxybenzene free radical monomer, and releasing nitrogen; the m-carboxyl benzene free radical monomer initiates the homolytic cleavage of the hydroxyl on the cotton fiber to generate oxygen free radicals, and simultaneously, other m-carboxyl benzene free radical monomers continue to generate in-situ free radical covalent grafting polymerization with the oxygen free radicals on the cotton fiber to form a carboxyl aromatic polymer chain brush, which is called a carboxylated cotton fabric.
(3) 3.8g of Cu (NO) 3 ) 2 ·3H 2 Dissolving O in 48 mL of mixed solvent of N, N-dimethylacetamide, ethanol and water in a ratio of 1:1:1 to prepare a metal ion-containing solution A; 1.35g of 1,3, 5-benzenetricarboxylic acid was dissolved in 48 mL of a mixed solvent of N, N-dimethylacetamide, ethanol and water in a ratio of 1:1:1 to prepare an organic ligand solution B.
(4) Soaking a piece of carboxylated cotton fabric of 5cm × 8cm in the solution A containing metal ions for 15min, taking out, washing in ethanol solution for 10s, taking out, washing in the solution B containing organic ligands for 15min, taking out, and washing in ethanol solution for 10 s; the above operation steps are a cycle process, and the process is cycled 20 times later. Finally the samples were taken out and washed by shaking in 50mL of fresh absolute ethanol solution, repeated 5 times to remove the remaining unbound metal ions and organic ligands, and finally dried in an oven at 50 ℃ for 3 hours to obtain MOF @ fabric.
(5) And (3) immersing the MOF @ fabric obtained in the step (4) in 20mL of n-octyltriethoxysilane methanol solution for 1h, taking out the fabric, and baking the fabric at 140 ℃ for 1h to obtain the hydrophobic MOF @ fabric.
(6) Ultraviolet resistance test
The UV resistance UPF value of the modified fabric is tested according to GB/T18830 by a UV-2000F textile sun protection index analyzer of blue-phenanthrene optics (Labsphere) Limited. Each single fabric sample was tested five times respectively and averaged. The UPF value of the finished fabric is 322.6 +/-6.0, and the modified fabric shows very excellent ultraviolet resistance.
(7) Contact Angle testing
A DSA100 type full-automatic microscopic droplet wettability measuring instrument of Kruss company in Germany is adopted to test the wettability of the hydrophobic modified MOF @ fabric, deionized 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. The surface contact angles of the MOF @ fabric after hydrophobic modification are respectively 169.2 +/-1.7 degrees, which shows that the MOF @ fabric after hydrophobic modification shows excellent super-hydrophobic performance. Particularly, the invention solves the technical defect that the prior art can obtain super-hydrophobicity only by adopting fluorine-containing materials, and obtains very good hydrophobic performance by adopting fluorine-free silane.
FIG. 7 is a Scanning Electron Microscope (SEM) image of a MOF @ fabric prepared according to example two, with the fiber surface coated with a MOF coating containing a crystalline structure of micron-sized regular octahedral.
EXAMPLE III
(1) To produce 5-amino isophthalic acid diazonium salt
The round bottom flask was equipped with a thermometer equipped with magnetic stirring. Adding 60 ml of 1M hydrochloric acid solution, cooling to 15 ℃ in a cold bath, adding 3.3 mmol of sodium nitrite, cooling to 0 ℃ in the cold bath, and stirring to dissolve to form sodium nitrite acid solution. Then 3 mmol of 5-amino isophthalic acid is added for heat preservation and diazotization for 1h, and dicarboxybenzene diazonium salt is generated.
(2) Formation of dicarboxybenzene radicals
Adding a piece of cotton fabric into the diazonium salt solution, then adding 53mg of a reducing agent VC, heating the temperature of the reaction solution to room temperature, keeping the temperature for 36 hours, reducing the dicarboxybenzene diazonium salt into a dicarboxybenzene free radical monomer, and releasing nitrogen; the dicarboxybenzene radical monomer initiates hydroxyl on the cotton fiber to generate homolytic cleavage to generate oxygen free radicals, and simultaneously other dicarboxybenzene radical monomers continue to generate in-situ free radical covalent grafting polymerization with the oxygen free radicals on the cotton fiber to form the carboxyl aromatic polymer chain brush.
(3) 3.8g of Cu (NO) 3 ) 2 ·3H 2 Dissolving O in 48 mL of mixed solvent of N, N-dimethylacetamide, ethanol and water in a ratio of 1:1:1 to prepare a metal ion-containing solution A; 1.35g of 1,3, 5-benzenetricarboxylic acid was dissolved in 48 mL of a mixed solvent of N, N-dimethylacetamide, ethanol and water in a ratio of 1:1:1 to prepare an organic ligand solution B.
(4) Firstly soaking a piece of carboxylated cotton fabric with the length of 5cm multiplied by 8cm into the solution A containing metal ions for 15min, taking out the piece of carboxylated cotton fabric, putting the piece of carboxylated cotton fabric into an ethanol solution, cleaning the piece of carboxylated cotton fabric for 10s, taking out the piece of carboxylated cotton fabric, putting the piece of carboxylated cotton fabric into the solution B containing an organic ligand, cleaning the piece of carboxylated cotton fabric for 15min, taking out the piece of carboxylated cotton fabric, and then putting the piece of carboxylated cotton fabric into the ethanol solution, and cleaning the piece of carboxylated cotton fabric for 10 s; the above operation steps are a cycle process, and then the process is operated circularly 10 times. Finally the samples were taken out and washed by shaking in 50mL of fresh absolute ethanol solution, repeated 5 times to remove the remaining unbound metal ions and organic ligands, and finally dried in an oven at 50 ℃ for 3 hours to obtain MOF @ fabric.
(5) And (3) immersing the MOF @ fabric obtained in the step (4) in 20mL of n-octyltriethoxysilane methanol solution for 1h, taking out the fabric, and baking the fabric at 140 ℃ for 1h to obtain the hydrophobic MOF @ fabric.
(6) Ultraviolet resistance test
The UV resistance UPF value of the finished fabric was measured according to GB/T18830 using a UV-2000F textile sun protection index Analyzer from blue-phenanthrene optics (Labsphere) Ltd. Each single fabric sample was tested five times and averaged. The UPF value of the finished MOF @ fabric is measured to be 222.6 +/-21.0, and the modified MOF @ fabric shows very excellent ultraviolet resistance.
(7) Contact Angle testing
A DSA100 type full-automatic microscopic droplet wettability measuring instrument of Kruss company in Germany is adopted to test the wettability of the hydrophobic modified MOF @ fabric, deionized water is selected as test droplets, the volume of each droplet is 5 mu L, and the average value is obtained by five times of test. The measured surface contact angles of the MOF @ fabric after hydrophobic modification are 167.6 +/-2.1 degrees respectively, which shows that the MOF @ fabric after hydrophobic modification shows excellent super-hydrophobic performance.
FIG. 8 is a Scanning Electron Microscope (SEM) image of a MOF @ fabric prepared according to example three, with the fiber surface coated with a MOF coating containing a crystalline structure of a micron-sized regular octahedral structure.
Comparative example 1
(1) 3.8g of Cu (NO) 3 ) 2 ·3H 2 Dissolving O in 48 mL of mixed solvent of N, N-dimethylacetamide, ethanol and water in a ratio of 1:1:1 to prepare a metal ion-containing solution A; 1.35g of 1,3, 5-benzenetricarboxylic acid was dissolved in 48 mL of a mixed solvent of N, N-dimethylacetamide, ethanol and water in a ratio of 1:1:1 to prepare an organic ligand solution B.
(2) Immersing a 5cm multiplied by 8cm non-carboxylated modified raw material cotton fabric into a solution A containing metal ions for 15min, taking out, putting into an ethanol solution, cleaning for 10s, taking out, putting into a solution B containing an organic ligand, cleaning for 15min, taking out, and then putting into the ethanol solution, and cleaning for 10 s; the above operation steps are a cycle process, and then the process is operated circularly 10 times. Finally, the sample is taken out, shaken and washed in 50mL of new absolute ethanol solution, repeated for 5 times to remove the residual unbound metal ions and organic ligands, and finally dried in an oven at 50 ℃ for 3 hours to obtain the sample.
(3) And (3) immersing the MOF @ fabric obtained in the step (2) in 20mL of n-octyltriethoxysilane methanol solution for 1h, taking out the fabric, and baking the fabric at 140 ℃ for 1h to obtain the hydrophobic MOF @ fabric.
(4) Ultraviolet resistance test
The UV resistance UPF value of the finished fabric was measured according to GB/T18830 using a UV-2000F textile sun protection index Analyzer from blue-phenanthrene optics (Labsphere) Ltd. Each single fabric sample was tested five times respectively and averaged. The UPF value of the finished fabric is measured to be 46.8 +/-2.2, and the fabric shows general ultraviolet resistance.
(5) Contact Angle testing
A DSA100 type full-automatic microscopic droplet wettability measuring instrument of Kruss company in Germany is adopted to test the wettability of the hydrophobic modified MOF @ fabric, deionized 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. The surface contact angles of the MOF @ fabrics after hydrophobic modification are respectively measured to be 129.2 +/-1.1 degrees, which indicates that the MOF @ fabrics after hydrophobic modification show general hydrophobic performance but do not reach super-hydrophobic effect.
FIG. 9 is a Scanning Electron Microscope (SEM) image of a non-carboxylated modified fabric long MOF prepared in comparative example one.
Comparative example No. two
(1) Adding a raw material cotton fabric (5 cm multiplied by 8 cm) into an aqueous solution containing 4wt% of citric acid and 4wt% of sodium hypophosphite, soaking for 5 minutes, then soaking for two times and rolling for two times, heating at 100 ℃ for 3 minutes, and then heating at 170 ℃ for 3 minutes to obtain the carboxylated cotton fabric.
(2) 3.8g of Cu (NO) 3 ) 2 ·3H 2 Dissolving O in 48 mL of mixed solvent of N, N-dimethylacetamide, ethanol and water in a ratio of 1:1:1 to prepare a metal ion-containing solution A; 1.35g of 1,3, 5-benzenetricarboxylic acid was dissolved in 48 mL of a mixed solvent of N, N-dimethylacetamide, ethanol and water in a ratio of 1:1:1 to prepare an organic ligand solution B.
(3) Soaking a piece of carboxylated cotton fabric of 5cm × 8cm in the solution A containing metal ions for 15min, taking out, washing in ethanol solution for 10s, taking out, washing in the solution B containing organic ligands for 15min, taking out, and washing in ethanol solution for 10 s; the above operation steps are a cycle process, and then the process is operated circularly 20 times. Finally the samples were taken out and washed by shaking in 50mL of fresh absolute ethanol solution, repeated 5 times to remove the remaining unbound metal ions and organic ligands, and finally dried in an oven at 50 ℃ for 3 hours to obtain MOF @ fabric.
(4) Immersing the MOF @ fabric obtained in the step (5) in 20mL of n-octyltriethoxysilane methanol solution for 1h, and then taking out the fabric and baking the fabric at 140 ℃ for 1h to obtain a hydrophobic MOF @ fabric instead of a super-hydrophobic fabric.
(5) Ultraviolet resistance test
The UV resistance UPF value of the modified fabric is tested according to GB/T18830 by a UV-2000F textile sun protection index analyzer of blue-phenanthrene optics (Labsphere) Limited. The MOF @ fabric had a UPF value of 96.6. + -. 8.7 as determined by five separate measurements for each fabric sample.
According to the invention, the fiber surface is subjected to carboxylation modification finishing by an aromatic diazo free radical covalent graft polymerization method, a carboxyl polymer chain brush is formed on the fiber surface, then self-assembly is carried out through coordination between metal ions and organic ligands, and a compact MOF crystal structure coating grows in situ on the fiber surface, for example, as shown in FIG. 4, so that the problems that the original length of MOF cannot be increased and the grown MOF crystal is small in sparse load are solved. This is of great importance for the in situ growth of MOF materials on the fiber surface for the preparation of a new generation of functionalized MOF @ fabrics. The invention discloses a functionalized MOF @ fabric and a preparation method thereof. The method comprises the following steps of diazotizing carboxyl aniline serving as a reaction monomer in an acid solution of sodium nitrite to generate carboxyl-containing benzene diazonium salt; adding the fabric into the diazonium salt solution, adding a reducing agent, heating to room temperature, reducing the carboxyl-containing benzene diazonium salt into carboxyl-containing benzene free radicals at the room temperature, and performing single electron free radical initiation on hydroxyl on the surface of the cellulose fiber fabric such as cotton, hemp and the like by using a free radical monomer to generate hydroxyl free radicals; then, free radical monomer generates free radical covalent grafting polymerization reaction on the surface of the fiber; sequentially adding the carboxylated fabric into a metal ion solution A, ethanol, an organic ligand solution B and ethanol, carrying out circulating layer-by-layer self-assembly growth to form an MOF coating structure, and reacting for a certain time to obtain an MOF @ fabric; and then carrying out hydrophobic coating finishing on the fabric to finally obtain the super-hydrophobic MOF @ fabric. The carboxylated fabric treatment process is completed by reduction polymerization in a dilute acid solution at room temperature by using a chemical reducing agent, the MOF in-situ growth is also completed at room temperature, the production process is simple, the reaction condition is mild, and the operation is safe. Based on the fact that carboxyl-containing aromatic polymer chains are bonded on the surface of the fiber through covalent bonds, and carboxyl active sites provide sufficient conditions for anchoring of a large number of metal ions and in-situ growth of MOF; the functional fabric has strong ultraviolet absorption and super-hydrophobic performance, and the original wearability of the fabric is not influenced; the method solves the problems of poor fastness and small load of the MOF @ fabric obtained by methods such as mechanical mixed finishing and the like, and simultaneously endows the fabric with more valuable additional function application potentials. The processing of the carboxylated fabric is completed by aromatic radical polymerization, the MOF crystal is completed by layer-by-layer self-assembly in-situ growth, and the special performance of the metal organic framework MOF porous structure is combined, so that the functionalized MOF @ fabric is obtained.
Claims (10)
1. An ultraviolet-proof super-hydrophobic fabric is characterized in that: the ultraviolet-proof super-hydrophobic fabric comprises a fabric, a carboxyl aromatic polymer chain grafted on the surface of the fabric, an MOF crystal structure and a hydrophobic coating; the MOF crystal structure is formed by coordination assembly of metal ions with organic ligands.
2. The ultraviolet-proof super-hydrophobic fabric as claimed in claim 1, wherein the fabric is a cotton fabric and/or a hemp fabric; the MOF is CuBTC.
3. The preparation method of the anti-ultraviolet superhydrophobic fabric according to claim 1, wherein the fabric is added into a carboxyl-containing aromatic diazonium salt solution, then a chemical reducing agent is added, and polymerization reaction is carried out to obtain the fabric with the surface grafted with carboxyl aromatic polymer chains; then, carrying out layer-by-layer self-assembly on the fabric with the surface grafted with the carboxyl aromatic polymer chain in a solution containing metal ions and an organic ligand solution to obtain an anti-ultraviolet fabric; and finally, performing hydrophobic finishing to obtain the ultraviolet-proof super-hydrophobic fabric.
4. The preparation method of the ultraviolet-proof super-hydrophobic fabric as claimed in claim 3, wherein the carboxyl-containing aromatic amine is diazotized in an acid solution of sodium nitrite to obtain an aromatic diazonium salt solution containing carboxyl; the polymerization reaction time is 6-72 h.
5. The method for preparing the ultraviolet-proof super-hydrophobic fabric as claimed in claim 3, wherein the fabric with the surface grafted with the carboxyl aromatic polymer chain is dipped in the solution containing the metal ions and then dipped in the organic ligand solution for self-assembly.
6. The preparation method of the ultraviolet-proof super-hydrophobic fabric as claimed in claim 5, wherein the dipping time is 3-60 min; the number of self-assembly of the layers is 3-30.
7. The method for preparing the ultraviolet-proof superhydrophobic fabric according to claim 3, wherein the hydrophobic finish is performed by using siloxane.
8. An anti-ultraviolet fabric is characterized in that the fabric is added into aromatic diazonium salt solution containing carboxyl, then chemical reducing agent is added, and the fabric with the surface grafted with carboxyl aromatic polymer chain is obtained through polymerization reaction; and then, carrying out layer-by-layer self-assembly on the fabric with the surface grafted with the carboxyl aromatic polymer chain in a solution containing metal ions and an organic ligand solution to obtain the ultraviolet-proof fabric.
9. The ultraviolet-proof fabric of claim 8, wherein the fabric with the surface grafted with carboxyl aromatic polymer chains is self-assembled by dipping the fabric in a solution containing metal ions and then dipping the fabric in a solution of organic ligands.
10. Use of the ultraviolet-proof superhydrophobic fabric of claim 1 or the ultraviolet-proof fabric of claim 8 in the preparation of a functional fabric.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549177A (en) * | 2014-12-18 | 2015-04-29 | 昆明理工大学 | Diazonium method coupling gelatin adsorption material and preparation method thereof |
| CN108642869A (en) * | 2018-04-12 | 2018-10-12 | 华南理工大学 | A kind of preparation method of super-hydrophobic anti-UV fabric |
| CN111472171A (en) * | 2020-05-18 | 2020-07-31 | 苏州大学 | Super-hydrophobic fabric and preparation method thereof |
| CN112900097A (en) * | 2021-01-21 | 2021-06-04 | 南通大学 | Durable super-hydrophobic anti-ultraviolet cotton fabric and preparation method thereof |
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| CN108976460B (en) * | 2018-08-16 | 2021-07-02 | 中国科学院长春应用化学研究所 | MOF (Metal organic framework) film material containing lubricating layer, preparation method of MOF film material and application of MOF film material in anti-icing field |
| CN110565398B (en) * | 2019-09-06 | 2021-12-21 | 东华大学 | Rare earth doped MOF (Metal organic framework) -based dyed fluorescent fabric and preparation method thereof |
| CN112691552B (en) * | 2019-10-23 | 2023-03-14 | 中国石油化工股份有限公司 | Method for preparing high-performance organic gas separation membrane |
| CN112755968B (en) * | 2020-12-31 | 2022-09-09 | 廊坊师范学院 | Application of MOFs fiber membrane in adsorption of micro-nano plastic in trapped water |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104549177A (en) * | 2014-12-18 | 2015-04-29 | 昆明理工大学 | Diazonium method coupling gelatin adsorption material and preparation method thereof |
| CN108642869A (en) * | 2018-04-12 | 2018-10-12 | 华南理工大学 | A kind of preparation method of super-hydrophobic anti-UV fabric |
| CN111472171A (en) * | 2020-05-18 | 2020-07-31 | 苏州大学 | Super-hydrophobic fabric and preparation method thereof |
| CN112900097A (en) * | 2021-01-21 | 2021-06-04 | 南通大学 | Durable super-hydrophobic anti-ultraviolet cotton fabric and preparation method thereof |
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