Universal polymer modified sponge hydrophobic material and preparation method thereof
By anchoring general-purpose polymers such as HDPE, PP, and ABS onto a melamine or polyurethane sponge skeleton, hydrophobic materials are prepared, solving the problems of complex preparation and low oil-water separation efficiency of existing materials, and achieving efficient and low-cost oil-water separation.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- CHINA PETROLEUM & CHEMICAL CORP
- Filing Date
- 2024-10-31
- Publication Date
- 2026-05-01
AI Technical Summary
Existing oil-absorbing porous materials have complex preparation processes, high costs, and low oil-water separation efficiency. Traditional materials have poor oil-water selectivity and slow oil absorption rates, making it difficult to meet the needs of emergency oil spill response.
Hydrophobic materials are prepared by repeatedly impregnating general-purpose polymer materials such as HDPE, PP, and ABS onto a melamine or polyurethane sponge skeleton. These materials are then used to achieve rapid and efficient oil-water separation by utilizing their strong hydrophobic and oleophilic properties.
The prepared hydrophobic material has an adsorption capacity of 80g/g-180g/g for oily substances, which is equivalent to 167 times its own weight. It has good acid and alkali resistance and recyclability, low cost and high mechanical strength, and is suitable for oil-water separation.
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Figure CN121949883A_ABST
Abstract
Description
A general-purpose polymer-modified hydrophobic sponge material and its preparation method Technical Field
[0001] This invention relates to the field of oil-water separation hydrophobic materials technology, specifically to a general-purpose polymer-modified sponge hydrophobic material and its preparation method. Background Technology
[0002] With the rapid development of offshore oil extraction and the increase in global crude oil trade, marine oil spills are occurring frequently, and oil pollution is becoming increasingly severe. To mitigate the environmental damage caused by oil spills, adsorption technology is often used for oil surface cleanup. Adsorption is a physical method that does not cause secondary pollution, has a high oil absorption rate, and most of the oil can be reused, aligning with the national policy of green and pollution-free development and representing the future direction of oil production.
[0003] Commonly used oil spill absorbent materials include: inorganic porous absorbent materials such as perlite, clay, and zeolite; natural organic materials such as wood fiber, straw, and sawdust; and synthetic absorbent materials such as polypropylene fiber felt, polyurethane foam, and polystyrene fiber. Because oil spills are prone to diffusion and volatilization, and easily emulsified by ocean waves, absorbent materials used for oil spill response must possess characteristics such as rapid oil absorption rate, high oil absorption ratio, and low water absorption rate. However, these traditional absorbent materials have poor oil-water selectivity, absorb water during the oil absorption process, and exhibit slow absorption rates and low efficiency for high-viscosity oils, thus limiting their application in oil spill emergencies.
[0004] Currently, many synthetic polymer materials are applied to oil-water separation materials. For example, Song Xiangning et al. (Preparation of silane-modified melamine sponge and its oil-water separation performance study [J]. Science Technology and Engineering, 2023, 23(08): 3552-3558) successfully prepared a hydrophobic and oleophilic sponge by coating the hydrolysate formed by the hydrolysis of methyltrimethoxysilane and dimethyldimethoxysilane onto melamine sponge through hydrogen bond condensation. The oil absorption capacity of the sponge for oil or organic reagents reached 47-60 times its own weight. Cao Yafei et al. (Urushiol and Fe3O4 Synergistic Superhydrophobic Modification of Melamine Sponge for High-Efficiency Oil-Water Separation [J]. Journal of Chemical Engineering of Chinese Universities, 2023, 37(05): 699-706) modified the surface of amphiphilic melamine sponge with nano Fe3O4 and urushiol by simple dip coating method. The modified urushiol-Fe3O4-urushiol melamine sponge material realizes the transformation of the sponge substrate from superhydrophilic to superoleophilic to superhydrophobic to superoleophilic, and the mass of organic solvents and oils absorbed is more than 21 times that of its own. Yin Ziting et al. (Study on Hydrophobic Modification of Polyurethane Sponge and Nonwoven Fabric by Interfacial Polymerization and Silane Coupling Method [J / OL]. Journal of Zhongkai University of Agriculture and Engineering, 1-15 [2024-07-24]) In order to achieve efficient oil-water separation, the interfacial polymerization method and silane coupling method were used to hydrophobically modify polyurethane sponge. First, a polymer is formed using trimesoyl chloride and polyethyleneimine, and then stearic acid is grafted onto a rough surface to obtain PU-IP-SA sponge. The PU-IP-SA sponge has a contact angle of 140°-143° and exhibits optimal absorption capacity for tea tree oil (45.1 times its own mass). However, the synthesis process of these synthetic polymers is relatively complex and costly, and due to the presence of hydrophilic groups, their oil absorption rate is relatively low.
[0005] CN111073031 discloses a method for preparing hydrophobically modified melamine sponge, comprising: impregnating melamine sponge with a hydrophobically modified solution; extruding the hydrophobically modified solution from the melamine sponge; and curing the melamine sponge under heating conditions to obtain the hydrophobically modified melamine sponge. The hydrophobically modified solution comprises nanoscale graphite particles, polymer monomers, initiators, crosslinking agents, surfactants, and water. However, this process requires control of polymerization reaction conditions and reactant ratios, is cumbersome, and expensive.
[0006] Therefore, in order to address the problems of complex preparation processes and low oil-water separation efficiency of traditional oil-absorbing porous materials, developing novel oil-absorbing porous materials and simple and efficient synthesis processes is an urgent issue that needs to be solved. Summary of the Invention
[0007] To address the aforementioned problems, the present invention aims to provide a general-purpose polymer-modified hydrophobic sponge material. Utilizing the strong hydrophobic and oleophilic properties of general-purpose polymer materials, the material is anchored onto the skeleton of melamine sponge or polyurethane sponge through repeated impregnation. The resulting hydrophobic material can achieve rapid and efficient oil-water separation, with an adsorption capacity for oily substances reaching 80g / g-180g / g, up to 167 times its own weight.
[0008] The technical solution of the present invention is as follows:
[0009] This invention provides a general-purpose polymer-modified sponge hydrophobic material, comprising a sponge and a general-purpose polymer anchored on the sponge. Based on the total weight of the hydrophobic material, the loading of the general-purpose polymer is 1-15% by weight, and the water contact angle of the hydrophobic material is 120-150°.
[0010] Furthermore, the general-purpose polymer includes at least one of HDPE (high-density polyethylene), PP (polypropylene), ABS (acrylonitrile-styrene-butadiene copolymer), polystyrene, and polyvinyl chloride.
[0011] Furthermore, the general polymer is selected from a combination of HDPE and PP or a combination of HDPE, PP and ABS.
[0012] Furthermore, in the combination of HDPE and PP, the mass ratio of HDPE to PP is 1:1.
[0013] Furthermore, in the combination of HDPE, PP and ABS, the mass ratio of HDPE, PP and ABS is 1:1:1.
[0014] Furthermore, the sponge includes at least one of melamine and polyurethane.
[0015] Furthermore, the sponge has a porosity of over 99%, a pore size of approximately 100 μm, and a cross-linked polymer backbone.
[0016] Furthermore, the density of the HDPE is from 0.941 to 0.960 g / cm³. 3 Its molecular weight is between 45,000 and 50,000.
[0017] Furthermore, the density of the PP is 0.90 to 0.96 g / cm³. 3 The molecular weight ranges from 5,000 to 200,000.
[0018] Furthermore, the density of the ABS is 1.04 to 1.06 g / cm³. 3 The molecular weight ranges from 30,000 to 1,500,000.
[0019] The present invention also provides a method for preparing the aforementioned hydrophobic sponge material, the method comprising the following steps:
[0020] Step S1: Dissolution of general polymers:
[0021] A general-purpose polymer is dissolved in a solvent to obtain a general-purpose polymer solution;
[0022] Step S2: Preparation of hydrophobic materials:
[0023] The general polymer solution obtained in step S1 is dipped onto a sponge and dried to obtain the hydrophobic material.
[0024] Further, in step S1, the ratio of the amount of the general polymer to the amount of the solvent is (0.1-1)g:100mL.
[0025] Further, in step S1, the solvent is toluene or xylene.
[0026] Furthermore, in step S1, the melting temperature is 100-130℃.
[0027] Further, in step S2, based on the total mass of the hydrophobic material, the loading of the general polymer is 1-15 wt%, preferably 3.5-12 wt%.
[0028] Furthermore, in step S2, the drying temperature is 100-150°C.
[0029] The superior effects of this invention are as follows:
[0030] (1) This invention utilizes porous melamine or polyurethane commercial sponges as a substrate, wherein the sponge itself possesses the characteristics of a porous superhydrophilic material and is capable of adsorbing water, oil, or organic solvents. By coating the rich pore structure of the sponge with hydrophobic polymers, the hydrophobic polymers are anchored to the sponge skeleton, thereby adjusting the sponge's properties from superhydrophilic to hydrophobic and oil-absorbing, thus preparing a hydrophobic material with high selectivity, good recyclability, and excellent absorption capacity.
[0031] (2) This invention replaces conventional synthetic polymers with inexpensive, hydrophobic, and oleophilic general-purpose polymers, reducing preparation difficulty and saving costs. The hydrophobic material prepared by this invention has an adsorption capacity of 80g / g-180g / g for oily substances, equivalent to 167 times its own weight. In addition, the material also exhibits good acid and alkali resistance, with a water contact angle of 135-150°C when immersed in an environment with a pH of 2-14, and it is recyclable, lightweight, and durable.
[0032] (3) The hydrophobic material maintains excellent superhydrophobicity and separation efficiency under different acid, alkali, and salt conditions, enabling continuous oil-water separation. These characteristics indicate that the hydrophobic material not only performs well in oil-water separation, but also improves performance while reducing preparation difficulty through low-cost universal polymer coating, demonstrating significant advantages in environmental friendliness and low cost.
[0033] (4) The hydrophobic material in this invention has excellent flexibility and mechanical strength, which provides a guarantee for the recycling of adsorbent materials and the subsequent squeezing and recovery of oil products. At the same time, it provides a new prospect for the development of environmentally friendly and low-cost advanced liquid-liquid separation or water treatment technologies. Attached Figure Description
[0034] Figure 1 is a SEM image of the general-purpose polymer-modified melamine sponge hydrophobic material prepared in Comparative Example 1 and Example 3 of the present invention.
[0035] Figure 2 shows the water contact angle of the general polymer-modified melamine sponge hydrophobic materials prepared in Comparative Example 1 and Examples 1-4 of this invention.
[0036] Figure 3 shows the water contact angle of the general-purpose polymer-modified melamine sponge hydrophobic material prepared in Example 3 of the present invention after soaking in different pH values for 12 hours.
[0037] Figure 4 shows the adsorption capacity of the general-purpose polymer-modified melamine sponge hydrophobic material prepared in Example 3 of the present invention for different oils.
[0038] Figure 5 shows the water contact angle results of the general polymer modified melamine sponge hydrophobic materials prepared in Examples 5-6 and Comparative Example 2 of the present invention.
[0039] Figure 6 shows the adsorption capacity of the general polymer-modified melamine sponge hydrophobic materials prepared in Examples 5-6 and Comparative Example 2 for different oils.
[0040] Figure 7 shows the adsorption capacity of the general-purpose polymer-modified polyurethane sponge hydrophobic material prepared in Example 7 of the present invention for different oils. Detailed Implementation
[0041] Preferred embodiments of the invention will now be described in more detail. While preferred embodiments of the invention are described below, it should be understood that the invention can be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that the invention will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
[0042] Example 1
[0043] This embodiment proposes a general-purpose polymer-modified melamine sponge hydrophobic material, consisting of HDPE-1, PP-1, and ABS-1. To physically anchor HDPE, PP, and ABS onto the melamine sponge skeleton, based on the total mass of the general-purpose polymer-modified melamine sponge hydrophobic material, the loading amounts of HDPE, PP, and ABS are 3.7 wt%, 3.8 wt%, and 3.9 wt%, respectively. The water contact angles of HDPE-1, PP-1, and ABS-1 are 120°, 128°, and 130°, respectively.
[0044] The preparation steps of the above-mentioned general polymer-modified melamine sponge hydrophobic material are as follows:
[0045] Step S1: Dissolve 0.5g HDPE in 200ml toluene and stir at 110℃ for 1h to obtain the first polymer solution;
[0046] Dissolve 0.5g of PP in 200ml of toluene and stir at 130℃ for 2h to obtain the second polymer solution;
[0047] Dissolve 0.5g of ABS in 200ml of toluene and stir at 150℃ for 3h to obtain a third polymer solution;
[0048] Step S2: The first polymer solution treated in step S1 is dipped into the sponge, and the dipped melamine sponge is placed in an oven and dried at 110°C for 1 hour to obtain the modified sponge. By repeating the dipping and drying once, the loading of the polymer solution on the melamine sponge is controlled to be 3.7% by weight.
[0049] The second polymer solution after step S1 was applied to the sponge, and the coated melamine sponge was placed in an oven and dried at 110°C for 1 hour to obtain the modified sponge. By repeating the impregnation and drying once, the loading of the polymer solution on the melamine sponge was controlled to be 3.8% by weight.
[0050] The third polymer solution after step S1 was applied to the sponge, and the coated melamine sponge was dried in an oven at 110°C for 1 hour to obtain the modified sponge. By repeating the impregnation and drying once, the loading of the polymer solution on the melamine sponge was controlled to be 3.9% by weight.
[0051] Example 2
[0052] This embodiment proposes a general-purpose polymer-modified melamine sponge hydrophobic material, HDPE-2, PP-2, and ABS-2. To physically anchor HDPE, PP, and ABS onto the melamine sponge skeleton, based on the total mass of the general-purpose polymer-modified melamine sponge hydrophobic material, the loading amounts of HDPE, PP, and ABS are 6.7 wt%, 5.2 wt%, and 5.7 wt%, respectively. The water contact angles of HDPE-2, PP-2, and ABS-2 are 128°, 133°, and 134°, respectively.
[0053] The preparation steps of the above-mentioned general polymer-modified melamine sponge hydrophobic material are as follows:
[0054] Step S1: Dissolve 0.5g HDPE in 200ml toluene and stir at 110℃ for 1h to obtain the first polymer solution;
[0055] Dissolve 0.5g of PP in 200ml of toluene and stir at 130℃ for 2h to obtain the second polymer solution;
[0056] Dissolve 0.5g of ABS in 200ml of toluene and stir at 150℃ for 3h to obtain a third polymer solution;
[0057] Step S2: The first polymer solution treated in step S1 is dipped into the sponge. The dipped melamine sponge is placed in an oven and dried at 110°C for 1 hour to obtain the modified sponge. By repeating the dipping and drying process twice, the loading of the polymer solution on the melamine sponge is controlled to be 6.7% by weight.
[0058] The second polymer solution after step S1 was applied to the sponge, and the coated melamine sponge was dried in an oven at 110°C for 1 hour to obtain the modified sponge. By repeating the impregnation and drying process twice, the loading amount of the polymer solution on the melamine sponge was controlled to be 5.2% by weight.
[0059] The third polymer solution after step S1 was applied to the sponge, and the coated melamine sponge was dried in an oven at 110°C for 1 hour to obtain the modified sponge. By repeating the impregnation and drying process twice, the loading of the melamine sponge with the polymer solution was controlled to be 5.7% by weight.
[0060] Example 3
[0061] This embodiment proposes a general-purpose polymer-modified melamine sponge hydrophobic material, consisting of HDPE-3, PP-3, and ABS-3. To physically anchor HDPE, PP, and ABS onto the melamine sponge skeleton, based on the total mass of the general-purpose polymer-modified melamine sponge hydrophobic material, the loading amounts of HDPE, PP, and ABS are 7.3 wt%, 7.5 wt%, and 7.7 wt%, respectively. The water contact angles of HDPE-3, PP-3, and ABS-3 are 135°, 137°, and 137°, respectively.
[0062] The preparation steps of the above-mentioned general-purpose polymer-modified melamine sponge hydrophobic material are as follows:
[0063] Step S1: Dissolve 0.5g HDPE in 200ml toluene and stir at 110℃ for 1h to obtain the first polymer solution;
[0064] Dissolve 0.5g of PP in 200ml of toluene and stir at 130℃ for 2h to obtain the second polymer solution;
[0065] Dissolve 0.5g of ABS in 200ml of toluene and stir at 150℃ for 3h to obtain a third polymer solution;
[0066] Step S2: The first polymer solution treated in step S1 is dipped into the sponge. The dipped melamine sponge is placed in an oven and dried at 110°C for 1 hour to obtain the modified sponge. By repeating the dipping and drying process 3 times, the loading of the polymer solution on the melamine sponge is controlled to be 7.3% by weight.
[0067] The second polymer solution after step S1 was applied to the sponge. The melamine sponge was then placed in an oven and dried at 110°C for 1 hour to obtain the modified sponge. By repeating the impregnation and drying process three times, the loading of the melamine sponge with the polymer solution was controlled to be 7.5% by weight.
[0068] The third polymer solution after step S1 was applied to the sponge, and the coated melamine sponge was dried in an oven at 110°C for 1 hour to obtain the modified sponge. By repeating the impregnation and drying process 3 times, the loading of the melamine sponge with the polymer solution was controlled to be 7.7% by weight.
[0069] Example 4
[0070] This embodiment proposes a general-purpose polymer-modified melamine sponge hydrophobic material, HDPE-4, PP-4, and ABS-4. To physically anchor HDPE, PP, and ABS onto the melamine sponge skeleton, based on the total mass of the general-purpose polymer-modified melamine sponge hydrophobic material, the loading amounts of HDPE, PP, and ABS are 10.7 wt%, 11.4 wt%, and 10.9 wt%, respectively. The water contact angles of HDPE-4, PP-4, and ABS-4 are 136°, 138°, and 138°, respectively.
[0071] The preparation steps of the above-mentioned general polymer-modified melamine sponge hydrophobic material are as follows:
[0072] Step S1: Dissolve 0.5g HDPE in 200ml toluene and stir at 110℃ for 1h to obtain the first polymer solution;
[0073] Dissolve 0.5g of PP in 200ml of toluene and stir at 130℃ for 2h to obtain the second polymer solution;
[0074] Dissolve 0.5g of ABS in 200ml of toluene and stir at 150℃ for 3h to obtain a third polymer solution;
[0075] Step S2: The first polymer solution treated in step S1 is dipped into the sponge. The dipped melamine sponge is placed in an oven and dried at 110°C for 1 hour to obtain the modified sponge. By repeating the dipping and drying process 5 times, the loading of the polymer solution on the melamine sponge is controlled to be 10.7% by weight.
[0076] The second polymer solution after step S1 was applied to the sponge. The melamine sponge was then dried in an oven at 110°C for 1 hour to obtain the modified sponge. By repeating the impregnation and drying process 5 times, the loading amount of the melamine sponge loaded with the polymer solution was controlled to be 11.4% by weight.
[0077] The third polymer solution after step S1 was applied to the sponge, and the coated melamine sponge was dried in an oven at 110°C for 1 hour to obtain the modified sponge. By repeating the impregnation and drying process 5 times, the loading of the melamine sponge with the polymer solution was controlled to be 10.9% by weight.
[0078] Example 5
[0079] This embodiment proposes a general-purpose polymer-modified melamine sponge hydrophobic material HDPE-PP. To physically anchor HDPE and PP onto the melamine sponge skeleton, based on the total mass of the general-purpose polymer-modified melamine sponge hydrophobic material, the total loading of HDPE and PP is 8.3% by weight, wherein the water contact angle of HDPE-PP is 139°.
[0080] The preparation steps of the above-mentioned general polymer-modified melamine sponge hydrophobic material are as follows:
[0081] Step S1: Dissolve 0.5g HDPE in 200ml toluene and stir at 110℃ for 1h to obtain the first polymer solution;
[0082] Dissolve 0.5g of PP in 200ml of toluene and stir at 130℃ for 2h to obtain the second polymer solution;
[0083] Step S2: The two polymer solutions treated in step S1 are dipped into the sponge. The dipped melamine sponge is placed in an oven and dried at 110°C for 1 hour to obtain the modified sponge. By repeating the dipping and drying process 5 times, the loading of the polymer solution on the melamine sponge is controlled to be 8.3% by weight.
[0084] Example 6
[0085] This embodiment proposes a general-purpose polymer-modified melamine sponge hydrophobic material HDPE-PP-ABS. To physically anchor HDPE, PP, and ABS onto the melamine sponge skeleton, based on the total mass of the general-purpose polymer-modified melamine sponge hydrophobic material, the total loading of HDPE, PP, and ABS is 8.7% by weight, wherein the water contact angle of HDPE-PP-ABS is 141°.
[0086] The preparation steps of the above-mentioned general polymer-modified melamine sponge hydrophobic material are as follows:
[0087] Step S1: Dissolve 0.5g HDPE in 200ml toluene and stir at 110℃ for 1h to obtain the first polymer solution;
[0088] Dissolve 0.5g of PP in 200ml of toluene and stir at 130℃ for 2h to obtain the second polymer solution;
[0089] Dissolve 0.5g of ABS in 200ml of toluene and stir at 150℃ for 3h to obtain a third polymer solution;
[0090] Step S2: The three polymer solutions treated in step S1 are dipped into the sponge. The dipped melamine sponge is placed in an oven and dried at 110°C for 1 hour to obtain the modified sponge. By repeating the dipping and drying process 5 times, the loading of the polymer solution-loaded melamine sponge is controlled to be 8.7% by weight.
[0091] Example 7
[0092] This embodiment proposes a general-purpose polymer-modified polyurethane sponge hydrophobic material, HDPE-7, PP-7, and ABS-7. To physically anchor HDPE, PP, and ABS onto the polyurethane sponge skeleton, based on the total mass of the general-purpose polymer-modified polyurethane sponge hydrophobic material, the loading amounts of HDPE, PP, and ABS are 10.9 wt%, 11.1 wt%, and 10.3 wt%, respectively. The water contact angles of HDPE-7, PP-7, and ABS-7 are 137°, 139°, and 139°, respectively.
[0093] The preparation steps of the above-mentioned general polymer-modified polyurethane sponge hydrophobic material are as follows:
[0094] Step S1: Dissolve 0.5g HDPE in 200ml toluene and stir at 110℃ for 1h to obtain the first polymer solution;
[0095] Dissolve 0.5g of PP in 200ml of toluene and stir at 130℃ for 2h to obtain the second polymer solution;
[0096] Dissolve 0.5g of ABS in 200ml of toluene and stir at 150℃ for 3h to obtain a third polymer solution;
[0097] Step S2: The first polymer solution treated in step S1 is dipped into the sponge. The dipped polyurethane sponge is placed in an oven and dried at 110°C for 1 hour to obtain the modified sponge. By repeating the dipping and drying process 5 times, the loading amount of the polymer solution on the polyurethane sponge is controlled to be 10.9% by weight.
[0098] The second polymer solution after step S1 was applied to the sponge. The applied polyurethane sponge was then dried in an oven at 110°C for 1 hour to obtain the modified sponge. By repeating the impregnation and drying process 5 times, the loading amount of the polyurethane sponge loaded with the polymer solution was controlled to be 11.1% by weight.
[0099] The third polymer solution after step S1 was applied to the sponge, and the applied polyurethane sponge was dried in an oven at 110°C for 1 hour to obtain the modified sponge. By repeating the impregnation and drying process 5 times, the loading amount of the polyurethane sponge loaded with the polymer solution was controlled to be 10.3% by weight.
[0100] Example 8
[0101] This embodiment proposes a general-purpose polymer-modified polyurethane sponge hydrophobic material HDPE-ABS. To physically anchor HDPE and ABS onto the polyurethane sponge skeleton, based on the total mass of the general-purpose polymer-modified polyurethane sponge hydrophobic material, the total load of HDPE and ABS is 8.5% by weight, wherein the water contact angle of HDPE-ABS is 139°.
[0102] The preparation steps of the above-mentioned general polymer-modified polyurethane sponge hydrophobic material are as follows:
[0103] Step S1: Dissolve 0.5g HDPE in 200ml toluene and stir at 110℃ for 1h to obtain the first polymer solution;
[0104] Dissolve 0.5g of ABS in 200ml of toluene and stir at 130℃ for 2h to obtain a second polymer solution;
[0105] Step S2: The two polymer solutions treated in step S1 are impregnated onto the sponge. The impregnated polyurethane sponge is placed in an oven and dried at 110°C for 1 hour to obtain the modified sponge. By repeating the impregnation and drying process 5 times, the loading amount of the polyurethane sponge loaded with polymer solution is controlled to be 8.5% by weight.
[0106] Comparative Example 1
[0107] The difference between Comparative Example 1 and the Example is that the melamine sponge was not coated with a general polymer.
[0108] Comparative Example 2
[0109] Graphene oxide (GO) was prepared using a modified Hummers method, by cutting commercial melamine sponge into a fixed shape (2×2×2cm). 3 The samples were ultrasonically cleaned three times with ethanol and pure water respectively, and then dried for later use.
[0110] A 2 mg / mL graphene oxide solution was ultrasonically dispersed for 30 min to obtain a graphene oxide dispersion. Then, a melamine sponge was immersed in the graphene oxide dispersion for 30 min and then removed and vacuum dried at 40 °C for 24 h. After reduction in hydrazine hydrate vapor at 80 °C for 24 h, the sponge was repeatedly rinsed with distilled water and vacuum dried at 80 °C to constant weight to obtain a reduced graphene oxide-based melamine sponge.
[0111] Test case
[0112] 1. Testing of general polymer loading
[0113] Modified sponges with different general-purpose polymer loadings were prepared by repeated impregnation and drying.
[0114] Calculate the loading of the general-purpose polymer according to Formula 1:
[0115] In the formula: W represents the weight of the sponge after being loaded with general polymer, and W0 represents the initial weight of the sponge.
[0116] 2. Surface morphology analysis
[0117] As shown in Figure 1, the clean, unmodified melamine (MS) sponge possesses a smooth skeleton. These skeletons are interwoven and interconnected, forming a multi-level microporous structure, allowing oils or organic solvents to freely pass through the sponge's internal pores. The sponge's skeletal structure can also effectively support the mass of the adsorbed oil, giving the sponge a large oil absorption capacity. However, the unmodified MS skeleton has a smooth and flat surface and contains a large number of hydrophilic groups, failing to meet the hydrophobic condition. If used directly for oil-water separation, the effect is very poor. After modification with a general-purpose polymer, as shown in Figure 1, the modified melamine sponge's skeletal structure exhibits irregularly distributed, layered loadings of varying sizes. This significantly increases the sponge's roughness, and the general-purpose polymer itself possesses good hydrophobic properties. In summary, the modified melamine sponge achieves a hydrophobic yet superoleophilic effect due to changes in its roughness and surface energy.
[0118] 2. Contact angle test
[0119] The water contact angles of various general-purpose polymer-modified melamine sponge hydrophobic materials were tested using a contact angle tester (DSA-100, KRUSS GmbH, Germany) to study their wetting properties. The results are shown in Figure 2.
[0120] As shown in Figure 2, the water contact angle of Comparative Example 1 is 0°. The water contact angle of the general-purpose polymer-modified melamine sponge hydrophobic materials prepared in Examples 1-4 increases with the increase of the general-purpose polymer loading. When the loadings of HDPE, PP, and ABS are 7.3%, 7.5%, and 7.7% by weight, respectively, the water contact angle of the modified melamine sponge is 135°, 137°, and 137°. Further increasing the loading of the general-purpose polymer does not significantly change the water contact angle of the hydrophobic material and may affect the oil adsorption effect of the oil-absorbing sponge.
[0121] As shown in Figure 3, the general-purpose polymer-modified melamine sponge hydrophobic material prepared in Example 3 was immersed in solutions with different pH values for 12 hours, and the water contact angle of the general-purpose polymer-modified melamine sponge hydrophobic material at different pH values was measured. The results show that the water contact angle of the polymer-modified melamine sponge hydrophobic material after immersion is above 130°, and the maximum water contact angle is 140° when the pH value is 7. This indicates that the polymer-modified melamine sponge hydrophobic material has good acid and alkali resistance.
[0122] Figure 5 shows the water contact angles of the hydrophobic materials prepared in Examples 5-6 and Comparative Example 2. The water contact angles of the three materials are 139°, 141° and 131°, respectively.
[0123] 3. Oil absorption capacity test
[0124] The general polymer-modified hydrophobic sponge materials prepared in Examples 3, 5, 6 and 7 were placed in different oil solvents to test their adsorption capacity. The results are shown in Figures 4, 6 and 7.
[0125] The adsorption capacity of general polymer-modified hydrophobic sponge materials can be calculated using the following formula:
[0126]
[0127] In the formula: m represents the weight of the sponge after absorbing oil, and m0 represents the weight of the initial hydrophobic sponge.
[0128] As can be seen from Figure 4, the general-purpose polymer-modified melamine sponge hydrophobic material of Example 3 has good adsorption performance for various oils. The absorption capacity of HDPE, PP and ABS modified melamine sponge hydrophobic materials for various oils and solvents is 87 to 190 times, 86 to 180 times and 85 to 176 times their weight, respectively.
[0129] As can be seen from Figure 7, the general-purpose polymer-modified polyurethane sponge hydrophobic material of Example 7 has good adsorption performance for various oils. The absorption capacity of the HDPE, PP and ABS modified polyurethane sponge hydrophobic materials for various oils and solvents is 88 to 192 times, 87 to 184 times and 89 to 194 times their weight, respectively.
[0130] This shows that general-purpose polymer-modified commercial sponge (melamine, polyurethane) hydrophobic materials have excellent oil absorption capacity, and the variation in absorption capacity may depend on the density of oil and organic solvent. Among them, general-purpose polymer-modified sponge (melamine, polyurethane) hydrophobic materials have the best adsorption performance for chloroform, and the adsorption capacity for other oils reaches more than 80g / g.
[0131] Figure 6 shows the oil absorption capacity of the modified melamine sponge hydrophobic materials prepared in Examples 5-6 and Comparative Example 2. As can be seen from Figure 6, the absorption capacity for chloroform is 170 g / g, 157 g / g, and 127 g / g; the absorption capacity for toluene is 94 g / g, 88 g / g, and 70 g / g.
[0132] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any other way. Any modifications or equivalent changes made based on the technical essence of the present invention shall still fall within the scope of protection claimed by the present invention.
Claims
1. A general-purpose polymer-modified hydrophobic sponge material, characterized in that, The material includes a sponge and a general-purpose polymer anchored on the sponge, wherein the general-purpose polymer has a loading of 1-15% by weight based on the total weight of the hydrophobic material, and the water contact angle of the hydrophobic material is 120-150°.
2. The general-purpose polymer-modified hydrophobic sponge material according to claim 1, characterized in that, The general-purpose polymer includes at least one of HDPE, PP, ABS, polystyrene, and polyvinyl chloride.
3. The general-purpose polymer-modified hydrophobic sponge material according to claim 2, characterized in that, The general-purpose polymer is selected from a combination of HDPE and PP or a combination of HDPE, PP and ABS.
4. The general-purpose polymer-modified hydrophobic sponge material according to claim 3, characterized in that, In the combination of HDPE and PP, the mass ratio of HDPE to PP is 1:
1.
5. The general-purpose polymer-modified hydrophobic sponge material according to claim 3, characterized in that, In the combination of HDPE, PP and ABS, the mass ratio of HDPE, PP and ABS is 1:1:
1.
6. The general-purpose polymer-modified hydrophobic sponge material according to claim 2, characterized in that, The sponge includes at least one of melamine and polyurethane.
7. A method for preparing a general-purpose polymer-modified hydrophobic sponge material according to any one of claims 1-6, characterized in that, The preparation method includes the following steps: Step S1: Dissolution of general polymer: Dissolve the general polymer in a solvent to obtain a general polymer solution; Step S2: Preparation of hydrophobic material: Dip the general polymer solution obtained in step S1 onto a sponge and dry it to obtain the hydrophobic material.
8. The preparation method according to claim 7, characterized in that, In step S1, the ratio of the amount of the general polymer to the amount of the solvent is (0.1-1)g:100mL.
9. The preparation method according to claim 8, characterized in that, In step S1, the solvent is toluene or xylene.
10. The preparation method according to claim 7, characterized in that, In step S1, the melting temperature is 100-130℃.