A silicone-modified dry paper for oil-water separation and a method for preparing the same

Abstract

The application belongs to the field of oil-water separation treatment, and specifically discloses an organic silicon modified dry paper for oil-water separation and a preparation method thereof, which comprises the following steps: mixing alkyl chain organosiloxane and cationic photoinitiator, uniformly stirring at room temperature in the dark to obtain a photosensitive organic silicon mixture; taking the prepared photosensitive organic silicon mixture, adding it into an airbrush, and uniformly spraying it on a dry paper to obtain the organic silicon modified dry paper for oil-water separation through photopolymerization. In the application, the organic polysiloxane obtained through hydrolysis and condensation has a three-dimensional network structure, excellent wear resistance and solvent resistance, and is combined with the good tensile strength and large pore size of the substrate dry fiber paper, so that the application has excellent oil-water separation performance and can be reused more than 50 times. The application has simple raw materials, low cost, degradable substrate, green environmental protection, simple preparation process, short time, no use of organic solvents, and small pollution. The reaction condition is easy to achieve, and the application is suitable for large-scale production and application.

Description

Technical Field

[0001] This invention relates to the field of oil-water separation, and particularly to an organosilicon-modified dry paper for oil-water separation and its preparation method. Background Technology

[0002] With the continuous development of society and the economy, the amount of wastewater generated and discharged by human production and daily life is constantly increasing. This wastewater is often a mixture of water and oil, and the oil components are generally toxic. Improper treatment can cause serious harm to local water bodies. In addition, oil spills at sea caused by human activities also seriously threaten the marine environment and the lives of marine life. Faced with the increasingly serious oil pollution problem, researchers have developed a series of oil-water separation methods, such as adsorption, combustion, flocculant methods, and microbial degradation. However, these methods are often not used in isolation, but rather in combination. This leads to drawbacks such as long separation time, low efficiency, large footprint, difficulty in combining technologies, and the potential for secondary pollution.

[0003] Superhydrophobic materials have important applications in many fields such as corrosion prevention, lubrication, and waterproofing, attracting great interest from scientists. Researchers have achieved superhydrophobic properties in substrates using porous metal meshes or fibrous fabrics by impregnating them with hydrophobic solutions, thus obtaining superhydrophobic oil-water separation materials. Although the superhydrophobic materials prepared by this method exhibit excellent oil-water separation performance, they still suffer from drawbacks such as low reusability and poor solvent resistance, and the substrate materials used are non-degradable. Therefore, choosing biodegradable materials to prepare oil-water separation materials not only meets environmental protection requirements but also satisfies cost constraints.

[0004] Cellulose is a renewable biomaterial with good mechanical properties, flexibility, air permeability, and recyclability. Dry-process paper made from cellulose can meet demand while maintaining low production costs. The cellulose macromolecule contains a large number of hydroxyl groups, making it a hydrophilic material, but this also facilitates hydrophobic modification. Chinese patent CN 113186756A discloses a method for preparing superhydrophobic cellulose paper for oil-water separation. The prepared superhydrophobic material for oil-water separation has advantages such as wear resistance, high strength, solvent resistance, and acid and alkali resistance. The prepared material is inexpensive and environmentally friendly. However, its complex preparation process, high drying and curing temperatures, and harsh reaction conditions limit its widespread application. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a method for preparing organosilicon-modified dry paper for oil-water separation. The raw materials of the present invention have low pollution and low cost, the preparation process is simple, the time is short, and the reaction conditions are easy to achieve, which can effectively solve the problems in the background technology.

[0006] This invention is achieved through the following technical solution: A method for preparing organosilicon-modified dry-laid paper for oil-water separation includes the following steps: S1: Mix alkyl chain organosiloxane with cationic photoinitiator and stir evenly at room temperature in the dark to obtain photosensitive organosilicone mixture; S2: Add the above-prepared photosensitive organosilicone mixture to a spray gun and spray it evenly onto dry paper. Photopolymerize to obtain organosilicone modified dry paper for oil-water separation.

[0007] A further improvement to the present invention is as follows: In S1, the mass ratio of the alkyl chain organosiloxane to the cationic photoinitiator is 100:2-12.

[0008] Furthermore, the alkyl chain organosiloxane is one or a mixture of two or more of the following: dodecyltrimethoxysilane, hexadecyltrimethoxysilane, octadecyltrimethoxysilane, 1H,1H,2H,2H-perfluorooctyltrimethoxysilane, and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane.

[0009] Furthermore, the cationic photoinitiator is one or a mixture of two of bis(dodecylphenyl)iodohexafluoroantimonate (UV1242) and 2-methyl-α-[2-[[propanesulfonyl]imine]-3(2H)-thiophene-methylene-phenylacetonitrile (PAG103).

[0010] Furthermore, in S2, the dry paper is air-formed dry fiber paper.

[0011] Furthermore, in S2, the spraying amount of the photosensitive organosilicon mixture is 10-300 g / m². 2 .

[0012] Furthermore, in S2, the light source used in the photopolymerization process is a mercury lamp with a light intensity of 20-500 mW / cm². 2 .

[0013] Furthermore, in S1, the stirring time in the dark is 60-120 min; and in S2, the photopolymerization time is 10-60 min.

[0014] A further improvement of the present invention is as follows: An organosilicon-modified dry-process paper for oil-water separation was prepared by the above method. Beneficial effects

[0015] Compared with the prior art, the present invention has the following obvious advantages: I. This invention uses air-flow shaped dry-laid fiber paper as a substrate, and modifies the surface of the fiber paper by polymerizing alkyl chain organosiloxanes through a cationic-initiated hydrolysis-condensation reaction to prepare organosilicone-modified dry-laid paper for oil-water separation. The organopolysiloxane material formed by the hydrolysis-condensation reaction has a three-dimensional network structure, exhibiting excellent wear resistance and solvent resistance. Combined with the good tensile strength and large pore size of the dry-laid fiber paper, the prepared modified fiber paper possesses excellent oil-water separation performance and can be reused more than 50 times.

[0016] Second, the raw materials of this invention are simple and low in cost, using only alkyl chain organosiloxanes, a small amount of cationic photoinitiator, and dry fiber paper as the substrate material. The dry fiber paper is degradable, renewable, and environmentally friendly. The preparation process is simple and quick, does not use any organic solvents, and has low pollution. The reaction conditions are easy to achieve, and the polymerization reaction only needs to be carried out under light at room temperature, making it suitable for large-scale production applications. Attached Figure Description

[0017] Figure 1 The images are scanning electron microscope (SEM) images of dry fiber paper before and after modification, where (a) is the dry fiber paper before modification and (b) is the dry fiber paper after modification according to Example 2. Detailed Implementation

[0018] The present invention will be further described in detail below with reference to embodiments, but the embodiments of the present invention are not limited thereto. Example 1

[0019] At room temperature, 35 g of octadecyltrimethoxysilane (C18TMS) and 4.2 g of the cationic photoinitiator bis(dodecylphenyl)iodohexafluoroantimonate (UV1242) were added to a brown screw-top bottle. After shielding from light, the mixture was stirred for 120 min. The mixed photosensitive silicone solution was then evenly sprayed onto dry fiber paper using a spray gun at a spray rate of 100 g / m². The paper was then placed under a light intensity of 100 mW / cm². 2 The paper was obtained by irradiating it under a mercury lamp for 30 minutes, and the paper was modified with organosilicon. Example 2

[0020] At room temperature, 35g of hexadecyltrimethoxysilane (C16TMS) and 3.5g of the cationic photoinitiator bis(dodecylphenyl)iodohexafluoroantimonate (UV1242) were added to a brown screw-top bottle. After shielding from light, the mixture was stirred for 80 minutes. The mixed photosensitive silicone solution was then evenly sprayed onto dry fiber paper using a spray gun at a rate of 150g / m². The paper was then placed under a light intensity of 100mW / cm². 2 The paper was obtained by irradiating it under a mercury lamp for 30 minutes, and the paper was modified with organosilicon. Example 3

[0021] At room temperature, 35g of dodecyltrimethoxysilane (C12TMS) and 2.4g of the cationic photoinitiator bis(dodecylphenyl)iodohexafluoroantimonate (UV1242) were added to a brown screw-top bottle. After shielding from light, the mixture was stirred for 60 minutes. The mixed photosensitive organosilicon solution was then evenly sprayed onto dry fiber paper using a spray gun at a rate of 300g / m². The paper was then placed under a light intensity of 200mW / cm². 2 Organosilicon-modified dry-process paper was obtained by irradiating the paper under a mercury lamp for 60 minutes. Example 4

[0022] At room temperature, 35g of 1H,1H,2H,2H-perfluorooctyltrimethoxysilane and 3g of the cationic photoinitiator 2-methyl-α-[2-[[propanesulfonyl]imine]-3(2H)-thiophene-methylene-phenylacetonitrile (PAG103) were placed in a brown screw-top bottle, protected from light, and stirred for 60 min. The mixed photosensitive organosilicon solution was then evenly sprayed onto dry fiber paper using a spray gun at a spray rate of 150g / m², and then placed under a light intensity of 100mW / cm². 2 The paper was obtained by irradiating it under a mercury lamp for 30 minutes, and the paper was modified with organosilicon. Example 5

[0023] At room temperature, 35g of octadecyltrimethoxysilane (C18TMS) and 1.5g of the cationic photoinitiator 2-methyl-α-[2-[[propanesulfonyl]imine]-3(2H)-thiophene-methylene-phenylacetonitrile (PAG103) were placed in a brown screw-top bottle, protected from light, and stirred for 60min. The mixed photosensitive organosilicon solution was then uniformly sprayed onto dry fiber paper using a spray gun at a spray rate of 40g / m², and then placed under a light intensity of 100mW / cm². 2 The paper was irradiated under a mercury lamp for 10 minutes to obtain organosilicon-modified dry paper. Example 6

[0024] At room temperature, 35g of octadecyltrimethoxysilane (C18TMS) and 1g of bis(dodecylphenyl)iodohexafluoroantimonate (UV1242) as the cationic photoinitiator were placed in a brown screw-top bottle. After shielding from light, the mixture was stirred for 60 minutes. The mixed photosensitive organosilicon solution was then evenly sprayed onto dry fiber paper using a spray gun at a spray rate of 100g / m². The paper was then placed under a light intensity of 20mW / cm². 2 Organosilicon-modified dry-process paper was obtained by irradiating the paper under a mercury lamp for 60 minutes.

[0025] The test descriptions for Examples 1 to 6 specifically include tests on hydrophobic properties, separation flux, initial separation efficiency, and separation efficiency after 50 cycles, as shown in Table 1.

[0026] Table 1 Performance test results of silicone-modified dry paper prepared in different embodiments

[0027] As shown in Table 1, the water contact angles of the embodiments of the present invention are all above 135°, exhibiting high hydrophobicity, and the initial separation efficiency can reach above 96%. In the embodiments, as the amount of photosensitive organosilicon mixture sprayed increases, the separation throughput of the sample decreases. After 50 repeated oil-water separations, the high amount of photosensitive organosilicon mixture sprayed still maintains good separation effect, demonstrating strong repeatability and practicality.

[0028] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be construed as limiting the scope of protection of the present invention. All equivalent transformations or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A method for preparing organosilicon-modified dry-process paper for oil-water separation, characterized in that, Includes the following steps: S1: Mix alkyl chain organosiloxane with cationic photoinitiator, stir evenly at room temperature in the dark to obtain photosensitive organosilicon mixture; S2: Take the photosensitive organosilicon mixture prepared above and add it to the spray gun. Spray it evenly onto the dry paper and polymerize it under light to obtain organosilicon modified dry paper for oil-water separation. In S1, the mass ratio of the alkyl chain organosiloxane to the cationic photoinitiator is 100:2-12; The alkyl chain organosiloxane is one or a mixture of two or more of the following: dodecyltrimethoxysilane, hexadecyltrimethoxysilane, octadecyltrimethoxysilane, 1H,1H,2H,2H-perfluorooctyltrimethoxysilane, and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane. The cationic photoinitiator is one or a mixture of two of bis(dodecylphenyl)iodohexafluoroantimonate (UV1242) and 2-methyl-α-[2-[[propanesulfonyl]imine]-3(2H)-thiophene-methylene-phenylacetonitrile (PAG103).

2. The method for preparing organosilicon-modified dry paper for oil-water separation according to claim 1, characterized in that: In S2, the dry paper is air-formed dry fiber paper.

3. The method for preparing organosilicon-modified dry paper for oil-water separation according to claim 1, characterized in that: In S2, the spraying amount of the photosensitive organosilicon mixture is 10-300 g / m2.

4. The method for preparing organosilicon-modified dry paper for oil-water separation according to claim 1, characterized in that: In S2, the light source used in the photopolymerization process is a mercury lamp with a light intensity of 20-500 mW / cm2.

5. The method for preparing organosilicon-modified dry paper for oil-water separation according to claim 1, characterized in that: In S1, the stirring time in the dark is 60-120 min; and in S2, the photopolymerization time is 10-60 min.

6. An organosilicon-modified dry-process paper for oil-water separation prepared by the preparation method according to any one of claims 1-5.

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