Composite fabric material and method of making the same

Abstract

The application belongs to the technical field of environment-friendly fabrics, and discloses a composite fabric material and a preparation method thereof. The preparation method of the composite fabric material comprises the following steps: soaking cellulose fabric in a N,N-dimethylformamide solution containing zirconium chloride, stirring, and then ultrasonic treatment to obtain an initial solution; adding a DMF solution containing terephthalic acid and 4-aminoisophthalic acid into the initial solution, uniformly mixing to obtain a mixed solution; adding a pH regulator into the mixed solution, and performing reaction on the cellulose fabric through water bath heating; washing the cellulose fabric after the reaction is completed with an organic solvent; and drying the cellulose fabric to obtain cellulose fabric with surface growth of UiO-66-3C4N. Through the compounding with metal organic framework (MOF) material, the cellulose-based material is endowed with greater specific surface area and excellent hydrophilic performance. Meanwhile, the loading rate of MOF on the surface energy of the cellulose fabric is high, and the fiber surface is completely covered, so the cellulose fabric can be widely used for the treatment of uranium-containing wastewater.

Description

Technical Field

[0001] This invention relates to the field of environmentally friendly fabric technology, and in particular to a composite fabric material and its preparation method. Background Technology

[0002] As the world's largest textile producer, my country generates over 20 million tons of waste textiles annually, with a recycling rate of only about 20%. This easily leads to resource waste and environmental pollution. Traditional waste textile processing generates a large amount of solid waste, which in turn affects the ecological environment. In particular, the process of landfilling or incineration releases harmful gases, causing air, water, and soil pollution.

[0003] Existing technologies involve converting waste textiles into high-value-added materials to adsorb pollutants. However, existing modified waste textile products often suffer from low adsorption efficiency, poor selectivity, and high cost, making it difficult to meet the needs of industrial-scale production. Summary of the Invention

[0004] The main objective of this invention is to provide a composite fabric material and its preparation method, aiming to solve the problem that existing recycled textile products cannot meet the needs of industrial-scale production.

[0005] To achieve the above objectives, the present invention provides a method for preparing a composite fabric material, comprising the following steps: The cellulose fabric was soaked in a solution containing zirconium chloride and N,N-dimethylformamide, stirred, and then sonicated to obtain the initial solution. Add a DMF solution containing terephthalic acid and 4-aminoisophthalic acid to the initial solution, mix well to obtain a mixed solution; A pH adjuster is added to the mixed solution, and the mixture is heated in a water bath to react on the cellulose fabric.

[0006] The cellulose fabric after the reaction was completed was washed with an organic solvent; The cellulose fabric is dried to obtain a cellulose fabric with UiO-66-3C4N grown on its surface.

[0007] In one embodiment, in the step of immersing the cellulose fabric in an N,N-dimethylformamide solution containing zirconium chloride, stirring, and then ultrasonically treating it to obtain an initial solution, the stirring is mechanical stirring at a speed of 280 to 320 r / min for a time of 30 to 50 min.

[0008] In one embodiment, the cellulose fabric includes any one of cotton fabric, viscose, Tencel, and cotton-polyester blend.

[0009] In one embodiment, the pH adjuster in the step of adding a pH adjuster to the mixed solution is acetic acid.

[0010] In one embodiment, in the step of washing the cellulose fabric after the reaction is completed with an organic solvent, the organic solvent is N,N-dimethylformamide or methanol.

[0011] In one embodiment, prior to the step of drying to obtain a cellulose fabric with UiO-66-3C4N grown on its surface, the method further includes: The cellulose fabric is rinsed with deionized water to remove the organic solvent.

[0012] In one embodiment, in the step of drying the cellulose fabric to obtain a cellulose fabric with UiO-66-3C4N grown on its surface, the drying is vacuum drying, the drying temperature is 60~80℃, and the time is 10h~18h.

[0013] In one embodiment, the zirconium chloride accounts for 1% to 1.5% by mass percentage, the terephthalic acid accounts for 0.5% to 1%, the 4-aminoisophthalic acid accounts for 0.2% to 0.5%, and the pH adjuster accounts for 5% to 12%.

[0014] The present invention also provides a composite fabric material, which is a cellulose fabric prepared according to the preparation method of the composite fabric material according to any one of the above.

[0015] This invention provides a method for preparing a composite fabric material. The composite fabric material is prepared by in-situ growth of UiO-66-3C4N from cellulose. Due to the unique mechanical properties, processability, and chemical modification potential of cellulose, and by combining it with metal-organic frameworks (MOFs), the problems of small specific surface area and low uranium selectivity in pure cellulose fabrics are further improved. This results in a larger specific surface area and excellent hydrophilicity in the cellulose-based material, which are beneficial for the selection of uranyl ions (UO2-) in seawater. 2+ The adsorption of uranium-containing wastewater by MOFs is effective. At the same time, MOFs have a high loading rate on the surface of cellulose fabrics, and the fiber surface is completely covered. They can be widely used in the treatment of uranium-containing wastewater to meet the needs of industrial-scale applications. Attached Figure Description

[0016] Figure 1 These are SEM images of embodiments 1 to 4 provided by the present invention; Figure 2 These are X-ray structural characterization diagrams of embodiments 1 to 4 provided by the present invention; Figure 3 These are test graphs of the uranium adsorption performance of embodiments 1 to 4 provided by the present invention; Figure 4These are MOF load rate diagrams for embodiments 1 to 4 provided by the present invention.

[0017] The realization of the objective, functional features and advantages of the present invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0018] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0019] It should be noted that if the embodiments of the present invention involve directional indicators (such as up, down, left, right, front, back, etc.), the directional indicators are only used to explain the relative positional relationship and movement of the components in a certain specific posture (as shown in the figure). If the specific posture changes, the directional indicators will also change accordingly.

[0020] Furthermore, if the embodiments of this invention involve descriptions such as "first" or "second," these descriptions are for descriptive purposes only and should not be construed as indicating or implying their relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined with "first" or "second" may explicitly or implicitly include at least one of those features. Additionally, the meaning of "and / or" throughout the text includes three parallel solutions; for example, "A and / or B" includes solution A, solution B, or a solution where both A and B are satisfied simultaneously. Furthermore, the technical solutions of the various embodiments can be combined with each other, but this must be based on the ability of those skilled in the art to implement them. When the combination of technical solutions is contradictory or impossible to implement, it should be considered that such a combination of technical solutions does not exist and is not within the scope of protection claimed by this invention.

[0021] Please see Figure 1 This invention provides a method for preparing a composite fabric material, comprising the following steps: S10. Soak the cellulose fabric in an N,N-dimethylformamide solution containing zirconium chloride, stir, and then sonicate to obtain the initial solution. S20. Add a DMF solution containing terephthalic acid and 4-aminoisophthalic acid to the initial solution and mix thoroughly to obtain a mixed solution; S30. Add a pH adjuster to the mixed solution and heat in a water bath to react on the cellulose fabric; S40. The cellulose fabric after the reaction is completed is washed with an organic solvent; S50. Dry the cellulose fabric to obtain a cellulose fabric with UiO-66-3C4N grown on its surface.

[0022] This invention provides a method for preparing a composite fabric material. The composite fabric material is prepared by in-situ growth of UiO-66-3C4N from cellulose. Due to the unique mechanical properties, processability, and chemical modification potential of cellulose, and by combining it with metal-organic frameworks (MOFs), the problems of small specific surface area and low uranium selectivity in pure cellulose fabrics are further improved. This results in a larger specific surface area and excellent hydrophilicity in the cellulose-based material, which are beneficial for the selection of uranyl ions (UO2-) in seawater. 2+ The composite fabric material prepared by MOF is suitable for different types of cellulose fabrics. Due to the differences in physical structure, surface functional groups and porosity, it exhibits different uranium adsorption performance after being combined with MOF. The preparation of cellulose fabrics is simple, low cost and widely applicable to the recycling of waste textiles. Moreover, MOF has a high surface energy loading rate on cellulose fabrics and the fiber surface is completely covered. It can be widely used in the treatment of uranium-containing wastewater with high selectivity to meet the needs of industrial scale.

[0023] Furthermore, in step S10, the stirring is mechanical, with a stirring speed of 280 to 320 r / min and a stirring time of 30 to 50 min. This ensures uniform stirring between the cellulose fabric and the N,N-dimethylformamide solution containing zirconium chloride.

[0024] Preferably, in this application, the stirring speed is 300 r / min.

[0025] In the embodiments provided by this invention, the cellulose fabric can be implemented in various ways, including any one of cotton fabric, viscose, Tencel, and cotton-polyester blends. Its different physical structures, surface functional groups, and porosities, when combined with MOF, exhibit different uranium adsorption properties, resulting in a cellulose fabric that is simple to prepare, low in cost, and widely applicable to the recycling of waste textiles.

[0026] On the other hand, in step S30, the pH adjuster can be implemented in various ways. In this embodiment, the pH adjuster is acetic acid.

[0027] Similarly, in step S40, the organic solvent can be implemented in various ways. In this embodiment, the organic solvent is N,N-dimethylformamide or methanol.

[0028] On the other hand, prior to step S50, the following is also included: S501. Rinse the cellulose fabric with deionized water to remove the organic solvent, in order to avoid the influence of the organic solvent on the cellulose fabric during the drying process.

[0029] Furthermore, in step S50, the drying is vacuum drying, the drying temperature is 60~80℃, and the time is 10h~18h.

[0030] On the other hand, in the embodiments provided by the present invention, the zirconium chloride is 1% to 1.5% by mass, the terephthalic acid is 0.5% to 1%, the 4-aminoisophthalic acid is 0.2% to 0.5%, and the acetic acid is 5% to 12%.

[0031] Based on the above-described method for preparing composite fabric materials, the present invention also provides a composite fabric material, which is a cellulose fabric prepared according to the above-described method for preparing composite fabric materials. That is, it also has all the technical features of the cellulose fabric prepared by the above-described method for preparing composite fabric materials, and therefore also has the technical effects brought about by all the above-described technical features, which will not be elaborated here.

[0032] Based on the above-described method for preparing composite fabric materials, the present invention provides the following specific embodiments.

[0033] Example 1:

[0034] The cotton fabric was soaked in an N,N-dimethylformamide solution containing zirconium chloride, mechanically stirred, and then ultrasonically treated.

[0035] Add a DMF solution containing terephthalic acid and 4-aminoisophthalic acid, and mix well.

[0036] A certain amount of acetic acid is added to the solution, mixed evenly, and then heated in a water bath at 60℃~120℃ for 12~24 hours.

[0037] After the reaction is complete, wash the cotton fabric 3-6 times with N,N-dimethylformamide or methanol.

[0038] Rinse cotton fabrics with deionized water to remove any organic solvents they contain.

[0039] Finally, vacuum dry for 12-24 hours.

[0040] The composition includes zirconium chloride (1%–1.5% by mass), terephthalic acid (0.5%–1%), 4-aminoisophthalic acid (0.2%–0.5%), acetic acid (5%–12%), and the remainder is DMF.

[0041] The mechanical stirring speed is 300 r / min, and the time is 30 min to 50 min; the vacuum drying temperature is 60 to 80℃, and the time is 10 h to 18 h.

[0042] Example 2:

[0043] The adhesive was immersed in a solution containing zirconium chloride and then subjected to ultrasonic treatment after mechanical stirring.

[0044] Add a DMF solution containing terephthalic acid and 4-aminoisophthalic acid, and mix well.

[0045] A certain amount of acetic acid is added to the solution, mixed evenly, and then heated in a water bath at 60℃~120℃ for 12~24 hours.

[0046] After the reaction is complete, wash with N,N-dimethylformamide or methanol 3-6 times.

[0047] Rinse the adhesive with deionized water.

[0048] Finally, vacuum dry for 12-24 hours.

[0049] Of which, by mass percentage, zirconium chloride is 1%–1.5%, terephthalic acid is 0.5%–1%, 4-aminoisophthalic acid is 0.2%–0.5%, acetic acid is 5%–12%, and the remainder is DMF.

[0050] The mechanical stirring speed is 300 r / min, and the time is 30 min to 50 min; the vacuum drying temperature is 60 to 80℃, and the time is 10 h to 18 h.

[0051] Example 3:

[0052] Tencel was immersed in a solution containing zirconium chloride and then subjected to ultrasonic treatment after mechanical stirring.

[0053] Add a DMF solution containing terephthalic acid and 4-aminoisophthalic acid, and mix well.

[0054] A certain amount of acetic acid is added to the solution, mixed evenly, and then heated in a water bath at 60℃~120℃ for 12~24 hours.

[0055] After the reaction is complete, wash with N,N-dimethylformamide or methanol 3-6 times.

[0056] Rinse Tencel with deionized water.

[0057] Finally, vacuum dry for 12-24 hours.

[0058] Of which, by mass percentage, zirconium chloride is 1%–1.5%, terephthalic acid is 0.5%–1%, 4-aminoisophthalic acid is 0.2%–0.5%, acetic acid is 5%–12%, and the remainder is DMF.

[0059] The mechanical stirring speed is 300 r / min, and the time is 30 min to 50 min; the vacuum drying temperature is 60 to 80℃, and the time is 10 h to 18 h.

[0060] Example 4:

[0061] The cotton-polyester blend was immersed in a solution containing zirconium chloride and then subjected to ultrasonic treatment after mechanical stirring.

[0062] Add a DMF solution containing terephthalic acid and 4-aminoisophthalic acid, and mix well.

[0063] Add a certain amount of vinegar to the solution, mix well, and then heat in a water bath at 60℃~120℃ for 12~24 hours.

[0064] After the reaction is complete, wash with N,N-dimethylformamide or methanol 3-6 times.

[0065] Rinse cotton-polyester blends with deionized water.

[0066] Finally, vacuum dry for 12-24 hours.

[0067] Of which, by mass percentage, zirconium chloride is 1%–1.5%, terephthalic acid is 0.5%–1%, 4-aminoisophthalic acid is 0.2%–0.5%, acetic acid is 5%–12%, and the remainder is DMF.

[0068] The mechanical stirring speed is 300 r / min, and the time is 30 min to 50 min; the vacuum drying temperature is 60 to 80℃, and the time is 10 h to 18 h.

[0069] Please see Figure 1 In Examples 1 to 4 of this invention, SEM images of the prepared UiO-66-3C4N / cotton fabric, UiO-66-3C4N / viscose, UiO-66-3C4N / Tencel, and UiO-66-3C4N / cotton-polyester blended composite materials are shown. As can be seen from the images, UiO-66-3C4N grows uniformly on the surface of the four cellulose fabrics, forming a dense coating that completely covers the fiber surface.

[0070] Please see Figure 2 The structures of the UiO-66-3C4N / cellulose composites prepared in Examples 1-4 were characterized by X-ray diffraction (XRD). The results showed that UiO-66-3C4N was successfully synthesized in the composites.

[0071] Please see Figure 3The uranium adsorption performance of the UiO-66-3C4N / cellulose composites prepared in Examples 1-4 was tested using inductively coupled plasma optical emission spectrometry (ICP-OES). The results showed that all four composites had good adsorption performance for uranium ions.

[0072] Please see Figure 4 The MOF loading rates of UiO-66-3C4N / cotton fabric, UiO-66-3C4N / viscose, UiO-66-3C4N / Tencel, and UiO-66-3C4N / cotton-polyester blended composites were measured. All prepared UiO-66-3C4N / cellulose composites exhibited high loading rates, with the UiO-66-3C4N / viscose composite showing the highest loading rate at 22%. This further demonstrates that the method of this invention can successfully prepare UiO-66-3C4N composites with high loading rates on various cellulose fabrics.

[0073] The above are merely preferred embodiments of the present invention and do not limit the scope of the patent. Any equivalent structural or procedural transformations made based on the description and drawings of the present invention, or direct or indirect applications in other related technical fields, are similarly included within the scope of patent protection of the present invention.

Claims

1. A method for preparing a composite fabric material, characterized in that, Includes the following steps: The cellulose fabric was soaked in a solution containing zirconium chloride and N,N-dimethylformamide, stirred, and then sonicated to obtain the initial solution. A DMF solution containing terephthalic acid and 4-aminoisophthalic acid was added to the initial solution and mixed thoroughly to obtain a mixed solution. A pH adjuster is added to the mixed solution, and the mixture is heated in a water bath to carry out the reaction on the cellulose fabric; The cellulose fabric after the reaction is completed is washed with an organic solvent; The cellulose fabric is dried to obtain a cellulose fabric with UiO-66-3C4N grown on its surface.

2. The method for preparing the composite fabric material according to claim 1, characterized in that, In the step of immersing the cellulose fabric in an N,N-dimethylformamide solution containing zirconium chloride, stirring, and then ultrasonically treating it to obtain the initial solution, the stirring is mechanical stirring at a speed of 280 to 320 r / min for 30 to 50 min.

3. The method for preparing the composite fabric material according to claim 1, characterized in that, The cellulose fabric includes any one of cotton fabric, viscose, Tencel, and cotton-polyester blends.

4. The method for preparing the composite fabric material according to claim 1, characterized in that, In the step of adding a pH adjuster to the mixed solution, the pH adjuster is acetic acid.

5. The method for preparing the composite fabric material according to claim 1, characterized in that, In the step of washing the cellulose fabric with an organic solvent after the reaction is completed, the organic solvent is N,N-dimethylformamide or methanol.

6. The method for preparing the composite fabric material according to claim 1, characterized in that, Prior to the step of drying to obtain a cellulose fabric with UiO-66-3C4N grown on its surface, the method further includes: The cellulose fabric is rinsed with deionized water to remove the organic solvent.

7. The method for preparing the composite fabric material according to claim 1, characterized in that, In the step of drying the cellulose fabric to obtain a cellulose fabric with UiO-66-3C4N grown on its surface, the drying is vacuum drying, the drying temperature is 60~80℃, and the time is 10h~18h.

8. The method for preparing the composite fabric material according to claim 1, characterized in that, The zirconium chloride comprises 1% to 1.5% by mass, the terephthalic acid comprises 0.5% to 1%, the 4-aminoisophthalic acid comprises 0.2% to 0.5%, and the pH adjuster comprises 5% to 12%.

9. A composite fabric material, characterized in that, Cellulose fabric prepared according to the method for preparing composite fabric material according to any one of claims 1 to 8.

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