CN114106408A

CN114106408A - Hydrophobic modifier composition, hydrophobic sponge material, preparation method and application thereof

Info

Publication number: CN114106408A
Application number: CN202010898034.2A
Authority: CN
Inventors: 谢谚; 盛学佳; 闫茜; 赵诗琳; 王昕喆; 周志国; 杨洋洋
Original assignee: China Petroleum and Chemical Corp; Sinopec Qingdao Safety Engineering Institute
Current assignee: China Petroleum and Chemical Corp; Sinopec Qingdao Safety Engineering Institute
Priority date: 2020-08-31
Filing date: 2020-08-31
Publication date: 2022-03-01

Abstract

The invention relates to the field of removal of organic pollutants in water, in particular to a hydrophobic modifier composition, a hydrophobic sponge material, a preparation method and an application thereof. The hydrophobic modifier composition comprises polyvinyl chloride, nano-silica and liquid siloxane; wherein the mass ratio of the polyvinyl chloride to the nano silicon dioxide to the liquid siloxane is (800-1200): (200-4800): 1. the hydrophobic sponge material obtained by using the hydrophobic modifier composition can quickly and effectively separate oil/water, can still keep higher adsorption capacity after being recycled for many times, and can be used for emergency treatment of oil leakage on water.

Description

Hydrophobic modifier composition, hydrophobic sponge material, preparation method and application thereof

Technical Field

The invention relates to the field of removal of organic pollutants in water, in particular to a hydrophobic modifier composition, a hydrophobic sponge material, a preparation method and an application thereof.

Background

With the development of the petrochemical industry, the types and the quantity of dangerous chemicals (hereinafter referred to as dangerous chemicals) used in the world are remarkably increased, and the import and export of the dangerous chemicals are mostly dependent on ship transportation, so that the risk of water leakage accidents is high. The physical behavior of benzene series hazardous chemicals after leaking into water belongs to the floating volatilization (FE) class, namely: the leaked benzene series can not only pollute air in the form of steam, but also float on the water surface and deteriorate the water quality. In addition, the benzene series has medium and high toxicity to some microalgae, fishes and crustaceans, and threatens the safety of aquatic ecology after entering water. Therefore, effective measures must be taken to recover or remove benzene series and other dangerous chemicals leaked from the water surface so as to reduce the pollution degree of the benzene series and other dangerous chemicals to the atmospheric environment and the water environment.

Adsorption is one of the most effective methods for removing organic contaminants from water. In view of the characteristics of low viscosity and easy diffusion of benzene series into a film on the water surface, a high-efficiency adsorption material is selected to realize quick and effective recovery. In recent years, the selective separation of organic pollutants by using super-hydrophobic porous materials is receiving more and more attention. In the prior art, a large number of macroporous adsorption materials (such as CN106145256A, CN107312196A, CN107312198A and CN108410005A) which take polymer sponges as substrates exist. However, these materials still have a number of disadvantages: although some materials have better adsorption performance and better adsorption selectivity, the materials generally have the problems of reduced adsorption capacity, poor hydrophobic effect and poor recycling performance after long-term use, and the commercialization application process of the super-hydrophobic porous material is seriously hindered.

In order to overcome many defects of the existing super-hydrophobic porous material, a new material which has high adsorption capacity, strong selective adsorption and good recycling performance is urgently needed to be provided.

Disclosure of Invention

Aiming at the problem of poor recycling performance of an adsorption material in the prior art, the invention provides a hydrophobic modifier composition, a hydrophobic sponge material, a preparation method and an application thereof, which have the advantages of poor recycling performance of the hydrophobic sponge material, absorption performance and absorption selectivity of the hydrophobic sponge material, and the hydrophobic sponge material modified by the hydrophobic modifier composition provided by the invention has the advantages of high absorption capacity, strong selective absorption and good recycling performance.

The invention provides a hydrophobic modifier composition in a first aspect, wherein the hydrophobic modifier composition contains polyvinyl chloride, nano silicon dioxide and liquid siloxane; wherein the mass ratio of the polyvinyl chloride to the nano silicon dioxide to the liquid siloxane is (800-1200): (200-4800): 1.

in a second aspect, the invention provides a hydrophobic sponge material comprising a sponge matrix and a hydrophobic coating, wherein the hydrophobic coating is obtained by curing the hydrophobic modifier composition of the first aspect of the invention.

In a third aspect the present invention provides a method of making a hydrophobic sponge material comprising: the hydrophobic modifier composition of the first aspect of the invention is uniformly dispersed by a solvent, then is impregnated on the surface of a sponge matrix, and is dried and cured.

In a fourth aspect, the invention provides a hydrophobic sponge material obtainable by the process of the third aspect of the invention.

Preferably, the hydrophobic sponge material has a surface contact angle to water of more than 139.7 °, further preferably more than 144 °, more preferably more than 150 °.

Preferably, the hydrophobic sponge material has a density of 0.007 to 0.105g/cm³More preferably 0.009-0.102g/cm³The porosity is 79.5 to 97.5%, more preferably 81.5 to 97.5%.

In a fifth aspect, the invention provides the use of the hydrophobic sponge material of the fourth aspect in the removal of oil products leaked from a water surface;

preferably, the oil is selected from at least one of toluene, xylene, ethylbenzene, dichloromethane, n-hexane, styrene, benzene, tetrahydrofuran, diesel oil, and engine oil.

The hydrophobic modifier composition provided by the invention can improve the hydrophobicity and lipophilicity of the sponge and improve the adsorption performance and the recycling performance of the hydrophobic sponge material. The hydrophobic sponge material modified by the hydrophobic modifier composition or the hydrophobic sponge material provided by the invention can realize the quick and effective separation of low-viscosity oil products/water, can still keep higher adsorption capacity after being recycled for many times, and can be used for the emergency treatment of oil product leakage on water. For example, the sponge material modified by the hydrophobic modifier composition provided by the invention has a water contact angle of more than 139.7 degrees, the initial xylene adsorption capacity can reach more than 27g/g, the adsorption capacity can still be kept more than 65% of the initial adsorption capacity after being recycled in xylene for 500 times, and the recycling performance is much higher than that of other super-hydrophobic sponges.

Drawings

FIG. 1 is a Scanning Electron Microscope (SEM) image of an unmodified nanosponsive material and the hydrophobic sponge material obtained in example 1;

FIG. 2 is a photograph of the water contact angle of the hydrophobic sponge obtained in example 1;

FIG. 3 is a graph showing the test results of test example 4;

FIG. 4 is a diagram showing the state of diesel/water adsorption separation in test example 6.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

preferably, the mass ratio of the polyvinyl chloride to the nano-silica to the liquid siloxane is (900- & 1100): (300-2200): 1.

preferably, the mass ratio of the polyvinyl chloride to the nano silicon dioxide is (0.25-4): 1, more preferably (0.5-3): 1.

preferably, the mass ratio of polyvinyl chloride to liquid silicone is 1200:1 to 800:1, more preferably 1100:1 to 900: 1.

Preferably, the particle size of the nano-silica is 1-100nm, and the specific surface area is 100-400m²(ii)/g; further preferably, the particle size of the nano-silica is 7-40nm, the specific surface area is 100-140m²/g。

Herein, the particle size of the nano silica is measured by a scanning electron microscope (feminome G5 Pro) and a transmission electron microscope (JEM-100 CX, japan electronics co., ltd.) and the specific surface area of the nano silica is BET specific surface area measured by a full automatic nitrogen physical adsorption apparatus (Quantachrome, Nova 1000 e).

Preferably, the nano-silica is hydrophobic nano-silica, and further preferably hydrophobic gas phase nano-silica.

Preferably, the polyvinyl chloride has a K-value (K-value) of less than 68, such as 68-65,65-55, and more preferably a K-value of 59-55. Wherein, the K value is obtained by measuring and calculating according to the national standard GB/T3401.

In the present invention, the liquid siloxane means a substance containing an Si-O bond which is liquid at normal temperature and pressure. Preferably, the liquid siloxane further contains one or more amino groups (which are aminosilanes, i.e., silane coupling agents), and the number of carbon atoms in the liquid siloxane is preferably 4 to 12. Further preferably, the liquid silicone contains aminopropyl and alkoxy functional groups.

Further preferably, the liquid siloxane is selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, (3-aminopropyl) dimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltriethoxysilane, at least one of N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane and N- (2-aminoethyl) -3-aminopropyltriethoxysilane, and more preferably 3-aminopropyltriethoxysilane (i.e., gamma-aminopropyltriethoxysilane).

Preferably, the hydrophobic modifier composition further comprises an organic solvent, wherein the solvent is not particularly limited in the present invention as long as it can dissolve/swell the polyvinyl chloride, and for example, the solvent may be at least one of tetrahydrofuran, cyclohexanone, and dichloroethane, and is preferably tetrahydrofuran.

Preferably, the mass content of the polyvinyl chloride in the solvent is 3-40mg/mL, more preferably 3-20mg/mL, and even more preferably 8-12 mg/mL.

In the hydrophobic modifier composition, polyvinyl chloride, nano-silica and liquid siloxane have a synergistic effect on super-hydrophobic performance, and simultaneously, the crosslinking performance of a hydrophobic coating and the toughness of the surface of a coated substrate can be improved together, so that the recycling performance is enhanced; and the pore structure of the sponge matrix can be basically not damaged, so that the adsorption performance of the material is ensured.

Preferably, the mass content of the sponge matrix is 55-95% and the mass content of the hydrophobic coating is 5-45% based on the total mass of the hydrophobic sponge.

The mass content of the hydrophobic coating can be calculated by the mass of the hydrophobic sponge material and the mass of the sponge matrix.

Preferably, the density of the sponge matrix is 0.007-0.058g/cm³More preferably 0.009-0.056g/cm³The porosity is 80 to 98%, and more preferably 82 to 98%.

In the present invention, the sponge matrix can be any commercially available sponge product, and preferably, the sponge matrix is at least one selected from melamine sponge, polyurethane sponge, and polyether sponge, and is preferably melamine sponge. Among them, the melamine sponge is more preferably a nanosponge.

Wherein the nanometer sponge is also called melamine sponge, and the density of the nanometer sponge is 0.013-0.018g/cm³The porosity is 95-98%.

In the present invention, the solvent is not particularly limited as long as it can dissolve/swell polyvinyl chloride, and for example, the solvent may be at least one of tetrahydrofuran, cyclohexanone, and dichloroethane.

Preferably, the solvent is used in an amount such that the mass content of the polyvinyl chloride in the obtained impregnation liquid is 3-40mg/mL, more preferably 3-20mg/mL, and even more preferably 8-12 mg/mL.

The mass content of polyvinyl chloride in the present invention refers to the volume ratio of polyvinyl chloride to the solvent used.

Preferably, the impregnation conditions include: immersing the sponge matrix into the impregnation liquid for at least 6h, preferably 6-48h, and 8-24 h.

In the present invention, the impregnation method is not particularly limited as long as the sponge base can be completely impregnated in the impregnation solution. The invention is not limited to room temperature, and the room temperature can be 20-35 ℃.

Preferably, before the sponge matrix is immersed in the immersion liquid, the sponge matrix is ultrasonically washed in deionized water and absolute ethyl alcohol respectively, and after washing is finished, the sponge matrix is dried.

In the present invention, the means used for drying after completion of impregnation is not particularly limited as long as the organic solvent can be removed, and it is preferable to perform air drying at room temperature.

Preferably, the curing conditions include: the temperature is 40-70 ℃, more preferably 50-70 ℃, and more preferably 50-60 ℃; the time is at least 3 hours, more preferably 3 to 24 hours, and still more preferably 3 to 6 hours.

In a fourth aspect, the present invention provides a hydrophobic sponge material obtainable by the process of the third aspect of the invention.

The larger the surface contact angle of the hydrophobic sponge material to water is, the stronger the hydrophobicity is, the more difficultly water is adsorbed by sponge, the better the interception effect of the hydrophobic sponge material to water is, and the better the separation effect is when oil/water is separated.

Preferably, the hydrophobic sponge material has a micro-nano structure.

Preferably, the sponge material modified by the hydrophobic modifier composition is used for adsorbing xylene, and the initial adsorption capacity of the xylene is more than 27g/g, preferably more than 35 g/g. After 500 cycles, the adsorption capacity of xylene still reaches more than 65%, preferably more than 75%, and more preferably more than 93% of the initial adsorption capacity.

Preferably, when the nano sponge material modified by the hydrophobic modifier composition adsorbs xylene dissolved in water, the removal rate of the xylene can be improved by 10-12 times compared with natural volatilization. For example, when the concentration of the xylene is 150mg/L, after the nano sponge material modified by the hydrophobic modifier composition is used for adsorption for 24 hours in a closed environment, the xylene in the water body can be reduced to 17.52mg/L, and compared with the open placement, the removal rate can be improved to 88.32% from 7.9% of natural volatilization.

Preferably, the nano sponge material modified by the hydrophobic modifier composition has the adsorption capacity for n-hexane of more than 28.45g/g, the adsorption capacity for styrene of more than 37.27g/g, the adsorption capacity for benzene of more than 46.33g/g, the adsorption capacity for tetrahydrofuran of more than 66.6g/g, the adsorption capacity for diesel oil of more than 31.54g/g and the adsorption capacity for engine oil of more than 72.5 g/g.

The hydrophobic sponge material provided by the invention has high adsorption capacity, the recycling performance is much higher than that of other super-hydrophobic sponges, the concentration of benzene series in a water body can be effectively reduced, and the hydrophobic sponge material has good application prospect in the field of emergency treatment of low-viscosity oil leakage.

In a fifth aspect, the invention provides the use of the hydrophobic sponge material according to the fourth aspect of the invention for removing oil products from a water surface leak.

Compared with the prior art, the invention has the following beneficial effects: the preparation method of the hydrophobic sponge material is simple, and the obtained hydrophobic sponge material has high adsorption capacity, strong selective adsorption and excellent recycling performance. For example, when xylene is adsorbed by a sponge material modified by the hydrophobic modifier composition, the initial adsorption capacity of xylene is as high as 27g/g or more, preferably 35g/g or more. After 500 cycles, the adsorption capacity of xylene still reaches more than 65%, preferably more than 75%, and more preferably more than 93% of the initial adsorption capacity.

The present invention will be described in detail below with reference to specific embodiments thereof, but it should be understood that the scope of the present invention is not limited by the examples.

The following examples and comparative examples used the following starting materials:

the sponge bases used in the examples and comparative examples are all commercially available common sponges, wherein, unless otherwise specified, the melamine sponges mentioned in the examples and comparative examples are all common melamine sponges with a density of 0.009-0.011g/cm³The porosity was 85.2%. The nano sponge has a density of 0.013-0.015g/cm³Melamine sponge with a porosity of 97.5%.

The density of the polyurethane sponge is 0.022-0.026g/cm³The porosity is 90.8 percent, and the density of the polyether sponge is 0.054 to 0.056g/cm³The porosity was 82.1%.

3-aminopropyltriethoxysilane was purchased from Shanghai Allantin Biotechnology Ltd under the trade designation A107147-100ml, purity 99%.

The polyvinyl chloride SG-8 is purchased from Shanghai Aladdin Biotechnology, Inc., and has the following powder and quality indexes: the viscosity number is 86-73mL/g, the absolute viscosity is 1.4-1.5mPa.s, the K value is 59-55, and the average polymerization degree is 650-740.

Polyvinyl chloride SG-5, purchased from Shanghai Allantin Biotechnology GmbH, quality index: the powder has a viscosity number of 118-107 mL/g, an absolute viscosity of 1.7-1.8 mPa.s, a K value of 68-65 and an average polymerization degree of 981-1135.

Hydrophobic fumed nanometer silica, Hydrophobic-120, available from Shanghai Aladdin Biotechnology Ltd, with particle diameter of 7-40nm and specific surface area of 120 + -15 m²/g。

Hydrophilic gas phase nano silicon dioxide, purchased from Shanghai Aladdin Biotechnology GmbH, with particle diameter of 7-40nm and specific surface area of 380m²/g。

Methyl silicone resin, available from new materials of denna silicon, ltd, powdered, chemically pure.

The test methods involved in the examples and comparative examples are as follows:

(1) testing of surface topography

The topographical features were characterized by scanning electron microscopy (Phenom G5 Pro, femina).

(2) Measurement of Water contact Angle

The measurements were carried out 5 times in total using a contact angle tester, model OCA20, from Dataphysics, Germany, and the average of the 5 measurements was taken.

(3) Measurement of adsorption Capacity

Take 1cm³Volume of sponge sample, recording its mass before oil absorption M₁Then the sponge sample is put into 100ml of organic solvent or oil and soaked fully until the weight of the sponge does not change any more, at which time the sponge sample is taken out and the mass M of the sponge sample is recorded₂The adsorption capacity Q is then calculated from the following formula:

wherein, the adsorption capacity measured for the first time is the initial adsorption capacity, then the sponge sample is extruded, and the test operation is repeated to test the cycle performance of the sponge sample.

(4) Measurement of xylene concentration

In the test examples, the xylene concentration was measured according to "gas chromatography for measuring Water quality benzene series GB 11890-89".

(5) Sponge density test method

Cutting sponge into regular cubes, calculating the volume, and weighing the mass m of the sponge with balance₀And calculating the sponge density using the formula:

ρ＝m₀/V₀

where ρ is the density of the sponge, m₀Is the mass of the sponge, V₀Is the volume of the sponge.

(6) Method for testing porosity of sponge

Soaking unmodified sponge (sponge matrix) in water for 30min, soaking modified hydrophobic sponge in m-xylene solution for 30min, squeezing with tweezers, and removing bubbles; the measured weight was then quickly removed and the porosity calculated using the formula.

P＝(m₂-m₁)/ρV

P is the porosity of the sample, m₁Mass of sponge before soaking, m₂Is the mass of the sponge after soaking, ρ is the density of the soaking liquid, and V is the volume of the sponge. Wherein the density of water is 1g/cm³The density of the meta-xylene solution was 0.8599g/cm³。

Example 1

Mixing sponge matrix (nanometer sponge, 1 × 1 × 1 cm)³) And ultrasonic cleaning in deionized water and absolute ethyl alcohol for multiple times in sequence, washing with deionized water, and drying in an oven for later use.

(1) Dispersing 1g of polyvinyl chloride SG-8 and 0.5g of hydrophobic fumed nano silicon dioxide in 100mL of tetrahydrofuran, placing the mixture in a glass bottle with a cover, stirring the mixture by using a magnetic stirrer until the mixture is uniformly dispersed, adding 1mg of 3-aminopropyltriethoxysilane, and continuously stirring the mixture for 1h until the mixture is uniformly dispersed to obtain an impregnation liquid with the polyvinyl chloride mass content of 10 mg/mL.

(2) Drying the nanometerSponge (1X 1 cm)³) Soaking in the soaking solution in the step (1) for 12 h. And (3) taking out the sponge, ventilating and drying at room temperature for 3h to volatilize the organic solvent, and then placing the sponge in an oven to be cured for 6h at the temperature of 60 ℃ to obtain the hydrophobic sponge material A1. Wherein the density of the hydrophobic sponge material A1 is 0.020g/cm³The porosity was 96.96%.

Example 2

A hydrophobic sponge material was prepared as described in example 1, except that 0.5g of polyvinyl chloride SG-8, 1g of hydrophobic fumed nano-silica and 0.5mg of 3-aminopropyltriethoxysilane were added in step (1), to obtain a hydrophobic sponge material A2. Wherein the density of the hydrophobic sponge material A2 is 0.019g/cm³The porosity was 96.99%.

Example 3

A hydrophobic sponge material was prepared as described in example 1, except that 1.5g of polyvinyl chloride SG-8, 0.5g of hydrophobic fumed nano-silica and 1.5mg of 3-aminopropyltriethoxysilane were added in step (1), to obtain a hydrophobic sponge material A3. Wherein the density of the hydrophobic sponge material A3 is 0.021g/cm³The porosity was 96.93%.

Example 4

A hydrophobic sponge material was prepared as described in reference to example 1, except that 2g of polyvinyl chloride SG-8, 0.5g of hydrophobic fumed nano-silica and 2mg of 3-aminopropyltriethoxy-silicon were added in the step (1), to obtain a hydrophobic sponge material A4. Wherein the density of the hydrophobic sponge material A4 is 0.021g/cm³The porosity was 96.92%.

Example 5

A hydrophobic sponge material was prepared as described in example 1, except that in step (2), the sponge material was cured in an oven at 80 ℃ for 6 hours, and the procedure was as in example 1, to give a hydrophobic sponge material A5. Wherein the density of the hydrophobic sponge material A5 is 0.020g/cm³The porosity was 96.95%.

Examples 6 to 8

Hydrophobic sponge materials were prepared as described in example 1, except that polyurethane sponge, melamine sponge, and polyether sponge were used instead of nano sponge, respectively, to obtain hydrophobic spongesCotton material A6-A8. Wherein the density of the hydrophobic sponge material A6 is 0.030g/cm³The porosity is 90.36%, and the density of the hydrophobic sponge material A7 is 0.016g/cm³The porosity is 84.73%, and the density of the hydrophobic sponge material A8 is 0.060g/cm³The porosity was 81.54%.

Example 9

A hydrophobic sponge was prepared as described in reference to example 1, except that in step (2), it was cured in an oven at 60 ℃ for 12h to give hydrophobic sponge A9. Wherein the density of the hydrophobic sponge material A9 is 0.020g/cm³The porosity was 96.96%.

Example 10

A hydrophobic sponge material was prepared as described in reference to example 1, except that polyvinyl chloride SG-5 was used instead of polyvinyl chloride SG-8, to obtain a hydrophobic sponge material A10. Wherein the density of the hydrophobic sponge material A10 is 0.023g/cm³The porosity was 96.82%.

Example 11

A hydrophobic sponge material was prepared as described in example 1, except that hydrophilic type fumed nano-silica was used instead of hydrophobic type fumed nano-silica, resulting in a hydrophobic sponge material a 11. Wherein the density of the hydrophobic sponge material A11 is 0.019g/cm³The porosity was 96.98%.

Comparative example 1

A hydrophobic sponge material was prepared as described in reference to example 6, except that no polyvinyl chloride SG-8 was added in step (1), yielding a hydrophobic sponge material D1.

Comparative example 2

A hydrophobic sponge material was prepared as described in example 6, except that the hydrophobic fumed nano silica was not added in step (1), to obtain a hydrophobic sponge material D2.

Comparative example 3

A hydrophobic sponge material was prepared as described with reference to example 6, except that the impregnation solution of step (1) was prepared by the following method:

acidifying 3g of expanded graphite for 24 hours by using a mixed solution of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 7:3, washing the expanded graphite to be neutral by using deionized water after filtering, drying, adding the expanded graphite into 200mL of ethanol, performing ultrasonic dispersion for 1 hour, and adding 3mg of 3-aminopropyltriethoxysilane to obtain an expanded graphite dispersion liquid serving as an impregnation liquid. A hydrophobic sponge material D3 was obtained.

Comparative example 4

A hydrophobic sponge material was prepared as described with reference to example 6, except that 1g of polyvinyl chloride SG-8 was replaced with 1g of methyl MQ silicone resin. A hydrophobic sponge material D4 was obtained.

Test example 1

Scanning Electron Microscope (SEM) characterization was performed on the unmodified nano-sponge and hydrophobic sponge material a1, and the results are shown in fig. 1. Wherein, fig. 1a and fig. 1b are SEM images of unmodified nano sponge material and hydrophobic sponge material a1 magnified 4000 times respectively.

As can be clearly seen from fig. 1, the surface of the unmodified nano sponge material is smooth (fig. 1a), the surface roughness of the modified hydrophobic sponge material a1 is greatly improved (fig. 1b), and the surface of the hydrophobic sponge material a1 shows the roughness with a micro-nano structure.

Test example 2

The hydrophobic sponge materials A1-A11, D1-D4 and the sponge matrix were tested for water contact angle, and the results are shown in Table 1.

Fig. 2 shows a water contact angle photograph of the hydrophobic sponge material a 1. The water contact angle of the hydrophobic sponge material a1 was >150 °, demonstrating that the hydrophobic sponge material a1 is superhydrophobic.

During testing, the nano sponge, the melamine sponge and the polyether sponge in the sponge matrix have good water absorption performance, and water drops absorb instantly, so that the contact angle of water cannot be measured, and the test is not carried out.

Test example 3

The initial adsorption capacity and the cycle performance of the hydrophobic sponge materials A1-A11, D1-D4 and the sponge matrix to the dimethylbenzene are tested.

Wherein, the sponge matrix which is not subjected to modification treatment is not subjected to cycle test. In the circulation process, 100 times of circulation test is taken as one period, the test is carried out for at least one period, the test is stopped when the retention rate of the adsorption capacity of the xylene after circulation use is lower than 50%, and the test results are detailed in table 1.

TABLE 1

The experimental results in table 1 show that the nano sponge material modified by the hydrophobic modifier composition of the present invention not only has improved adsorption performance, but also has significantly improved recycling performance, and the retention rate of the adsorption capacity of the hydrophobic nano sponge material after 500 times of recycling is more than 65%.

Test example 4

A1 (1X 1 cm) hydrophobic sponge material was prepared according to the method described in example 1³) It was mixed with unmodified nanosponges (1X 1 cm)³) The two portions were immersed in a sealed bottle containing 50mL of a 150mg/L aqueous xylene solution, and another portion of the same aqueous xylene solution was placed in the same bottle, left open, and used as a blank for measuring the amount of natural xylene volatilization. The residual xylene concentration in the water was measured by sampling at regular intervals and the results are shown in FIG. 3.

As can be seen from FIG. 3, the hydrophobic sponge material A1 also has a good effect of removing xylene dissolved in water, and can reduce the concentration of xylene from 150mg/L to 17.52 mg/L; the unmodified nano sponge also has a certain removal effect on xylene dissolved in a water body, and the concentration of the xylene can be reduced from 150mg/L to 91.22 mg/L; in the blank control experiment, the concentration of xylene in water was reduced from 150mg/L to 138.15mg/L due to xylene volatilization. The hydrophobic sponge material A1 can improve the removal rate of xylene from 7.9% of natural volatilization to 88.32%.

Test example 5

Hydrophobic sponge A1 was prepared according to the method described in example 1, taking hydrophobic sponge A1 and unmodified nanoparticlesThe sponge is respectively plugged into the front end of a syringe, and 5mL of the sponge is added into the syringe according to the volume ratio of 1: the xylene (sudan III)/water mixture of 1 was poured slowly into the syringe. In the syringe plugged with unmodified nanosponges, the xylene/water mixture all flowed rapidly through the sponge material into the beaker below. In the syringe filled with the hydrophobic sponge material A1, 2.5ml of xylene passes through the hydrophobic sponge material A1 in about 10 seconds, and water is intercepted above the hydrophobic sponge material A1, so that oil-water separation is realized. The xylene concentration in the xylene/water mixture before separation was 4.3X 10⁵mg/L, the concentration of dimethylbenzene in the upper water phase after separation is 103mg/L, and the removal rate is as high as 99%. The test example shows that the hydrophobic sponge material can quickly reduce the concentration of dimethylbenzene in the leaked water body.

Test example 6

The hydrophobic sponge material A1 was used to adsorb different organic substances, and the measured adsorption capacities are shown in Table 2.

TABLE 2 adsorption capacities of different organic substances

As can be seen from Table 2, the hydrophobic sponge material A1 has an adsorption capacity for xylene of 41.45g/g, an adsorption capacity for n-hexane of 28.45g/g, an adsorption capacity for styrene of 37.27g/g, an adsorption capacity for benzene of 46.33g/g, an adsorption capacity for tetrahydrofuran of 66.60g/g, an adsorption capacity for diesel oil of 31.54g/g, and an adsorption capacity for engine oil of 72.50 g/g.

Test example 7

2X 2cm were prepared as in example 1³Hydrophobic sponge material, which was placed in a mixture of 5ml xylene +25ml water, stained with a few drops of sudan III, and placed in the hydrophobic sponge material, the results are shown in fig. 4. Wherein 4a is the original state of the mixed xylene/water solution after mixing, and can beThe mixture was clearly seen to be two layers, the upper layer was red and the lower layer was colorless. 4b is the state after 5 seconds of adding the hydrophobic sponge material, at this time, the red liquid level is reduced, the color of the upper layer gradually becomes lighter, and the hydrophobic sponge material begins to turn red. 4c is the state 10 seconds after the hydrophobic sponge material is added, at this time, the upper red layer basically disappears, and the hydrophobic sponge material becomes darker in red. 4d is the state after the sponge is taken out after 10 seconds, the water body is basically clear and colorless, and the liquid level height is basically unchanged. From this, 2X 2cm³The hydrophobic sponge material can basically absorb 5ml of dimethylbenzene floating on the water surface within 10 seconds, and the water body adsorbed by the hydrophobic sponge material is basically clear and colorless, and the oil-water separation effect is good.

Test example 8

Preparation of 2X 2cm³Hydrophobic sponge material, xylene and water are mixed in a volume ratio of 1: 1, adding a few drops of Sudan III for dyeing to obtain 50mL of dimethylbenzene/water mixed solution, and placing the mixed solution into a beaker with scales to mark the position of an oil-water interface. And then putting a hydrophobic sponge material, vibrating and contacting the hydrophobic sponge material with the xylene/water mixed solution for 30s, taking out, extruding the liquid in the sponge in another beaker, and repeating the adsorption operation for 5-7 times until the red color disappears. In this case, it was observed that the height of the aqueous phase in the beaker was substantially unchanged and that no demixing occurred in the xylene phase obtained by separation. Therefore, the hydrophobic sponge material has super-hydrophobicity and lipophilicity, has good selective adsorption and can quickly recover xylene floating on water.

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and those skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims

1. A hydrophobic modifier composition characterized by: the hydrophobic modifier composition contains polyvinyl chloride, nano silicon dioxide and liquid siloxane; wherein the mass ratio of the polyvinyl chloride to the nano silicon dioxide to the liquid siloxane is (800-1200): (200-4800): 1.

2. the hydrophobic modifier composition of claim 1, wherein the mass ratio of polyvinyl chloride, nano-silica and liquid silicone is (900- & 1100): (300-2200): 1.

3. the hydrophobic modifier composition as claimed in claim 1 or 2, wherein the nano silica has a particle size of 1-100nm and a specific surface area of 100-400m²/g；

Preferably, the particle size of the nano-silica is 7-40nm, the specific surface area is 100-140m²/g；

4. The hydrophobic modifier composition of any one of claims 1-3, wherein the polyvinyl chloride has a K value of less than 68, preferably 59-55;

preferably, the liquid silicone further contains one or more amino groups; more preferably, the liquid siloxane is selected from at least one of 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, (3-aminopropyl) dimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane.

5. A hydrophobic sponge material comprising a sponge matrix and a hydrophobic coating, wherein the hydrophobic coating is obtained by curing a hydrophobic modifier composition according to any one of claims 1 to 4.

6. The hydrophobic sponge material according to claim 5, wherein the mass content of the sponge matrix is 55-95% and the mass content of the hydrophobic coating is 5-45% based on the total mass of the hydrophobic sponge.

7. A method of making a hydrophobic sponge material comprising: the hydrophobic modifier composition of any one of claims 1-4 is dispersed with a solvent uniformly, impregnated onto the surface of a sponge matrix, dried and cured.

8. A process according to claim 7, wherein the solvent is used in an amount such that the polyvinyl chloride content of the resulting impregnation solution is 3-40mg/mL, more preferably 8-12 mg/mL.

9. The method of claim 7 or 8, wherein the curing conditions comprise: the temperature is 40-70 ℃ and the time is 3-24 h.

10. A process according to any one of claims 7 to 9, wherein the impregnation time is from 6 to 48 hours, preferably from 8 to 24 hours.

11. The method of any one of claims 7-10, wherein the sponge matrix has a density of 0.007-0.058g/cm³More preferably 0.009-0.056g/cm³The porosity is 80 to 98%, and preferably 82 to 98%;

preferably, the sponge matrix is selected from at least one of melamine sponge, polyurethane sponge and polyether sponge, and is preferably melamine sponge; among them, the melamine sponge is more preferably a nanosponge.

12. A hydrophobic sponge material made by the method of any one of claims 7-11;

preferably, the hydrophobic sponge material has a surface contact angle to water of more than 139.7 °, further preferably more than 144 °, more preferably more than 150 °;

13. The hydrophobic sponge material according to claim 12, wherein the sponge material modified with the hydrophobic modifier composition has an initial adsorption capacity for xylene of 27g/g or more, preferably 35g/g or more;

preferably, the adsorption capacity of para-xylene is maintained above 65%, preferably above 75% of the initial adsorption capacity after 500 cycles.

14. The hydrophobic sponge material of claim 12 or 13, wherein the nano-sponge material modified with the hydrophobic modifier composition has an adsorption capacity for n-hexane of 28.45g/g or more, an adsorption capacity for styrene of 37.27g/g or more, an adsorption capacity for benzene of 46.33g/g or more, an adsorption capacity for tetrahydrofuran of 66.60g/g or more, an adsorption capacity for diesel of 31.54g/g or more, and an adsorption capacity for engine oil of 72.50g/g or more.

15. Use of a hydrophobic sponge material according to any one of claims 12 to 14 for the removal of oil products from surface leaks;