Preparation method of exfoliated zirconium phosphate-based hydrophobic modified nano composite oil-absorbing film

Abstract

The invention discloses a method for preparing a peeled zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing film, comprising the following steps: using 3-amino-1-propanol as a guest molecule to intercalate α-zirconium phosphate to obtain a hydroxylated intercalated zirconium phosphate; grafting dodecyl glycidyl ether on the surface and between the intercalated zirconium phosphate through a ring-opening reaction between a hydroxyl group and an epoxy group to obtain a hydrophobically modified peeled zirconium phosphate; adding glutaraldehyde to a hydrophobically modified peeled zirconium phosphate and polyvinylidene fluoride system, fully stirring, scraping and forming a film, and immersing in an acid solution for cleaning to obtain a peeled zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing film. The invention effectively improves the oil-water separation performance of zirconium phosphate and solves the problem of its difficulty in separation and recovery.

Description

Technical Field

[0001] The present invention relates to the technical field of aerogels, and particularly to a preparation method of a exfoliated zirconium phosphate-based hydrophobic modified nano composite oil-absorbing film. Background Art

[0002] Zirconium phosphate has a large specific surface area and rich porous structure characteristics, and can be used in the field of oil-water separation. However, the inherent hydrophilic property of zirconium phosphate leads to inevitable water absorption during its application, which significantly weakens its oil absorption capacity. Therefore, it is particularly important to perform effective hydrophobic treatment on zirconium phosphate. Unfortunately, most of the current hydrophobic treatment methods are limited to simply coating hydrophobic substances on the surface of zirconium phosphate, which is prone to cause the problem of shedding of the hydrophobic layer; or attempting to graft hydrophobic modifiers onto the surface or edge of the zirconium phosphate lamellae, while the interlayer region remains unmodified and hydrophilic. More importantly, due to the failure to achieve effective exfoliation, the huge specific surface area advantage of zirconium phosphate cannot be fully utilized. On the other hand, the particles of zirconium phosphate powder are extremely fine and are extremely easy to be uniformly dispersed in the oil-water mixture. This highly dispersed state makes it difficult for zirconium phosphate particles to be effectively separated and recovered by conventional physical methods (such as filtration, precipitation, etc.). These problems together constitute a major obstacle to the application of zirconium phosphate in the field of oil-water separation and urgently need to be solved by effective methods. Summary of the Invention

[0003] Aiming at the above-mentioned defects of the prior art, the present invention provides a preparation method of a exfoliated zirconium phosphate-based hydrophobic modified nano composite oil-absorbing film, which solves the problems that the hydrophobic modification of zirconium phosphate in the past is prone to cause the shedding of the hydrophobic layer and it is difficult to utilize the large specific surface area advantage of zirconium phosphate, and at the same time solves the problem that zirconium phosphate is not easy to be separated and recovered.

[0004] The technical solution of the present invention is as follows: A preparation method of a exfoliated zirconium phosphate-based hydrophobic modified nano composite oil-absorbing film, comprising the following steps:

[0005] (1) Using 3-amino-1-propanol as a guest molecule, intercalating α-zirconium phosphate to obtain hydroxylated intercalated zirconium phosphate;

[0006] (2) Through the ring-opening reaction of hydroxyl groups and epoxy groups, grafting dodecyl glycidyl ether on the surface and between the layers of the intercalated zirconium phosphate to obtain hydrophobic modified exfoliated zirconium phosphate;

[0007] (3) Adding glutaraldehyde to the hydrophobic modified exfoliated zirconium phosphate and polyvinylidene fluoride system, fully stirring, scraping into a film, and immersing in acid solution for cleaning to obtain a exfoliated zirconium phosphate-based hydrophobic modified nano composite oil-absorbing film.

[0008] Further, step (1) specifically involves ultrasonically dispersing zirconium α-phosphate in deionized water, then slowly dropping an aqueous solution of 3-amino-1-propanol for an intercalation reaction, followed by suction filtration, washing, and drying.

[0009] Further, in step (1), the mass ratio of zirconium α-phosphate to 3-amino-1-propanol is 1:(0.7 - 0.9), and the concentration of the 3-amino-1-propanol aqueous solution is 12 - 18 mg / mL.

[0010] Further, in step (1), the intercalation reaction is carried out under ultrasonic waves of 40 - 60 kHz for 5 - 7 h.

[0011] Further, step (2) specifically involves ultrasonically dispersing the prepared hydroxylated intercalated zirconium phosphate in an ethanol solution of dodecyl glycidyl ether, adding a catalyst, and performing exfoliation and hydrophobic modification, followed by suction filtration, washing, and drying. The catalyst is one of formic acid and acetic acid.

[0012] Further, in step (2), the dosage ratio of hydroxylated intercalated zirconium phosphate, dodecyl glycidyl ether, and the catalyst is 1 g:(1 - 2) mL:(0.04 - 0.08) g.

[0013] Further, in step (2), the exfoliation and hydrophobic modification are carried out under ultrasonic waves of 100 - 160 kHz for 6 - 8 h.

[0014] Further, step (3) specifically involves ultrasonically dispersing the prepared hydrophobic modified exfoliated zirconium phosphate in a N , N N,N-dimethylformamide solution of polyvinylidene fluoride, adding glutaraldehyde to the system, continuously stirring at room temperature for 20 - 30 h to obtain a homogeneous casting solution, removing bubbles, scraping to form a film, and immersing it in an acid solution for crosslinking between the nano-fillers and N , N removing N,N-dimethylformamide, washing, and drying to obtain a hydrophobic modified nano-composite oil-absorbing film based on exfoliated zirconium phosphate.

[0015] Further, in step (3), the dosage ratio of hydrophobic modified exfoliated zirconium phosphate, polyvinylidene fluoride, N , N N,N-dimethylformamide solution, and glutaraldehyde is 1 g:(8 - 16) g:(100 - 250) mL:(1 - 3) g.

[0016] Further, in step (3), the crosslinking between the nano-fillers and N , NThe removal of -dimethylformamide specifically involves immersing the film-forming sample in an acid solution at 40 - 60 °C for 20 - 30 h, and changing the acid solution every 3 - 5 h. The acid solution is an aqueous hydrochloric acid solution with a concentration of 1 - 2 mol / L.

[0017] In this invention, 3-amino-1-propanol is first used as the guest molecule to intercalate zirconium phosphate, and hydroxyl groups are introduced on its surface and between the layers. Subsequently, through the ring-opening reaction of hydroxyl groups and epoxy groups, dodecyl glycidyl ether is modified on the surface and between the layers of zirconium phosphate. With the insertion of the long chain of dodecyl glycidyl ether, not only the zirconium phosphate lamellae are exfoliated, but also the hydrophobic and lipophilic properties of zirconium phosphate are effectively improved. Finally, glutaraldehyde is added to the hydrophobic modified exfoliated zirconium phosphate and polyvinylidene fluoride system. After thorough mixing, a film is formed, and the film is immersed in an aqueous hydrochloric acid solution. Using the newly generated hydroxyl groups on the zirconium phosphate surface from the ring-opening reaction as cross-linking active sites and glutaraldehyde as the cross-linking agent, cross-linking modification between the nano-fillers is carried out while removing the solvent, thus obtaining a nano-composite membrane with excellent hydrophobic and lipophilic properties and durability.

[0018] The advantages of this invention compared with the prior art are as follows:

[0019] (1) This invention constructs a micro-nano multi-level structure with the help of exfoliated zirconium phosphate, and covalently grafts the hydrophobic modifier tightly onto each surface of zirconium phosphate through stable covalent bonds. At the same time, the hydrophobic resin matrix is firmly coated on the filler surface through effective cross-linking between the fillers, effectively solving the problems of poor hydrophobic modification effect of zirconium phosphate and easy shedding of the hydrophobic layer.

[0020] (2) This invention firmly covalently cross-links the exfoliated zirconium phosphate into the resin matrix, not only effectively improving the durability of the composite membrane, but also effectively avoiding the problem that zirconium phosphate powder is difficult to recycle and reuse in water.

[0021] (3) The composite membrane prepared by this invention not only has excellent hydrophobic properties, but also can fully combine and synergistically enhance the oil absorption performance of the hydrophobic modified exfoliated zirconium phosphate and polyvinylidene fluoride. Therefore, this composite membrane has excellent oil-water separation ability and realizes a significant improvement in oil absorption performance. Description of the Drawings

[0022] Figure 1 It is the SEM image of the original α-zirconium phosphate.

[0023] Figure 2 It is the SEM image of the exfoliated zirconium phosphate obtained in Example 1.

[0024] Figure 3 It is the SEM image of the hydrophobic modified nano-composite oil-absorbing membrane based on the exfoliated zirconium phosphate obtained in Example 1.

[0025] Figure 4The adsorption amount of the exfoliated zirconium phosphate-based hydrophobic modified nano-composite oil-absorbing film prepared in Example 1 varies with the number of cycles for engine oil.

[0026] Figure 5 The contact angle of the exfoliated zirconium phosphate-based hydrophobic modified nano-composite oil-absorbing film prepared in Example 1 with water varies with the number of cycles. Detailed implementation manners

[0027] The present invention will be further described below in conjunction with embodiments, but it is not intended to limit the present invention.

[0028] Example 1

[0029] A preparation method of an exfoliated zirconium phosphate-based hydrophobic modified nano-composite oil-absorbing film includes the following steps:

[0030] (1) 1 g of α-zirconium phosphate (13772-29-7, Shanghai Aladdin Reagent Co., Ltd.) was ultrasonically dispersed in deionized water, and then 58 mL of an aqueous solution of 3-amino-1-propanol with a concentration of 12 mg / mL was slowly added dropwise. Under the action of 40 kHz ultrasonic waves, an intercalation reaction was carried out for 7 h, followed by suction filtration, washing, and drying to obtain hydroxylated intercalated zirconium phosphate;

[0031] (2) 1 mL of dodecyl glycidyl ether was stirred and dissolved in ethanol, then 1 g of the obtained hydroxylated intercalated zirconium phosphate was added, ultrasonically dispersed evenly, 0.04 g of formic acid was added, and the reaction was carried out for 8 h under the action of 100 kHz ultrasonic waves. After suction filtration, washing, and drying, hydrophobic modified exfoliated zirconium phosphate was obtained. Its SEM image is as Figure 2 shown. It can be seen that effective exfoliation of zirconium phosphate occurred, and the stacking phenomenon was greatly reduced, and it spread out in the form of thin flakes on the substrate surface;

[0032] (3) 8 g of polyvinylidene fluoride was heated and dissolved in 100 ml of N , N N,N-dimethylformamide solution, 1 g of the obtained hydrophobic modified exfoliated zirconium phosphate was added, ultrasonically dispersed evenly, 1 g of glutaraldehyde was added to the system, and continuous stirring was carried out at room temperature for 20 h to obtain a homogeneous casting solution. After degassing, it was cast into a film on a glass plate. The film sample was immersed in a hydrochloric acid aqueous solution with a concentration of 1 mol / L at 40 °C for 30 h, and the hydrochloric acid aqueous solution was changed every 5 h. After washing and drying, an exfoliated zirconium phosphate-based hydrophobic modified nano-composite oil-absorbing film was obtained. Its SEM image is as Figure 3 shown. It can be seen that the obtained film has a rich pore structure due to the removal of N,N N,N-dimethylformamide.

[0033] The relevant performance experiments of the exfoliated zirconium phosphate-based hydrophobic modified nano-composite oil-absorbing film prepared in Example 1 are as follows:

[0034] Water contact angle test: A contact angle tester (model SDC-350H) was used to characterize the hydrophobicity of the material. The sample was adhered to a glass slide and 5 μl of water was added to the sample surface using a syringe. Five different locations of each sample were measured and the average value was taken. The results are listed in Table 1.

[0035] Oil absorption capacity test: First, the sample was placed in a 60℃ oven for 2 hours and then weighed. The initial weight was recorded as M 0. Then place the sample in a mixture of engine oil and water. After 15 minutes, take out the sample and place it on a metal filter. After it has been allowed to drip for 3 minutes, place the sample in a 60°C oven and dry it for 4 hours. The weight is recorded as M t Each sample was measured three times and the average value was taken. The oil absorption capacity (AR) of the sample was calculated according to the following formula. The results are listed in Table 1.

[0036] .

[0037] Reusability: The oil adsorbed by the impregnated sample was squeezed out by mechanical squeezing. Each oil-water separation and each squeezing was regarded as one cycle. The changes of the sample water contact angle and oil absorption capacity with the squeezing times were recorded to judge the reusability of the sample. The results of Example 1 are shown in the figure. Figure 4 and Figure 5 As shown in the graph, with increasing cycles, the prepared peeled zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing membrane shows only a slight decrease in oil absorption and water contact angle, while maintaining its excellent oil absorption capacity and outstanding hydrophobic properties. This demonstrates that the modification technology employed in this invention effectively enhances the durability of the zirconium phosphate-based composite membrane. Specifically, the cross-linking treatment between fillers effectively improves the structural and performance stability of the composite membrane.

[0038] Example 2

[0039] A method for preparing a peeled zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing film comprises the following steps:

[0040] (1) 1 g of α-zirconium phosphate (13772-29-7, Shanghai Aladdin Reagent Co., Ltd.) was ultrasonically dispersed in deionized water, and then 53 mL of a 15 mg / mL aqueous solution of 3-amino-1-propanol was slowly added dropwise. Under the action of 50 kHz ultrasound, the intercalation reaction was carried out for 6 h. The mixture was filtered, washed, and dried to obtain hydroxylated intercalated zirconium phosphate.

[0041] (2) Stir and dissolve 1.5 mL of dodecyl glycidyl ether in ethanol, then add 1 g of the prepared hydroxylated intercalated zirconium phosphate, ultrasonically disperse it evenly, add 0.06 g of acetic acid, and react for 7 h under the action of 130 kHz ultrasonic waves. Filter, wash, and dry to obtain hydrophobically modified exfoliated zirconium phosphate;

[0042] (3) Heat and dissolve 12 g of polyvinylidene fluoride in 175 ml of N , N N,N-dimethylformamide solution, add 1 g of the prepared hydrophobically modified exfoliated zirconium phosphate, ultrasonically disperse it evenly, add 1.5 g of glutaraldehyde to the system, continuously stir at room temperature for 25 h to obtain a homogeneous casting solution. After degassing, scrape and form a film on a glass plate. Immerse the formed film sample in a hydrochloric acid aqueous solution at 50 °C with a concentration of 1.5 mol / L for 25 h, and change the hydrochloric acid aqueous solution every 4 h. Wash and dry to obtain an exfoliated zirconium phosphate-based hydrophobically modified nano composite oil-absorbing film. Its water contact angle and oil absorption capacity are measured according to the relevant performance experiments of the product in Example 1, and the results are listed in Table 1.

[0043] Example 3

[0044] A preparation method of an exfoliated zirconium phosphate-based hydrophobically modified nano composite oil-absorbing film, comprising the following steps:

[0045] (1) Ultrasonically disperse 1 g of α-zirconium phosphate (13772-29-7, Shanghai Aladdin Reagent Co., Ltd.) in deionized water, then slowly dropwise add 50 mL of an aqueous solution of 3-amino-1-propanol with a concentration of 18 mg / mL, and carry out an intercalation reaction for 5 h under the action of 60 kHz ultrasonic waves. Filter, wash, and dry to obtain hydroxylated intercalated zirconium phosphate;

[0046] (2) Stir and dissolve 2 mL of dodecyl glycidyl ether in ethanol, then add 1 g of the prepared hydroxylated intercalated zirconium phosphate, ultrasonically disperse it evenly, add 0.08 g of acetic acid, and react for 6 h under the action of 160 kHz ultrasonic waves. Filter, wash, and dry to obtain hydrophobically modified exfoliated zirconium phosphate;

[0047] (3) Heat and dissolve 16 g of polyvinylidene fluoride in 250 ml of N , NIn a solution of N,N-dimethylformamide, 1 g of the prepared hydrophobic modified exfoliated zirconium phosphate was added, and it was ultrasonically dispersed evenly. Then, 3 g of glutaraldehyde was added to the system, and it was continuously stirred at room temperature for 30 h to obtain a homogeneous casting solution. After degassing, it was cast into a film on a glass plate. The film sample was immersed in a hydrochloric acid aqueous solution at 60 °C with a concentration of 2 mol / L for 20 h, and the hydrochloric acid aqueous solution was changed every 3 h. After washing and drying, a hydrophobic modified nano-composite oil-absorbing film based on exfoliated zirconium phosphate was obtained. Its water contact angle and oil absorption capacity were measured according to the relevant performance experiments of the product in Example 1, and the results are listed in Table 1.

[0048] Comparative Example 1

[0049] 8 g of polyvinylidene fluoride was heated and dissolved in 100 ml of N , N -dimethylformamide solution, 1 g of raw α-zirconium phosphate (13772-29-7, Shanghai Aladdin Reagent Co., Ltd.) was added, and it was ultrasonically dispersed evenly. Then, 1 g of glutaraldehyde was added to the system, and it was continuously stirred at room temperature for 20 h to obtain a homogeneous casting solution. After degassing, it was cast into a film on a glass plate. The film sample was immersed in a hydrochloric acid aqueous solution at 40 °C with a concentration of 1 mol / L for 30 h, and the hydrochloric acid aqueous solution was changed every 5 h. After washing and drying, a composite oil-absorbing film was obtained. Its water contact angle and oil absorption capacity were measured according to the relevant performance experiments of the product in Example 1, and the results are listed in Table 1.

[0050] Comparative Example 2

[0051] 8 g of polyvinylidene fluoride was heated and dissolved in 100 ml of N , N -dimethylformamide solution, 1 g of hydrophobic modified exfoliated zirconium phosphate (prepared according to steps (1) and (2) in Example 1) was added, and it was ultrasonically dispersed evenly. Then, it was continuously stirred at room temperature for 20 h to obtain a homogeneous casting solution. After degassing, it was cast into a film on a glass plate and dried to obtain a composite oil-absorbing film. Its water contact angle and oil absorption capacity were measured according to the relevant performance experiments of the product in Example 1, and the results are listed in Table 1.

[0052] Table 1 Water contact angles and adsorption amounts of engine oil of the oil-absorbing films prepared in Examples 1-3 and Comparative Examples 1-2

[0053]

[0054] It can be seen from the results that the hydrophobic modified nano-composite oil-absorbing film based on exfoliated zirconium phosphate prepared by the present invention not only has excellent hydrophobic performance, but also can achieve double enhancement and synergistic optimization in the oil absorption performance of hydrophobic modified exfoliated zirconium phosphate and polyvinylidene fluoride. Therefore, the hydrophobic modified nano-composite oil-absorbing film based on exfoliated zirconium phosphate prepared in the examples has excellent oil-water separation ability, and the maximum adsorption capacity for engine oil can reach 15.6 g / g.

[0055] In contrast, in Comparative Example 1, zirconium phosphate was not effectively exfoliated and hydrophobically modified; in Comparative Example 2, although zirconium phosphate was effectively exfoliated and hydrophobically modified, effective crosslinking was not carried out, reducing the interfacial binding force between the filler and the matrix and unable to fully exert the synergistic effect between the filler and the matrix. Therefore, the composite membranes prepared in these two comparative examples cannot compare with the exfoliated zirconium phosphate-based hydrophobic modified nano composite oil-absorbing membrane obtained in the examples in terms of hydrophobicity and synergistic effect, which also directly led to a significant decrease in their hydrophobicity and the oil adsorption capacity for engine oil.

Claims

1. A preparation method of a stripped zirconium phosphate-based hydrophobic modified nano composite oil-absorbing film, characterized in that, It includes the following steps: (1) Using 3-amino-1-propanol as the guest molecule, intercalate α-zirconium phosphate to obtain hydroxylated intercalated zirconium phosphate; (2) Through the ring-opening reaction of hydroxyl group and epoxy group, graft dodecyl glycidyl ether on the surface and between layers of hydroxylated intercalated zirconium phosphate to obtain hydrophobically modified exfoliated zirconium phosphate; (3) Add glutaraldehyde to the hydrophobically modified exfoliated zirconium phosphate and polyvinylidene fluoride system, stir well, scrape to form a film, and immerse it in acid solution for cleaning to obtain a hydrophobically modified nano-composite oil-absorbing film based on exfoliated zirconium phosphate.

2. The preparation method of the exfoliated zirconium phosphate-based hydrophobic modified nano composite oil-absorbing film according to claim 1, characterized in that, Specifically, in step (1), α-zirconium phosphate is ultrasonically dispersed in deionized water, and then an aqueous solution of 3-amino-1-propanol is slowly added dropwise for intercalation reaction, followed by suction filtration, washing, and drying.

3. The preparation method of the exfoliated zirconium phosphate-based hydrophobic modified nano composite oil-absorbing film according to claim 2, characterized in that, In step (1), the mass ratio of α-zirconium phosphate to 3-amino-1-propanol is 1:(0.7 - 0.9), and the concentration of the 3-amino-1-propanol aqueous solution is 12 - 18 mg / mL.

4. The preparation method of the exfoliated zirconium phosphate-based hydrophobic modified nano-composite oil-absorbing film according to claim 2, characterized in that, In step (1), the intercalation reaction is carried out under the action of ultrasonic waves at 40 - 60 kHz for 5 - 7 h.

5. The preparation method of the exfoliated zirconium phosphate-based hydrophobic modified nano composite oil-absorbing film according to claim 1, characterized in that, Specifically, in step (2), the hydroxylated intercalated zirconium phosphate prepared in step (1) is ultrasonically dispersed in an ethanol solution of dodecyl glycidyl ether, and a catalyst is added for exfoliation and hydrophobic modification, followed by suction filtration, washing, and drying. The catalyst is one of formic acid and acetic acid.

6. The preparation method of the exfoliated zirconium phosphate-based hydrophobic modified nano composite oil-absorbing film according to claim 5, characterized in that, In step (2), the dosage ratio of hydroxylated intercalated zirconium phosphate, dodecyl glycidyl ether, and the catalyst is 1 g:(1 - 2) mL:(0.04 - 0.08) g.

7. The preparation method of the exfoliated zirconium phosphate-based hydrophobic modified nano composite oil-absorbing film according to claim 5, characterized in that, In step (2), the exfoliation and hydrophobic modification are carried out under the action of ultrasonic waves at 100 - 160 kHz for 6 - 8 h.

8. The preparation method of the exfoliated zirconium phosphate-based hydrophobic modified nano-composite oil-absorbing film according to claim 1, characterized in that, Step (3) specifically involves ultrasonically dispersing the prepared hydrophobically modified exfoliated zirconium phosphate in a N , N -dimethylformamide solution, adding glutaraldehyde to the system, continuously stirring at room temperature for 20 - 30 h to obtain a homogeneous casting solution, de-bubbling, scraping to form a film, and immersing it in an acid solution to carry out cross-linking between nano-fillers and N , N removal of dimethylformamide, washing, and drying to obtain a hydrophobically modified nano-composite oil-absorbing membrane based on exfoliated zirconium phosphate.

9. The preparation method of the exfoliated zirconium phosphate-based hydrophobic modified nano-composite oil-absorbing film according to claim 8, wherein, In the step (3), the dosage ratio of the hydrophobic modified exfoliated zirconium phosphate, polyvinylidene fluoride, N , N N,N-dimethylformamide solution and glutaraldehyde is 1 g: (8 - 16) g: (100 - 250) mL: (1 - 3) g.

10. The preparation method of the exfoliated zirconium phosphate-based hydrophobic modified nano composite oil-absorbing film according to claim 8, characterized in that, The crosslinking between the nano-fillers in the step (3) and N , N the removal of N,N-dimethylformamide are specifically carried out by immersing the film prepared by scraping in an acid solution at 40-60 °C for 20-30 h, and changing the acid solution every 3-5 h. The acid solution is an aqueous hydrochloric acid solution with a concentration of 1-2 mol / L.

Images