PDMS (Polydimethylsiloxane) functionalized MOFs (Metal-Organic Frameworks) modified super-hydrophobic paper and preparation method and application thereof
By growing MOF particles in situ on the surface of cellulose paper and modifying them with PDMS, a superhydrophobic surface is constructed, which solves the problem of the hydrophilicity limitation of cellulose paper and achieves self-cleaning and oil-water separation properties, making it suitable for transport packaging and waterproof and moisture-proof protection.
Patent Information
- Application Number
- CN202411295053.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-15
- Publication Date
- 2026-03-17
AI Technical Summary
Existing technologies make it difficult to efficiently prepare hydrophobic paper. The hydrophilicity of cellulose paper limits its waterproof and stain-resistant properties, and commonly used methods are complex and difficult to mass-produce.
MOF particles were grown in situ on the surface of cellulose paper using a solvothermal method, and then modified with PDMS solution to construct a superhydrophobic surface. By constructing a rough structure on the surface of cellulose paper, the superhydrophobic effect was achieved by combining the three-dimensional nano/micro hierarchical structure of MOFs with the low surface energy of PDMS.
The prepared PDMS-functionalized MOFs-modified superhydrophobic paper has good self-cleaning and oil-water separation properties, and is suitable for transport packaging, waterproof and moisture-proof protection and oil-water separation. It is simple to operate, low in cost, and suitable for large-scale production.
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Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of super-hydrophobic paper, and particularly relates to a PDMS functionalized MOFs modified super-hydrophobic paper and a preparation method and application thereof. TECHNICAL BACKGROUND
[0002] The information disclosed in this background section is intended to increase an understanding of the general context of the application and is not necessarily recognized in the prior art.
[0003] In recent years, super-hydrophobic materials have attracted much attention due to their excellent antifouling, self-cleaning and oil-water separation properties. At present, the commonly used methods for preparing hydrophobic surfaces mainly include gas phase chemical deposition, electrochemical method and nanoparticle deposition, which have the disadvantages of complex process and high equipment requirement, and to some extent, limit the practical application of hydrophobic materials. Cellulose paper has the characteristics of renewable, biodegradable and low cost, and is widely used in packaging, culture and daily life. However, cellulose fibers contain a large number of hydrophilic groups and have good hydrophilicity, poor water and antifouling properties, which seriously limit its application. Therefore, it is urgent to prepare a new type of hydrophobic paper by using a simple and efficient technology. Super-hydrophobic surface is mainly affected by low surface energy and surface roughness, and constructing a suitable rough structure on the substrate surface is the key to preparing a super-hydrophobic surface. A super-hydrophobic paper can be prepared by constructing a rough structure on the surface of cellulose paper.
[0004] Metal-organic frameworks (MOFs) materials have attracted much attention due to their high porosity, adjustable structure and high surface area. MOFs particles can greatly improve the surface roughness of the substrate material due to their three-dimensional nano / micro-layer structure. It is a promising technology to combine MOFs with cellulose paper to prepare super-hydrophobic paper. SUMMARY
[0005] In view of the problems existing in the prior art, a first object of the present application is to provide a preparation method of a PDMS functionalized MOFs modified super-hydrophobic paper, which has the advantages of simple operation, high efficiency and the like, and is easy to mass produce efficiently.
[0006] A second object of the present application is to provide a super-hydrophobic paper prepared by the above method, which has good self-cleaning and oil-water separation properties.
[0007] A third object of the present application is to provide the application of the above-mentioned PDMS functionalized MOFs modified super-hydrophobic paper, which can be used in the fields of transportation packaging, waterproof and moisture-proof protection and oil-water separation.
[0008] To achieve the above objects, the technical solutions adopted by the present application are as follows: A method for preparing PDMS-functionalized MOFs-modified superhydrophobic paper, the method comprising the following steps: (1) Place the cellulose paper in a zirconium ion solution and stir and sonicate; (2) Add organic ligand solution to the solution obtained in step (1) to obtain MOFs modified cellulose paper; (3) The MOFs-modified cellulose paper obtained in step (2) is immersed in a polydimethoxysiloxane (PDMS) solution to obtain the superhydrophobic paper.
[0009] Further, in step (1), the cellulose paper is made from cotton pulp with a basis weight of 80 g / m³. 2 ; The zirconium ion solution is prepared by the following steps: 0.25-1.25 g ZrCl4 is dissolved in 10-50 mL N,N-dimethylformamide and 2-10 mL hydrochloric acid, and stirred at 400-500 rpm for 15-20 min; The mass-to-volume ratio of the cellulose paper and the zirconium ion solution is (0.14~1.55) g : (12~60) mL.
[0010] Furthermore, the zirconium ion solution needs to be stirred during preparation, with a stirring speed of 400-500 rpm and a stirring time of 15-20 min; the concentration of the hydrochloric acid is 36%-37%.
[0011] Further, in step (2), the organic ligand solution is prepared by the following steps: 0.268~1.34 g of 2-aminoterephthalic acid is dissolved in 20~100 mL of N,N-dimethylformamide and stirred at 400 rpm for 15 min; The mass-to-volume ratio of the cellulose paper and the organic ligand solution is (0.14~1.55) g : (20~100) mL.
[0012] Furthermore, in step (2), after adding the organic ligand solution, stirring, heating, washing, and drying are also required.
[0013] Furthermore, the stirring rate is 400~500 rpm, and the stirring temperature is 80~100℃; The heating temperature is 80~100℃, and the time is 3~12 h; The washing method is to wash three times each with N,N-dimethylformamide and anhydrous ethanol; The drying temperature is 45~60℃, and the time is 12~24 h.
[0014] Further, in step (3), the PDMS solution is prepared by the following steps: 1g of PDMS (as the main agent) and 0.1g of PDMS (as the curing agent) are dissolved in 30-50 mL of n-hexane and stirred at 400 rpm for 10 min; The mass-to-volume ratio of the cellulose paper in step (1) to the PDMS solution in step (3) is (0.14~1.55) g: (30~50) mL.
[0015] Furthermore, in step (3), the soaking time is 10-15 min; After soaking, the material needs to be dried; the drying temperature is 80~85℃ and the time is 2~3 hours.
[0016] The PDMS-functionalized MOFs-modified superhydrophobic paper prepared by the above method.
[0017] The above-mentioned PDMS functionalized MOFs modified superhydrophobic paper is used in the fields of transport packaging, waterproof and moisture-proof protection, and marine oil spill cleanup.
[0018] Beneficial effects: (1) This invention provides a PDMS-functionalized MOFs-modified superhydrophobic paper and its preparation method. The preparation method of the MOFs-modified cellulose paper is a solvothermal method. First, the cellulose paper is immersed in a zirconium ion solution, then an organic ligand solution is added and heated to obtain the paper. Finally, the MOFs-modified cellulose paper is immersed in a PDMS solution to obtain PDMS-functionalized MOFs-modified superhydrophobic paper. The solvothermal method involves growing MOFs in situ on the surface of cellulose fibers. The preparation method has the advantages of simple operation and high efficiency.
[0019] (2) The PDMS functionalized MOFs modified superhydrophobic paper provided by the present invention has good self-cleaning performance and oil-water separation performance, and is renewable and low in cost. It has broad application prospects in the fields of transport packaging, waterproof and moisture-proof protection and oil-water separation. Attached Figure Description
[0020] The accompanying drawings, which form part of this specification, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. Hereinafter, embodiments of the invention will be described in detail with reference to the accompanying drawings, wherein: Figure 1 Scanning electron microscope (SEM) images of pure cellulose paper, MOF-modified cellulose paper, and PDMS-functionalized MOF-modified hydrophobic paper prepared in Example 1. Figure 1 (a) is a scanning electron microscope image of pure cellulose paper. Figure 1 (b) is a scanning electron microscope image of MOF-modified cellulose paper.Figure 1 (c) is a scanning electron microscope image of the PDMS-functionalized MOFs-modified hydrophobic paper prepared in Example 1; Figure 2 The contact angle test diagram of the PDMS-functionalized MOF-modified hydrophobic paper prepared in Example 1 is shown. (This refers to pure cellulose paper and MOF-modified cellulose paper.) Figure 2 (a) is a test diagram of the contact angle of pure cellulose paper. Figure 2 (b) is a contact angle test diagram of MOF-modified cellulose paper. Figure 2 (c) is a contact angle test diagram of the PDMS functionalized MOFs modified hydrophobic paper prepared in Example 1; Figure 3 The image shows the antifouling effect of the PDMS-functionalized MOF-modified hydrophobic paper prepared in Example 1, which is pure cellulose paper and MOF-modified cellulose paper. Figure 3 (a) is a diagram showing the stain resistance of pure cellulose paper. Figure 3 (b) is a diagram showing the stain resistance of MOF-modified cellulose paper. Figure 3 (c) is a diagram showing the antifouling effect of the PDMS-functionalized MOFs-modified hydrophobic paper prepared in Example 1; Figure 4 The image shows the self-cleaning effect of the PDMS-functionalized MOF-modified hydrophobic paper prepared in Example 1, which is a pure cellulose paper and MOF-modified cellulose paper. Figure 4 (a) is a diagram showing the self-cleaning effect of pure cellulose paper. Figure 4 (b) is a diagram showing the self-cleaning effect of MOF-modified cellulose paper. Figure 4 (c) is a diagram showing the self-cleaning effect of the PDMS-functionalized MOFs-modified hydrophobic paper prepared in Example 1; Figure 5 This is a schematic diagram of the oil-water separation process of the PDMS-functionalized MOFs-modified hydrophobic paper prepared in Example 1. Figure 6 The image shows the oil-water separation efficiency of the PDMS-functionalized MOFs-modified hydrophobic paper prepared in Example 1. Detailed Implementation
[0021] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0022] Example 1 Preparation of cellulose paper: 2.77 g of cotton pulp board (purchased from Sun Paper Co., Ltd., with a moisture content of 10%) was weighed and placed in a defrosting machine, and defrosted at 900 rpm for 2 min. The defrosted fiber mixture was then passed through a paper forming machine to obtain cellulose paper with a diameter of 20 cm.
[0023] Preparation of zirconium ion solution: Dissolve 0.25 g ZrCl4 in 10 mL N,N-dimethylformamide and 2 mL hydrochloric acid, and stir at 400 rpm for 15 min.
[0024] Preparation of organic ligand solution: 0.268 g of 2-aminoterephthalic acid was dissolved in 20 mL of N,N-dimethylformamide and stirred at 400 rpm for 15 min.
[0025] Preparation of polydimethoxysiloxane (PDMS) solution: Dissolve 1 g PDMS (as main agent) and 0.1 g PDMS (as curing agent) in 30-50 mL n-hexane and stir at 400 rpm for 10 min.
[0026] First, 0.14 g of cellulose paper was immersed in 12 mL of zirconium ion solution, stirred at 400 rpm for 10 min, and sonicated at 400 kHz for 20 min. Then, 20 mL of organic ligand solution was added to the above solution, stirred at 400 rpm to 80 °C, and the mixture was heated at 80 °C for 3 h. The resulting composite paper was washed three times each with N,N-dimethylformamide and anhydrous ethanol, and dried at 60 °C for 12 h to obtain MOFs-modified cellulose paper. Finally, the obtained MOFs-modified cellulose paper was immersed in 50 mL of PDMS solution for 10 min and dried at 80 °C for 3 h to obtain the PDMS-functionalized MOFs-modified superhydrophobic paper.
[0027] Example 2 Preparation of zirconium ion solution: 1.25 g ZrCl4 was dissolved in 50 mL N,N-dimethylformamide and 10 mL hydrochloric acid, and stirred at 400 rpm for 15 min.
[0028] Preparation of organic ligand solution: 1.34 g of 2-aminoterephthalic acid was dissolved in 100 mL of N,N-dimethylformamide and stirred at 400 rpm for 15 min.
[0029] Preparation of PDMS solution: Dissolve 1 g PDMS (as main agent) and 0.1 g PDMS (as curing agent) in 30 mL n-hexane and stir at 400 rpm for 10 min.
[0030] First, 1.55 g of cellulose paper was immersed in 60 mL of zirconium ion solution, stirred at 400 rpm for 10 min, and sonicated at 400 kHz for 20 min. Then, 100 mL of organic ligand solution was added to the above solution, stirred at 400 rpm to 80 °C, and the mixture was heated at 80 °C for 3 h. The resulting composite paper was washed three times each with N,N-dimethylformamide and anhydrous ethanol, and dried at 60 °C for 12 h to obtain MOFs-modified cellulose paper. Finally, the obtained MOFs-modified cellulose paper was immersed in 30 mL of PDMS solution for 10 min and dried at 80 °C for 2 h to obtain the PDMS-functionalized MOFs-modified superhydrophobic paper.
[0031] Performance testing (1) Scanning electron microscopy test The morphology of the samples was studied using a field emission scanning electron microscope (FE-SEM, Regulus 8220, Japan). Figure 1 (a) The results showed that the fiber surface of pure cellulose paper was smooth and free of adhesion; Figure 1 (b) The results showed that a large number of MOFs were distributed on the fiber surface of MOF-modified cellulose paper; Figure 1 (c) The results show that a layer of PDMS film is uniformly distributed on the fiber surface of the PDMS-functionalized MOFs-modified composite paper.
[0032] (2) Contact angle test The water contact angle of the sample surface (3 μL water droplet) was measured using an optical contact angle meter (Attension Theta Flex, Biolin Scientific, Finland). Figure 2 (a) and Figure 2 (b) shows that both pure fiber paper and MOF-modified cellulose paper have a contact angle of 0° and no hydrophobic effect; Figure 2 (c) shows that the PDMS-functionalized MOFs-modified composite paper prepared in Example 1 has a contact angle of 162°, achieving a superhydrophobic effect.
[0033] (3) Anti-fouling and self-cleaning properties Antifouling performance was tested using methylene blue solution as a model pollutant. Figure 3 (a) and (b) are the stain resistance test results for cellulose paper and MOF-modified cellulose paper, respectively. The results show that after immersing both in methylene blue solution and removing them, blue contaminants were present on the surface of the paper. Figure 3 (c) is a stain resistance test diagram of the PDMS-functionalized MOFs-modified hydrophobic paper prepared in Example 1. The results show that the surface of the superhydrophobic paper is dry and leaves no trace after being removed from the methylene blue aqueous solution.
[0034] In addition, self-cleaning performance was tested using methylene blue powder as a model contaminant. The sample was placed at an angle in a glass dish, then methylene blue powder was placed on the surface of the sample, and the sample was rinsed with a stream of water. Figure 4 (a) and (b) are test results of the self-cleaning properties of cellulose paper and MOF-modified cellulose paper, respectively. The results show that a large number of blue marks are present on the surface of both. Figure 4 (c) is a test diagram of the self-cleaning performance of the PDMS-functionalized MOFs-modified hydrophobic paper prepared in Example 1. The results show that when water comes into contact with the superhydrophobic paper, the methylene blue powder is immediately washed away, leaving no trace on its surface.
[0035] (4) Oil-water separation performance The oil-water separation experiment was conducted under the influence of gravity. Figure 5 This is a schematic diagram of the oil-water separation process for the fluorinated MOFs-modified hydrophobic paper prepared in Example 1. Before separation, stable oil-water mixtures were prepared by mixing deionized water with oils (dichloromethane, carbon tetrachloride, toluene, petroleum ether, n-hexane, and kerosene) at a volume ratio of 1:1, resulting in six different oil-water mixtures. The specific separation process was as follows: 5 mL of the oil-water mixture was slowly poured onto a paper funnel. The oil quickly permeated through the paper, while the water was repelled. The remaining water in the funnel was collected. The oil-water separation efficiency was calculated as (m1 / m0) × 100%, where m0 is the weight of the original water before separation, and m1 is the weight of the water after separation.
[0036] like Figure 6 As shown, the superhydrophobic paper has a separation efficiency of over 98% for all six oil / water mixtures, demonstrating excellent oil-water separation performance.
[0037] Table 1 shows the comparison results of the average oil-water separation efficiency between the PDMS functionalized MOFs modified superhydrophobic paper prepared in Example 1 and the existing superhydrophobic paper in the prior art.
[0038] Table 1. Comparison of oil-water separation efficiency
[0039] The above description merely illustrates several embodiments of the present invention and should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make modifications, substitutions, and improvements without departing from the concept and scope of the present invention, and these all fall within the protection scope of the present invention. Therefore, the patent protection scope of the present invention should be determined by the described claims.
Claims
1. A method for preparing a PDMS functionalized MOFs modified superhydrophobic paper, characterized in that, The preparation method adopts the following steps: (1) stirring and ultrasonicating the cellulose paper in a zirconium ion solution; (2) adding an organic ligand solution to the solution obtained in step (1) to obtain MOFs modified cellulose paper; (3) immersing the MOFs modified cellulose paper obtained in step (2) in a polydimethylsiloxane (PDMS) solution to obtain the super-hydrophobic paper.
2. The production method according to claim 1, characterized by, In step (1), the cellulose paper is made from cotton pulp, having a basis weight of 80 g / m 2 ; The zirconium ion solution is prepared by the following steps: dissolving 0.25-1.25 g ZrCl4 in 10-50 mL N, N-dimethylformamide and 2-10 mL hydrochloric acid, and stirring at 400-500 rpm for 15-20 min; The mass-volume ratio of the cellulose paper and the zirconium ion solution is (0.14-1.55) g:(12-60) mL.
3. The preparation method according to claim 2, characterized in that, The concentration of the hydrochloric acid is 36%-37%.
4. The production method according to claim 1, characterized by, In step (2), the organic ligand solution is prepared by the following steps: dissolving 0.268-1.34 g 2-amino terephthalic acid in 20-100 mL N, N-dimethylformamide, and stirring at 400 rpm for 15 min; The mass-volume ratio of the cellulose paper and the organic ligand solution is (0.14-1.55) g:(20-100) mL.
5. The preparation method according to claim 1, characterized in that, In step (2), after adding the organic ligand solution, stirring, heating, washing and drying are further needed.
6. The production method according to claim 5, characterized by The stirring rate is 400-500 rpm, and the stirring is performed to 80-100℃; The heating temperature is 80-100℃, and the heating time is 3-12 h; The washing mode is washing with N, N-dimethylformamide and anhydrous ethanol for 3 times respectively; The drying temperature is 45-60℃, and the drying time is 12-24 h.
7. The production method according to claim 1, characterized by, In step (3), the PDMS solution is prepared by the following steps: dissolving 1 g PDMS (as a main agent) and 0.1 g PDMS (as a curing agent) in 30-50 mL n-hexane, and stirring at 400 rpm for 10 min; The mass-volume ratio of the cellulose paper in step (1) and the PDMS solution in step (3) is (0.14-1.55) g:(30-50) mL.
8. The preparation method according to claim 1, characterized in that, In step (3), the immersion time is 10-15 min; After the immersion, drying is further needed; the drying temperature is 80-85℃, and the drying time is 2-3 h.
9. The PDMS functionalized MOFs modified super-hydrophobic paper prepared by the method of claim 1.
10. The PDMS functionalized MOFs modified superhydrophobic paper prepared by the method of claim 1 and / or the use of the PDMS functionalized MOFs modified superhydrophobic paper of claim 9, characterized in that, The super-hydrophobic paper is used in the fields of transportation packaging, waterproof and moisture-proof protection, and cleaning of marine oil spills.