Polymeric membrane and preparation method thereof

Abstract

The invention belongs to the technical field of polymer functional materials, and relates to a polymer film and a preparation method thereof. The invention provides a preparation method of a polymeric membrane, which comprises the following steps: mixing, stirring and heating a membrane-forming substance and water to obtain a membrane-forming substance solution with the mass concentration of 10-15wt%; mixing the film-forming substance solution, a functional monomer and a cross-linking agent in a mass ratio of (10-15): (1-5): (1-3), and reacting to obtain a polymeric film solution; drying the polymeric membrane solution to obtain a polymeric membrane; the preparation method disclosed by the invention is simple and easy to operate, and the chemical crosslinking modified polymeric membrane disclosed by the invention can be recycled, so that the cost can be saved, and the chemical crosslinking modified polymeric membrane has a better application prospect in the field of water dye treatment.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer functional materials and relates to a polymer film and a preparation method thereof. Background Art

[0002] Dye particles in water bodies mainly come from dye manufacturing, printing and dyeing, and textile industries. Dye particles are mainly aromatic and anthraquinone organic compounds, which have certain biological toxicity and can cause organ lesions after entering the human body. If water bodies containing dye particles are directly discharged into the natural environment, it will seriously affect the surrounding soil, water sources and ecological environment. The treatment of dye particles in water bodies has always been one of the problems that need to be solved urgently in China's environmental protection field.

[0003] The adsorption process has the characteristics of high adsorption efficiency, large adsorption capacity and simple operation, and is a common method for removing dye particles from water. However, most of the adsorbents currently used are in the form of powders. While achieving excellent adsorption effects, the powders are difficult to remove from the water, and the regeneration and recycling rate is low.

[0004] Membrane adsorption has become a new adsorption method with considerable competitiveness in recent years because it is easy to remove from water bodies. The membrane adsorption process also has the characteristics of high adsorption efficiency, large adsorption capacity and simple adsorption process operation. The present invention solves the problem that powder adsorbents are not easy to reuse by preparing polymer membrane adsorption materials. Summary of the invention

[0005] The purpose of the present invention is to provide a polymer film and a preparation method thereof. The film-forming material is chemically cross-linked by a cross-linking agent to obtain a chemically cross-linked modified polymer film. The polymer film has the advantages of simple preparation method, recyclability, strong applicability, and excellent performance in adsorbing dye particles.

[0006] Based on the above purpose, the present application solves this need in the field by providing a method for preparing a polymer film.

[0007] In one aspect, the present invention relates to a method for preparing a polymer film, comprising:

[0008] The film-forming substance and water are mixed, stirred, and heated to obtain a film-forming substance solution with a mass concentration of 10 to 15 wt %;

[0009] A film-forming substance solution, a functional monomer and a cross-linking agent are mixed in a mass ratio of 10 to 15:1 to 5:1 to 3, and reacted to obtain a polymer film solution; the polymer film solution is dried to obtain a polymer film;

[0010] The structure of the film-forming substance is m is an integer ranging from 500 to 2400;

[0011] The structure of the functional monomer is n = 0, 1, 2;

[0012] The structure of the crosslinking agent is R1 is a hydrocarbon group with 1 to 4 carbon atoms;

[0013] The structure of the polymer film is as follows:

[0014]

[0015] Furthermore, in a method for preparing a polymer film provided by the present invention, in the step of mixing the film-forming substance and water, stirring, and heating, the heating temperature is 95 to 100 °C, and stirring is carried out for 3 to 8 h to obtain a film-forming substance solution.

[0016] Furthermore, in a method for preparing a polymer film provided by the present invention, in the step of mixing the film-forming substance, the functional monomer, and the crosslinking agent, heating and stirring are carried out in a constant temperature water bath, the heating temperature is 70 to 80 °C, and stirring is carried out for 4 to 6 h to obtain a polymer film solution.

[0017] Furthermore, in a method for preparing a polymer film provided by the present invention, in the step of drying the polymer film solution to obtain the polymer film, the polymer film solution is dried at 50 to 60 °C for 24 to 48 h to obtain the polymer film.

[0018] Preferably, in a method for preparing a polymer film provided by the present invention, R1 is a hydrocarbon group with 1 to 2 carbon atoms.

[0019] Furthermore, in a method for preparing a polymer film provided by the present invention, in the structural formula of the film-forming substance, m takes a value of 1700 to 2400.

[0020] On the other hand, the present invention relates to a polymer film, and by adding a chemical crosslinking agent, the prepared polymer film has excellent stability and adsorption performance.

[0021] On the other hand, the polymer film prepared by the present invention has certain adsorption performance, and can especially adsorb wastewater containing methylene blue, methyl violet, and basic fuchsin. Therefore, the present invention requests protection for the application of the polymer film in treating wastewater containing dye particles.

[0022] On the other hand, the present invention overcomes the disadvantages of powder adsorbents, has a simple preparation method and is easy to operate, and has a better application prospect in the field of water body dye treatment. Therefore, the present invention requests protection for the application of the above-mentioned polymer film in water body dye adsorption.

[0023] The present invention has the following beneficial effects or advantages compared with the prior art:

[0024] (1) The present invention uses a basic film-forming substance with excellent adsorption and film-forming properties as the base material. By adding a chemical cross-linking agent, the stability and adsorption performance of the polymer film are further improved, and it can be used for the removal of dye particles in water bodies.

[0025] (2) The chemically cross-linked modified polymer film obtained in the present invention contains a carboxyl structure, has a strong electrostatic adsorption effect on cationic dyes, and has excellent adsorption performance. The removal rate of basic fuchsin can reach 97.87%, and the purification of water bodies can be efficiently achieved.

[0026] (3) The present invention overcomes the shortcomings of powder adsorbents. The preparation method is simple and easy to operate. Moreover, the chemically cross-linked modified polymer film of the present invention can be recycled and reused, which can save costs and has good application prospects in the field of water body dye treatment. Description of the Drawings

[0027] Figure 1 Shows the adsorption and removal rates of methylene blue, methyl violet and basic fuchsin by the polymer film.

[0028] Figure 2 Shows the effect diagram of the repeated use performance test of the polymer film. Detailed Embodiments

[0029] Next, the technical solutions of the present invention will be described in conjunction with the embodiments. However, the present invention is not limited to the following embodiments.

[0030] In order to enable those skilled in the art to better understand and implement the technical solutions of the present invention, the present invention will be further described below in conjunction with specific embodiments and drawings, but the embodiments given are not intended to limit the present invention.

[0031] In the following embodiments, the experimental methods and detection methods are all conventional methods unless otherwise specified; the reagents and materials can all be purchased on the market unless otherwise specified.

[0032] Embodiments

[0033] Example 1

[0034] This example provides a preparation method of a polymer film.

[0035] Weigh 15.6 g of the film-forming substance and add it to a three-necked flask. Add 100 ml of distilled water, stir and heat in a constant temperature water bath. The heating temperature is 98 °C, and stir for 5 h to obtain a film-forming substance solution, and cool it to room temperature.

[0036] Weigh 26 g of the film-forming substance solution, 6 g of the functional monomer, and 4 g of the cross-linking agent, and sequentially add them to a three-necked flask. Stir and heat in a constant-temperature water bath at a heating temperature of 75 °C for 5 h to obtain a polymer film solution. Slowly pour the obtained polymer film solution into a petri dish and dry it in an oven at 55 °C for 40 h to obtain a polymer film.

[0037] The structural formula of the film-forming substance is The structural formula of the functional monomer is The structural formula of the cross-linking agent is The structural formula of the polymer film is

[0038]

[0039] Example 2

[0040] This example provides a method for preparing a polymer film.

[0041] Weigh 10 g of the film-forming substance and add it to a three-necked flask. Add 90 ml of distilled water, stir and heat in a constant-temperature water bath at a heating temperature of 95 °C for 3 h to obtain a film-forming substance solution, and cool it to room temperature;

[0042] Weigh 20 g of the film-forming substance solution, 2 g of the functional monomer, and 2 g of the cross-linking agent, and sequentially add them to a three-necked flask. Stir and heat in a constant-temperature water bath at a heating temperature of 70 °C for 4 h to obtain a polymer film solution. Slowly pour the obtained polymer film solution into a petri dish and dry it in an oven at 50 °C for 24 h to obtain a polymer film.

[0043] The structural formula of the film-forming substance is The structural formula of the functional monomer is The structural formula of the cross-linking agent is The structural formula of the polymer film is

[0044]

[0045] Example 3

[0046] This example provides a method for preparing a polymer film.

[0047] Weigh 15 g of the film-forming substance and add it to a three-necked flask. Add 85 ml of distilled water, stir and heat in a constant-temperature water bath at a heating temperature of 100 °C for 8 h to obtain a film-forming substance solution, and cool it to room temperature;

[0048] Weigh 30 g of the film-forming substance solution, 10 g of the functional monomer, and 6 g of the cross-linking agent, and add them to a three-necked flask in sequence. Stir and heat in a constant-temperature water bath at a heating temperature of 80 °C for 6 h to obtain a polymer film solution. Slowly pour the obtained polymer film solution into a petri dish and dry it in an oven at 60 °C for 48 h to obtain a polymer film.

[0049] The structural formula of the film-forming substance is The structural formula of the functional monomer is The structural formula of the cross-linking agent is The structural formula of the polymer film is

[0050]

[0051] Example 4

[0052] This example provides a method for preparing a polymer film.

[0053] The difference from Example 1 is that the structural formula of the film-forming substance is The structural formula of the polymer film is

[0054]

[0055] Example 5

[0056] This example provides a method for preparing a polymer film.

[0057] The difference from Example 1 is that the structural formula of the film-forming substance is The structural formula of the functional monomer is The structural formula of the polymer film is

[0058]

[0059] Example 6

[0060] This example provides a method for preparing a polymer film.

[0061] The difference from Example 2 is that the mass ratio of the film-forming substance solution, the functional monomer, and the cross-linking agent is 8:0.8:0.8. The specific preparation steps are as follows: Weigh 16 g of the film-forming substance solution, 1.6 g of the functional monomer, and 1.6 g of the cross-linking agent, and add them to a three-necked flask in sequence. Stir and heat in a constant-temperature water bath at a heating temperature of 80 °C for 6 h to obtain a polymer film solution. Slowly pour the obtained polymer film solution into a petri dish and dry it in an oven at 60 °C for 48 h to obtain a polymer film.

[0062] Example 7

[0063] This example provides a method for preparing a polymer film.

[0064] The difference from Example 3 is that the mass ratio of the film-forming substance solution, functional monomer and crosslinking agent is 18:9:5. The specific preparation steps are as follows: Weigh 36 g of the film-forming substance solution, 18 g of the functional monomer and 10 g of the crosslinking agent, and add them to a three-necked flask in sequence. Stir and heat in a constant temperature water bath. The heating temperature is 80 °C, and stir for 6 h to obtain a polymer film solution. Slowly pour the obtained polymer film solution into a petri dish and place it in an oven at 60 °C for drying for 48 h to obtain a polymer film.

[0065] Example 8

[0066] This example provides a method for preparing a polymer film.

[0067] The difference from Example 2 is that the mass concentration of the film-forming substance is 8 wt%. The specific preparation steps are as follows: Weigh 8 g of the film-forming substance and add it to a three-necked flask, add 92 ml of distilled water, stir and heat in a constant temperature water bath. The heating temperature is 100 °C, and stir for 8 h to obtain a film-forming substance solution, and cool it to room temperature.

[0068] Example 9

[0069] This example provides a method for preparing a polymer film.

[0070] The difference from Example 3 is that the mass concentration of the film-forming substance is 17 wt%. The specific preparation steps are as follows: Weigh 17 g of the film-forming substance and add it to a three-necked flask, add 83 ml of distilled water, stir and heat in a constant temperature water bath. The heating temperature is 100 °C, and stir for 8 h to obtain a film-forming substance solution, and cool it to room temperature.

[0071] Example 10

[0072] This example conducts performance tests on the polymer films prepared in Examples 1-9:

[0073] (1) Removal rate test: Cut the polymer film into 1 cm × 1 cm squares. Prepare methylene blue, methyl violet and basic fuchsin solutions with a dye concentration of 20 mg / L respectively. Add the cut square polymer films to the prepared dye solutions and place them in a constant temperature oscillator for oscillation for 24 h. Test the concentrations c0 and c of methylene blue, methyl violet and basic fuchsin before and after the polymer film adsorption e , and calculate the removal rate of the polymer film through the following formula.

[0074]

[0075] Among them, R is the removal rate of the polymer film for the dye (%), c0 is the initial concentration of the dye solution (mg / L), and c e is the concentration of the dye solution after adsorption (mg / L).

[0076] (2) Reusability test: Take out the polymer membrane after the adsorption test experiment and dry it. Place the dried polymer membrane in a sealed beaker containing 10 mL of distilled water. Put the beaker into an ultrasonic machine and ultrasonicate for 4 h. Take out the membrane, dry it again, and conduct the next adsorption experiment.

[0077] Figure 1 are the adsorption removal rates of the polymer membrane for methylene blue, methyl violet, and basic fuchsin. X1 - X5 respectively correspond to the adsorption effects of the polymer membranes in Examples 1 - 5. From Figure 1 it can be seen that the polymer membrane prepared by the present invention has good adsorption effects on cationic dyes methylene blue, methyl violet, and basic fuchsin, especially for basic fuchsin. For the polymer membrane prepared in Example 4, the removal rate for methylene blue is 83.15%, the removal rate for methyl violet is 72.12%, and the removal rate for basic fuchsin is 97.87%, and the adsorption effects are all good. Figure 2 is the effect diagram of the reusability test using the polymer membrane prepared in Example 4. It can be seen from the figure that after 5 reusability tests, the polymer membrane can still exhibit good adsorption performance.

[0078] The test results of the adsorption removal rates of the polymer membranes prepared in Examples 6 - 9 for methylene blue, methyl violet, and basic fuchsin show that the removal rates of the polymer membranes prepared in Examples 6 - 9 for methylene blue are generally lower than 64.15%, the removal rates for methyl violet are generally lower than 55.13%, and the removal rates for basic fuchsin are generally lower than 70.53%; and after 5 reusability tests of the polymer membranes prepared in Examples 6 - 9, the adsorption performance of the polymer membranes drops significantly, and compared with the polymer membranes prepared in Examples 1 - 5, the recycling performance decreases.

[0079] As described above, the present invention can be preferably implemented. The above - mentioned embodiments are only descriptions of the preferred implementation modes of the present invention, and do not limit the scope of the present invention. Without departing from the design spirit of the present invention, various changes and improvements made by those of ordinary skill in the art to the technical solutions of the present invention should all fall within the protection scope determined by the present invention.

Claims

1. A method for preparing a polymer membrane, characterized in that, Including: Mix the film-forming substance and water, stir, and heat to obtain a film-forming substance solution with a mass concentration of 10-15 wt%. Mix the film-forming substance solution, functional monomer, and cross-linking agent with a mass ratio of 10-15:1-5:1-3, and react to obtain a polymer film solution. Dry the polymer film solution to obtain the polymer film. The structure of the film-forming substance is m is an integer with a value ranging from 500 to 2400; The structure of the functional monomer is n = 0, 1, 2; The structure of the crosslinking agent is R1 is a hydrocarbon group having 1 to 4 carbon atoms; The structure of the polymer film is:

2. The preparation method of the polymer film according to claim 1, characterized in that, In the step of mixing the film-forming substance and water, stirring, and heating, the heating temperature is 95-100 °C, and stirring is carried out for 3-8 h to obtain the film-forming substance solution.

3. The preparation method of the polymer film according to claim 1, characterized in that In the step of mixing the film-forming substance, functional monomer, and cross-linking agent, heat and stir in a constant temperature water bath, the heating temperature is 70-80 °C, and stirring is carried out for 4-6 h to obtain the polymer film solution.

4. The preparation method of the polymer membrane according to claim 1, characterized in that, In the step of drying the polymer film solution to obtain the polymer film, dry the polymer film solution at 50-60 °C for 24-48 h to obtain the polymer film.

5. The preparation method of the polymer membrane according to claim 1, wherein, The R1 is a hydrocarbon group of C1-C2.

6. The method for preparing the polymer membrane according to claim 1, wherein In the structural formula of the film-forming substance, m takes a value of 1700-2400.

7. A polymer film prepared by the preparation method of the polymer film according to any one of claims 1-6.

8. Application of the polymer film according to claim 7 in wastewater treatment.

9. The application according to claim 8, characterized in that, The wastewater contains one or more of methylene blue, methyl violet, and basic fuchsin.

10. Application of the polymer film according to claim 7 in water body dye adsorption.

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