Preparation method of stripping-state zirconium phosphate-based hydrophobic modified nano-composite oil absorption film

Abstract

The invention discloses a preparation method of an exfoliated zirconium phosphate-based hydrophobic modified nano-composite oil absorption film, which comprises the following steps: carrying out intercalation treatment on alpha-zirconium phosphate by using 3-amino-1-propanol as a guest molecule to obtain hydroxylated intercalated zirconium phosphate; through ring-opening reaction of hydroxyl and epoxy group, grafting dodecyl glycidyl ether on the surface and between layers of intercalated zirconium phosphate to obtain hydrophobic modified exfoliated zirconium phosphate; the preparation method comprises the following steps: adding glutaraldehyde into a hydrophobic modified stripping state zirconium phosphate and polyvinylidene fluoride system, fully stirring, blade-coating to form a film, and immersing into an acid solution for cleaning to obtain the stripping state zirconium phosphate-based hydrophobic modified nano composite oil absorption film. The oil-water separation performance of the zirconium phosphate is effectively improved, and the problem that the zirconium phosphate is difficult to separate and recycle is solved.

Description

Technical Field

[0001] The invention relates to the technical field of aerogels, and in particular to a method for preparing a peeled zirconium phosphate-based hydrophobically 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 hydrophilicity of zirconium phosphate causes it to inevitably absorb water during the application process, which significantly weakens its oil absorption capacity. Therefore, it is particularly important to implement effective hydrophobic treatment on zirconium phosphate. Unfortunately, most of the current hydrophobic treatment methods are limited to simply coating the surface of zirconium phosphate with hydrophobic substances, which is easy to cause the hydrophobic layer to fall off; or try to graft hydrophobic modifiers to the surface or edge of the zirconium phosphate layer, while the interlayer region remains unmodified and hydrophilic. More importantly, due to the failure to achieve effective peeling, 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 can be evenly dispersed in the oil-water mixture. This highly dispersed state makes it difficult to effectively separate and recover zirconium phosphate particles through 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 they need to be solved by effective methods. Summary of the invention

[0003] In view of the above-mentioned defects in the prior art, the present invention provides a method for preparing a peeled zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing membrane, which solves the problem that the hydrophobic modification of zirconium phosphate in the past easily causes the hydrophobic layer to fall off and it is difficult to utilize the advantage of the large specific surface area of ​​zirconium phosphate, and at the same time solves the problem that zirconium phosphate is not easy to separate and recover.

[0004] The technical solution of the present invention is as follows: A method for preparing a peeled zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing film comprises the following steps: (1) Using 3-amino-1-propanol as a guest molecule, α-zirconium phosphate was intercalated to obtain hydroxylated intercalated zirconium phosphate; (2) Through the ring-opening reaction of hydroxyl and epoxy groups, dodecyl glycidyl ether is grafted on the surface and interlayer of the intercalated zirconium phosphate to obtain a hydrophobically modified exfoliated zirconium phosphate; (3) Add glutaraldehyde to the hydrophobically modified exfoliated zirconium phosphate and polyvinylidene fluoride system, stir thoroughly, apply the film by scraping, and immerse in acid solution for cleaning to obtain an exfoliated zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing membrane.

[0005] Furthermore, the step (1) specifically comprises ultrasonically dispersing α-zirconium phosphate in deionized water, then slowly dropping an aqueous solution of 3-amino-1-propanol, performing an intercalation reaction, and then filtering, washing, and drying.

[0006] Furthermore, 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.

[0007] Furthermore, the intercalation reaction in step (1) is carried out under the action of 40-60 kHz ultrasonic waves for 5-7 hours.

[0008] Furthermore, the step (2) specifically comprises ultrasonically dispersing the prepared hydroxylated intercalated zirconium phosphate in an ethanol solution of dodecyl glycidyl ether, adding a catalyst, performing stripping and hydrophobic modification, filtering, washing and drying, and the catalyst is one of formic acid and acetic acid.

[0009] Furthermore, in the step (2), the usage ratio of hydroxylated intercalated zirconium phosphate, dodecyl glycidyl ether and catalyst is 1 g: (1-2) mL: (0.04-0.08) g.

[0010] Furthermore, in step (2), the stripping and hydrophobic modification are carried out under the action of 100-160 kHz ultrasonic waves for 6-8 hours.

[0011] Furthermore, the step (3) specifically comprises ultrasonically dispersing the prepared hydrophobically modified exfoliated zirconium phosphate in polyvinylidene fluoride. N , N -dimethylformamide solution, add glutaraldehyde into the system, continue stirring at room temperature for 20 to 30 hours to obtain a homogeneous casting solution, and after degassing, apply the film by scraping and immerse in acid solution to crosslink and N , N -Dimethylformyl is removed, washed and dried to obtain a stripped zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing membrane.

[0012] Furthermore, in step (3), the hydrophobically modified peeled zirconium phosphate, polyvinylidene fluoride, N , N -The dosage ratio of dimethylformamide solution and glutaraldehyde is 1g: (8-16)g: (100-250)mL: (1-3)g.

[0013] Furthermore, in step (3), the crosslinking between the nanofillers and N , N The removal of -dimethylformyl is specifically performed by immersing the film-forming sample in an acid solution at 40-60°C for 20-30 hours, and replacing the acid solution every 3-5 hours, wherein the acid solution is a hydrochloric acid aqueous solution with a concentration of 1-2 mol / L.

[0014] The present invention first uses 3-amino-1-propanol as a guest molecule to perform intercalation treatment on zirconium phosphate, and simultaneously introduces hydroxyl groups on its surface and interlayer. Subsequently, through the ring-opening reaction of hydroxyl groups and epoxy groups, dodecyl glycidyl ether is modified on the surface and interlayer of zirconium phosphate, and along with the long chain insertion of dodecyl glycidyl ether, not only the zirconium phosphate sheet is peeled off, but also the hydrophobic lipophilicity of zirconium phosphate is effectively improved. Finally, glutaraldehyde is added to the hydrophobically modified peeled zirconium phosphate and polyvinylidene fluoride system, and film coating is performed after sufficient mixing, and the film is immersed in a hydrochloric acid aqueous solution, and the new hydroxyl groups generated by the ring-opening reaction of peeling the zirconium phosphate surface are used as cross-linking active points, glutaraldehyde is used as a cross-linking agent, and cross-linking modification between nano-fillers is performed while removing the solvent, thereby obtaining a nano-composite film with excellent hydrophobic lipophilic properties and durability.

[0015] The advantages of the present invention compared with the prior art are: (1) The present invention constructs a micro-nano multi-level structure with the help of exfoliated zirconium phosphate, and grafts the hydrophobic modifier to each surface of the zirconium phosphate through stable covalent bonds. At the same time, the hydrophobic resin matrix is ​​firmly coated on the surface of the filler through effective cross-linking between the fillers, which effectively solves the problem of poor hydrophobic modification effect of zirconium phosphate and easy detachment of the hydrophobic layer.

[0016] (2) The present invention firmly covalently cross-links the exfoliated zirconium phosphate in the resin matrix, which not only effectively improves the durability of the composite membrane, but also effectively avoids the problem of the difficulty of recycling and reusing the zirconium phosphate powder in water.

[0017] (3) The composite membrane prepared by the present invention not only has excellent hydrophobic properties, but also can fully hydrophobically modify the combined and synergistic effect of the peeled zirconium phosphate and poly(vinylidene fluoride) in oil absorption performance. Therefore, the composite membrane has excellent oil-water separation ability and achieves a significant improvement in oil absorption performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 This is the SEM image of the original α-zirconium phosphate.

[0019] Figure 2 This is the SEM image of the exfoliated zirconium phosphate obtained in Example 1.

[0020] Figure 3 This is the SEM image of the peeled zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing membrane obtained in Example 1.

[0021] Figure 4 The adsorption amount of engine oil by the stripped zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing film prepared in Example 1 changes with the number of cycles.

[0022] Figure 5The contact angle of the peeled zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing film prepared in Example 1 to water changes with the number of cycles. DETAILED DESCRIPTION

[0023] The present invention will be further described below in conjunction with the embodiments, but are not intended to limit the present invention.

[0024] Example 1

[0025] A method for preparing a peeled zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing film comprises the following steps: (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 ultrasound, the intercalation reaction was carried out for 7 h. The hydroxylated intercalated zirconium phosphate was filtered, washed, and dried. (2) 1 mL of dodecyl glycidyl ether was stirred and dissolved in ethanol, and then 1 g of the prepared hydroxylated intercalated zirconium phosphate was added and dispersed evenly by ultrasonication. 0.04 g of formic acid was added and reacted under 100 kHz ultrasonication for 8 h. The hydrophobically modified exfoliated zirconium phosphate was obtained by filtration, washing and drying. The SEM image of the hydrophobically modified exfoliated zirconium phosphate is shown in FIG. Figure 2 As shown, it can be seen that the zirconium phosphate has been effectively peeled off, the stacking phenomenon has been greatly reduced, and it has spread out on the substrate surface in the form of thin sheets; (3) Heat and dissolve 8g of polyvinylidene fluoride in 100ml of N , N -dimethylformamide solution, add 1g of the prepared hydrophobically modified exfoliated zirconium phosphate, ultrasonically disperse it evenly, add 1g of glutaraldehyde to the system, stir it continuously at room temperature for 20h to obtain a homogeneous casting solution, degas, and then apply it on a glass plate to form a film. The film-forming sample is immersed in a 40°C, 1mol / L hydrochloric acid aqueous solution for 30h, and the hydrochloric acid aqueous solution is replaced every 5h, washed and dried to obtain an exfoliated zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing film, and its SEM picture is shown as follows Figure 3 As shown, it can be seen that due to N,N The removal of dimethylformamide resulted in a membrane with a rich pore structure.

[0026] The relevant performance experiments of the peeled zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing membrane prepared in Example 1 are as follows: 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 water was dripped on the sample surface with a syringe. The amount of water added was 5 μl. Five different positions of each sample were measured and the average value was taken. The results are listed in Table 1.

[0027] Oil absorption capacity test: First, the sample was placed in a 60°C oven for 2 hours for drying and then weighed. The initial weight was recorded as M 0 The sample was then placed in a mixture of engine oil and water. After 15 minutes, the sample was taken out and placed on a metal filter. After 3 minutes of static dripping, the sample was placed in a 60°C oven for drying for 4 hours and weighed. The weight was 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.

[0028] .

[0029] Reusability: Mechanical extrusion is used to squeeze out the oil adsorbed by the impregnated sample. Each oil-water separation and each extrusion is regarded as one cycle. The changes in the sample water contact angle and oil absorption capacity with the number of extrusions are recorded to determine the reusability of the sample. The results of Example 1 are shown in Figure 4 and Figure 5 As shown in the figure, it can be seen that with the increase in the number of cycles, the prepared peeled zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing membrane only shows a slight decrease in oil absorption and water contact angle, and still maintains excellent oil absorption capacity and excellent hydrophobic properties. It shows that the modification technology adopted by the present 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.

[0030] Example 2

[0031] A method for preparing a peeled zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing film comprises the following steps: (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 an aqueous solution of 3-amino-1-propanol with a concentration of 15 mg / mL was slowly added dropwise. Under the action of 50 kHz ultrasonic waves, the intercalation reaction was carried out for 6 h. The hydroxylated intercalated zirconium phosphate was filtered, washed, and dried. (2) 1.5 mL of dodecyl glycidyl ether was stirred and dissolved in ethanol, and then 1 g of the prepared hydroxylated intercalated zirconium phosphate was added, and ultrasonic dispersion was performed uniformly. 0.06 g of acetic acid was added, and the mixture was reacted under 130 kHz ultrasonic wave for 7 h. The mixture was filtered, washed, and dried to obtain the hydrophobically modified exfoliated zirconium phosphate. (3) Heat and dissolve 12g of polyvinylidene fluoride in 175ml of N , N-dimethylformamide solution, add 1g of the prepared hydrophobically modified exfoliated zirconium phosphate, ultrasonically disperse it evenly, add 1.5g of glutaraldehyde into the system, stir it continuously at room temperature for 25h to obtain a homogeneous casting solution, degas, and then apply it on a glass plate to form a film. The film-forming sample is immersed in a 50°C, 1.5mol / L hydrochloric acid aqueous solution for 25h, and the hydrochloric acid aqueous solution is replaced every 4h, washed and dried to obtain an exfoliated zirconium phosphate-based hydrophobically modified nano-composite oil-absorbing film, and its water contact angle and oil absorption capacity are measured according to the relevant performance experiment of the product in Example 1, and the results are listed in Table 1.

[0032] Example 3

[0033] A method for preparing a peeled zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing film comprises the following steps: (1) 1 g of α-zirconium phosphate (13772-29-7, Shanghai Aladdin Reagent Co., Ltd.) was ultrasonically dispersed in deionized water, and then 50 mL of an aqueous solution of 3-amino-1-propanol with a concentration of 18 mg / mL was slowly added dropwise. Under the action of 60 kHz ultrasound, the intercalation reaction was carried out for 5 h. The hydroxylated intercalated zirconium phosphate was filtered, washed, and dried. (2) 2 mL of dodecyl glycidyl ether was stirred and dissolved in ethanol, and then 1 g of the prepared hydroxylated intercalated zirconium phosphate was added, and ultrasonic dispersion was uniformly performed. 0.08 g of acetic acid was added, and the mixture was reacted under 160 kHz ultrasonic wave for 6 h. The mixture was filtered, washed, and dried to obtain the hydrophobically modified exfoliated zirconium phosphate. (3) Heat and dissolve 16g of polyvinylidene fluoride in 250ml of N , N -dimethylformamide solution, add 1g of the prepared hydrophobically modified exfoliated zirconium phosphate, ultrasonically disperse it evenly, add 3g of glutaraldehyde into the system, stir it continuously at room temperature for 30h to obtain a homogeneous casting solution, degas, and then apply it on a glass plate to form a film, soak the film-forming sample in a 60°C, 2mol / L hydrochloric acid aqueous solution for 20h, and change the hydrochloric acid aqueous solution every 3h, wash and dry to obtain an exfoliated zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing film, the water contact angle and oil absorption capacity of which are measured according to the relevant performance experiment of the product in Example 1, and the results are listed in Table 1.

[0034] Comparative Example 1 Heat and dissolve 8g of polyvinylidene fluoride in 100ml of N , N-dimethylformamide solution, add 1g of original α-zirconium phosphate (13772-29-7, Shanghai Aladdin Reagent Co., Ltd.), ultrasonically disperse evenly, add 1g of glutaraldehyde to the system, and continue stirring at room temperature for 20h to obtain a homogeneous casting solution. After degassing, it is coated on a glass plate to form a film. The film-forming sample is immersed in a 40°C, 1mol / L hydrochloric acid aqueous solution for 30h, and the hydrochloric acid aqueous solution is replaced every 5h. The composite oil-absorbing film is washed and dried. The water contact angle and oil absorption capacity of the composite oil-absorbing film are measured according to the relevant performance experiment of the product in Example 1. The results are listed in Table 1.

[0035] Comparative Example 2 Heat and dissolve 8g of polyvinylidene fluoride in 100ml of N , N -dimethylformamide solution, add 1g of hydrophobically modified exfoliated zirconium phosphate (prepared according to steps (1) and (2) in Example 1), disperse evenly by ultrasonication, and continue stirring at room temperature for 20h to obtain a homogeneous casting solution. After degassing, the solution is scraped on a glass plate to form a film, and dried to obtain a composite oil-absorbing film. The water contact angle and oil absorption capacity of the composite oil-absorbing film are measured according to the relevant performance experiment of the product in Example 1. The results are listed in Table 1.

[0036] Table 1 Water contact angle and adsorption amount of engine oil of the oil absorption films prepared in Examples 1-3 and Comparative Examples 1-2

[0037] It can be seen from the results that the peeled zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing membrane prepared by the present invention not only has excellent hydrophobic properties, but also can achieve double enhancement of the oil absorption performance of the hydrophobically modified peeled zirconium phosphate and poly(divinylidene fluoride), and synergistic optimization. Therefore, the peeled zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing membrane prepared in the embodiment has excellent oil-water separation ability, and the adsorption capacity of the engine oil can reach up to 15.6 g / g.

[0038] In contrast, in Comparative Example 1, the zirconium phosphate was not effectively stripped and hydrophobically modified; in Comparative Example 2, although the zirconium phosphate was effectively stripped and hydrophobically modified, no effective crosslinking was performed, which reduced the interfacial bonding force between the filler and the matrix, and failed to fully exert the synergistic effect between the filler and the matrix. Therefore, the composite membranes prepared in these two comparative examples cannot be compared with the stripped zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing membrane obtained in the examples in terms of hydrophobicity and synergistic effect, which directly leads to a significant decrease in their hydrophobicity and oil adsorption.

Claims

1. A method for preparing a peeled zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing film, characterized in that: The following steps are involved: (1) Using 3-amino-1-propanol as a guest molecule, α-zirconium phosphate was intercalated to obtain hydroxylated intercalated zirconium phosphate; (2) Through the ring-opening reaction of hydroxyl and epoxy groups, dodecyl glycidyl ether is grafted on the surface and interlayer of the intercalated zirconium phosphate to obtain a hydrophobically modified exfoliated zirconium phosphate; (3) Add glutaraldehyde to the hydrophobically modified exfoliated zirconium phosphate and polyvinylidene fluoride system, stir thoroughly, apply the film by scraping, and immerse in acid solution for cleaning to obtain an exfoliated zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing membrane.

2. The method for preparing the peeled zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing film according to claim 1, characterized in that: The step (1) specifically comprises ultrasonically dispersing α-zirconium phosphate in deionized water, then slowly dropping an aqueous solution of 3-amino-1-propanol, performing an intercalation reaction, and then filtering, washing, and drying.

3. The method for preparing the peeled zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing film according to claim 2, characterized in that: In the 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 method for preparing the peeled zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing film according to claim 2, characterized in that: The intercalation reaction in step (1) is carried out under the action of 40-60 kHz ultrasonic waves for 5-7 hours.

5. The method for preparing the peeled zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing film according to claim 1, characterized in that: The step (2) specifically comprises ultrasonically dispersing the prepared hydroxylated intercalated zirconium phosphate in an ethanol solution of dodecyl glycidyl ether, adding a catalyst, performing stripping and hydrophobic modification, filtering, washing and drying, wherein the catalyst is one of formic acid and acetic acid.

6. The method for preparing the peeled zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing film according to claim 5, characterized in that: In the step (2), the usage ratio of hydroxylated intercalated zirconium phosphate, dodecyl glycidyl ether and catalyst is 1 g: (1-2) mL: (0.04-0.08) g.

7. The method for preparing the peeled zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing film according to claim 5, characterized in that: In the step (2), the stripping and hydrophobic modification are carried out under the action of 100-160 kHz ultrasonic waves for 6-8 hours.

8. The method for preparing the peeled zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing film according to claim 1, characterized in that: The step (3) specifically comprises ultrasonically dispersing the prepared hydrophobically modified exfoliated zirconium phosphate in polyvinylidene fluoride. N , N -dimethylformamide solution, add glutaraldehyde into the system, continue stirring at room temperature for 20 to 30 hours to obtain a homogeneous casting solution, and after degassing, apply the film by scraping and immerse in acid solution to crosslink and N , N -Dimethylformyl is removed, washed and dried to obtain a stripped zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing membrane.

9. The method for preparing the peeled zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing film according to claim 8, characterized in that: In the step (3), the hydrophobically modified peeled zirconium phosphate, polyvinylidene fluoride, N , N -The dosage ratio of dimethylformamide solution and glutaraldehyde is 1g: (8-16)g: (100-250)mL: (1-3)g.

10. The method for preparing the peeled zirconium phosphate-based hydrophobically modified nanocomposite oil-absorbing film according to claim 8, characterized in that: In step (3), the crosslinking between the nanofillers and N , N The removal of -dimethylformyl is specifically performed by immersing the film-forming sample in an acid solution at 40-60°C for 20-30 hours, and replacing the acid solution every 3-5 hours, wherein the acid solution is a hydrochloric acid aqueous solution with a concentration of 1-2 mol / L.

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