Preparation method and application of poly (hydroxyethyl methacrylate) porous material
By preparing polyhydroxyethyl methacrylate porous material, the formation of hydrophobic layer improves its self-cleaning ability, the problem of poor self-cleaning effect of existing polymer porous materials is solved, and the excellent hydrophobic characteristics and self-cleaning function of the material are achieved .
Patent Information
- Application Number
- CN202411352283.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-26
- Publication Date
- 2024-12-20
AI Technical Summary
The self-cleaning effect of existing polymer porous materials is poor, and it is difficult to effectively prevent the adsorption and adhesion of pollutants under the action of external forces, which limits its application in the fields of thermal insulation materials and other fields.
Using a preparation method of a polyhydroxyethyl methacrylate porous material, by mixing hydroxyethyl methacrylate monomer with deionized water, adding a photoinitiator and performing ultraviolet light induction, followed by methyltrimethoxysilane The reaction is to form a dense hydrophobic layer, which improves the hydrophobic properties of the material.
It realizes excellent hydrophobic properties and self-cleaning ability of polymer porous materials, can effectively prevent the adhesion and adsorption of pollutants, and expands its application range in the fields of thermal insulation materials and other fields.
Smart Images
Figure CN119161632A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of polymer material self-cleaning, and in particular relates to a preparation method and application of a polyhydroxyethyl methacrylate porous material. Background Art
[0002] Self-cleaning materials are a new type of material with broad application prospects. Their surfaces can automatically clean themselves under external stimuli and can effectively prevent the adsorption and adhesion of pollutants. This material has important application potential in many fields, including construction, energy, environment and medicine. In the past few decades, people have been committed to the research and development of self-cleaning materials to cope with the increasingly severe environmental and energy problems. Traditional cleaning methods require manual intervention and the use of chemical cleaners, which are not only time-consuming and labor-intensive, but may also have negative impacts on the environment. Therefore, the development of a material that can clean itself is of great significance to improving the quality of life, reducing energy consumption and protecting the environment.
[0003] Polymer porous materials are a type of porous materials formed by a high molecular polymer skeleton, with low density, high specific surface area and excellent adsorption performance. These characteristics make polymer porous materials widely used in various fields, such as adsorbents, radiant refrigeration and thermal insulation materials. Thermal insulation materials are often used in outdoor environments, such as tents and roofs of buildings. They will inevitably be contaminated by sewage and dust during use. If the hydrophobic properties of the material can be enhanced, it will help reduce the adhesion of pollutants on the surface of the thermal insulation material. Under the action of external forces, the stains will fall off by themselves, thereby expanding the application range of the thermal insulation material and enabling it to achieve the function of self-cleaning. However, the polymer porous materials prepared by the prior art still have the problem of poor self-cleaning effect. Summary of the invention
[0004] In order to solve the problem that the polymer porous material prepared by the prior art still has poor self-cleaning effect, the purpose of the present invention is to provide a preparation method and application of polyhydroxyethyl methacrylate porous material.
[0005] The purpose of the present invention can be achieved through the following technical solutions:
[0006] A method for preparing a poly(hydroxyethyl methacrylate) porous material comprises the following steps:
[0007] Step A1: uniformly mix and disperse hydroxyethyl methacrylate monomer and deionized water until transparent, and stir on a magnetic stirrer at 18-30° C. for 30 minutes to prepare a polymerizable eutectic solvent system;
[0008] The dosage ratio of hydroxyethyl methacrylate monomer to deionized water is 0.8-1.2 g: 5-10 mL.
[0009] Step A2: adding a photoinitiator to a polymerizable eutectic solvent system, continuously introducing nitrogen to remove bubbles, and then pouring into a polytetrafluoroethylene mold, inducing with ultraviolet light for 30 minutes to prepare poly(hydroxyethyl methacrylate) gel, and freeze-drying to obtain poly(hydroxyethyl methacrylate);
[0010] The usage ratio of the polymerizable eutectic solvent system to the photoinitiator is 5-10 mL: 0.01-0.05 g.
[0011] Step A3: adding methyltrimethoxysilane and deionized water to poly(hydroxyethyl methacrylate) respectively, reacting at 60-80° C. for 4 hours, washing away the unreacted methyltrimethoxysilane with anhydrous ethanol, and drying at room temperature to obtain a poly(hydroxyethyl methacrylate) porous material;
[0012] The dosage ratio of polyhydroxyethyl methacrylate, methyltrimethoxysilane and deionized water is 0.6-1.2 g: 0.6-1.2 g: 0.8-1.4 mL.
[0013] Furthermore, in step A2, the photoinitiator is any one of 2,2-diethoxy-1-acetophenone, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone, 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone, and 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone.
[0014] Furthermore, in step A2, the wavelength of the ultraviolet light is 365 nm and the light intensity is 80 mW / cm -2 .
[0015] Furthermore, a poly(hydroxyethyl methacrylate) porous material plays an important application in the field of self-cleaning materials.
[0016] Beneficial effects of the present invention:
[0017] 1. The present invention designs a new poly(hydroxyethyl methacrylate) porous structure system. In the system, the acrylic acid ester monomer containing double bonds can not only be miscible with deionized water, but also construct a porous structure during the freeze-drying process after forming a gel.
[0018] 2. The polymer hydroxyethyl methacrylate network in the present invention constructs a shape-stable porous structure system. The silanized polymer hydroxyethyl methacrylate porous skeleton forms a dense hydrophobic layer, further improving the hydrophobic properties of the material, thereby making the material have self-cleaning ability.
[0019] 3. The present invention designs a method for preparing a hydrophobic polymer porous material. The preparation process is simple, the method is easy to operate, the raw materials are cheap and easily available, and the polymer porous material prepared by the preparation method has excellent hydrophobic properties. BRIEF DESCRIPTION OF THE DRAWINGS
[0020] The present invention will be further described below in conjunction with the accompanying drawings.
[0021] Figure 1 For comparative example 1 ( Figure 1 A) Example 1 Figure 1 B), Example 2 ( Figure 1 C) Digital image of the prepared poly(hydroxyethyl methacrylate) porous material;
[0022] Figure 2 For comparative example 1 ( Figure 2 a), Example 1 ( Figure 2 b) Example 2 Figure 2 c) Example 3 Figure 2 d) SEM image of the prepared poly(hydroxyethyl methacrylate) porous material;
[0023] Figure 3 The digital images of the poly(hydroxyethyl methacrylate) porous material prepared in Example 1 in different solutions;
[0024] Figure 4 The dynamic contact angle diagrams of the poly(hydroxyethyl methacrylate) porous materials prepared in Comparative Example 1 and Example 1;
[0025] Figure 5 The contact angle diagram of the poly(hydroxyethyl methacrylate) porous material prepared in Comparative Example 1 and Example 2 in different solvents;
[0026] Figure 6 This is a diagram showing the self-cleaning application of the poly(hydroxyethyl methacrylate) porous material prepared in Comparative Example 1 in an aqueous solution of an organic dye, Rhodamine B;
[0027] Figure 7 This is a diagram showing the self-cleaning application of the poly(hydroxyethyl methacrylate) porous material prepared in Example 1 in an aqueous solution of Rhodamine B organic dye. DETAILED DESCRIPTION
[0028] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0029] In the present invention, hydroxyethyl methacrylate (98%, containing 200-600ppm MEHQ stabilizer) was purchased from Shanghai Titan Technology Co., Ltd.; photoinitiator (>95%) was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; methyltrimethoxysilane (RG, 99%) was purchased from Shanghai Titan Technology Co., Ltd.
[0030] Example 1
[0031] This embodiment provides a method for preparing a poly(hydroxyethyl methacrylate) porous material, comprising the following steps:
[0032] Step A1: 0.8 g of hydroxyethyl methacrylate monomer was uniformly mixed and dispersed with 5 mL of deionized water until transparent, and uniformly stirred on a magnetic stirrer at 18° C. for 30 min to prepare a polymerizable eutectic solvent system;
[0033] Step A2: Add 0.01 g of 2,2-diethoxy-1-acetophenone to 5 mL of the polymerizable eutectic solvent system obtained in step 1, continue to introduce nitrogen gas to remove bubbles, and then pour into a polytetrafluoroethylene mold, and induce under ultraviolet light for 30 min (ultraviolet light wavelength is 365 nm, maximum light intensity is 80 mW / cm -2 ), to prepare poly(hydroxyethyl methacrylate) gel, which was frozen by liquid nitrogen and then transferred to a freeze dryer for freeze drying to obtain poly(hydroxyethyl methacrylate);
[0034] Step A3: Place 0.6 g of poly(hydroxyethyl methacrylate) in a sealed container, then add 0.6 g of methyltrimethoxysilane and 0.8 mL of deionized water into the sealed container respectively, react at 60°C for 4 hours, wash away the unreacted methyltrimethoxysilane with deionized water, and dry at room temperature to obtain a poly(hydroxyethyl methacrylate) porous material.
[0035] Example 2
[0036] This embodiment provides a method for preparing a poly(hydroxyethyl methacrylate) porous material, comprising the following steps:
[0037] Step A1: 1 g of hydroxyethyl methacrylate monomer was uniformly mixed and dispersed with 8 mL of deionized water until transparent, and uniformly stirred on a magnetic stirrer at 25° C. for 30 min to prepare a polymerizable eutectic solvent system;
[0038] Step A2: 0.03 g of 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone was added to 8 mL of the polymerizable eutectic solvent system obtained in step A1, and nitrogen was continuously introduced to remove bubbles and then poured into a polytetrafluoroethylene mold, and induced under ultraviolet light for 30 min (ultraviolet light wavelength was 365 nm, light intensity was 80 mW / cm -2), to prepare poly(hydroxyethyl methacrylate) gel, which was frozen by liquid nitrogen and then transferred to a freeze dryer for freeze drying to obtain poly(hydroxyethyl methacrylate);
[0039] Step A3: Place 0.9 g of poly(hydroxyethyl methacrylate) in a sealed container, then add 0.9 g of methyltrimethoxysilane and 1 mL of deionized water into the sealed container respectively, react at 70°C for 4 hours, wash away the unreacted methyltrimethoxysilane with deionized water, and dry at room temperature to obtain a poly(hydroxyethyl methacrylate) porous material.
[0040] Example 3
[0041] This embodiment provides a method for preparing a poly(hydroxyethyl methacrylate) porous material, comprising the following steps:
[0042] Step A1: 1.2 g of hydroxyethyl methacrylate monomer was uniformly mixed and dispersed with 10 mL of deionized water until transparent, and uniformly stirred on a magnetic stirrer at 30° C. for 30 min to prepare a polymerizable eutectic solvent system;
[0043] Step A2: Add 0.05 g of 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone to 10 mL of the polymerizable eutectic solvent system obtained in step A1, continue to introduce nitrogen gas to remove bubbles, and then pour into a polytetrafluoroethylene mold, and induce under ultraviolet light for 30 min (ultraviolet light wavelength is 365 nm, light intensity is 80 mW / cm -2 ), to prepare poly(hydroxyethyl methacrylate) gel, which was frozen by liquid nitrogen and then transferred to a freeze dryer for freeze drying to obtain poly(hydroxyethyl methacrylate);
[0044] Step A3: Place 1.2 g of poly(hydroxyethyl methacrylate) in a sealed container, then add 1.2 g of methyltrimethoxysilane and 1.4 mL of deionized water into the sealed container respectively, react at 80°C for 4 hours, wash away the unreacted methyltrimethoxysilane with deionized water, and dry at room temperature to obtain a poly(hydroxyethyl methacrylate) porous material.
[0045] Comparative Example 1
[0046] This comparative example provides a method for preparing a poly(hydroxyethyl methacrylate) porous material, comprising the following steps:
[0047] Step A1: 0.8 g of hydroxyethyl methacrylate monomer was uniformly mixed and dispersed with 5 mL of deionized water until transparent, and uniformly stirred on a magnetic stirrer at 18° C. for 30 min to prepare a polymerizable eutectic solvent system;
[0048] Step A2: Add 0.01 g of 2,2-diethoxy-1-acetophenone to 5 mL of the polymerizable eutectic solvent system obtained in step 1, continue to introduce nitrogen to remove bubbles, and then pour it into a polytetrafluoroethylene mold, induce it under ultraviolet light for 30 minutes (ultraviolet light wavelength is 365 nm, light intensity is 80 mW / cm-2), and prepare poly(hydroxyethyl methacrylate) gel, which is frozen by liquid nitrogen and then transferred to a freeze dryer for freeze drying to obtain a poly(hydroxyethyl methacrylate) porous material.
[0049] The poly(hydroxyethyl methacrylate) porous materials prepared in Examples 1 to 3 and Comparative Example 1 were tested, and the results are as follows: Figure 1-Figure 7 As shown:
[0050] The products obtained in Comparative Example 1, Example 1 and Example 2 were photographed using a digital camera. The results are as follows: Figure 1 As shown by Figure 1 It can be seen that the comparative example 1 ( Figure 1 A) Example 1 Figure 1 B), Example 2 ( Figure 1 C) of poly(hydroxyethyl methacrylate) porous material was successfully prepared.
[0051] Comparative Example 1 and Examples 1-3 were observed by scanning electron microscopy. Figure 2 As shown by Figure 2 It can be seen that Example 1 ( Figure 2 b) Example 2 Figure 2 c) and Example 3 ( Figure 2 d) The prepared poly(hydroxyethyl methacrylate) porous material is compared with the comparative example 1 ( Figure 2 a) The prepared poly(hydroxyethyl methacrylate) porous material has a richer porous structure, and its microscopic pores have a further cross-linked skeleton. This shows that the poly(hydroxyethyl methacrylate) porous material after silanization treatment has a multi-level structure, which lays a foundation for the super-hydrophobicity of the material.
[0052] The hydrophobicity of the poly(hydroxyethyl methacrylate) porous material prepared in Example 1 in water, milk, hydrochloric acid solution (1 mol / L), sodium hydroxide solution (1 mol / L), cola and coffee was photographed using a digital camera. The results are as follows: Figure 3 As shown by Figure 3 It can be seen that the poly(hydroxyethyl methacrylate) porous material treated with methyltrimethoxysilane exhibits excellent hydrophobic properties to different solvents.
[0053] The dynamic contact angle behavior of water on the surface of the poly(hydroxyethyl methacrylate) porous material prepared in Comparative Example 1 and Example 1 was investigated by a contact angle measuring instrument. The results are as follows: Figure 4 As shown by Figure 4It can be seen that the poly(hydroxyethyl methacrylate) porous material prepared in Example 1 not only has high hydrophobicity, but also has significantly better dynamic contact angle stability than that of Comparative Example 1.
[0054] The contact angles of the porous poly(hydroxyethyl methacrylate) materials prepared in Comparative Example 1 and Example 2 in milk, sodium hydroxide solution (1 mol / L), coffee, cola, and water were measured by a contact angle measuring instrument. The results are as follows: Figure 5 As shown by Figure 5 It can be seen that the contact angles of Example 2 in different solvents are greater than those of Comparative Example 1, indicating that the hydrophobicity of the poly(hydroxyethyl methacrylate) porous material prepared in Example 2 is better than that of Comparative Example 1 in different solvents.
[0055] The poly(hydroxyethyl methacrylate) porous material prepared in Comparative Example 1 was placed in a 0.1 mol / L Rhodamine B organic dye aqueous solution, and taken out after immersion to observe whether it was stained. If it was stained, it means that the self-cleaning ability of the material was poor. If it was not stained, it means that the self-cleaning ability of the material was excellent. The results are as follows: Figure 6 As shown by Figure 6 It can be seen that the poly(hydroxyethyl methacrylate) porous material after being taken out shows an obvious color change, indicating that the poly(hydroxyethyl methacrylate) porous material that has not been silanized has poor self-cleaning ability.
[0056] The poly(hydroxyethyl methacrylate) porous material prepared in Example 1 was placed in a 0.1 mol / L Rhodamine B organic dye aqueous solution, and after immersion, it was taken out to observe whether it was stained. If it was stained, it means that the self-cleaning ability of the material was poor. If it was not stained, it means that the self-cleaning ability of the material was excellent. The results are as follows: Figure 7 As shown by Figure 7 It can be seen that the porous material did not change color after being taken out, indicating that the poly(hydroxyethyl methacrylate) porous material prepared in Example 1 has excellent self-cleaning ability, which further proves the important role of poly(hydroxyethyl methacrylate) porous material treated with methyltrimethoxysilane in the field of self-cleaning.
[0057] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.
[0058] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.
Claims
1. A method for preparing a porous poly(hydroxyethyl methacrylate) material. It is characterized in that The steps include: Step A1: mixing hydroxyethyl methacrylate monomer and deionized water, and stirring to obtain a polymerizable eutectic solvent system; Step A2: adding a photoinitiator to a polymerizable eutectic solvent system, continuously introducing nitrogen, and inducing with ultraviolet light for 30 minutes to obtain poly(hydroxyethyl methacrylate) gel, and freeze-drying to obtain poly(hydroxyethyl methacrylate); Step A3: adding methyltrimethoxysilane and deionized water to poly(hydroxyethyl methacrylate) respectively, reacting at 60-80° C. for 4 h under sealed conditions, washing, and drying to obtain a poly(hydroxyethyl methacrylate) porous material.
2. A method for preparing a poly(hydroxyethyl methacrylate) porous material according to claim 1, It is characterized in that In step A1, the usage ratio of hydroxyethyl methacrylate monomer and deionized water is 0.8-1.2 g: 5-10 mL.
3. The method for preparing a poly(hydroxyethyl methacrylate) porous material according to claim 1, It is characterized in that In step A2, the ratio of the polymerizable eutectic solvent system to the photoinitiator is 5-10 mL: 0.01-0.05 g.
4. The method for preparing a poly(hydroxyethyl methacrylate) porous material according to claim 1, It is characterized in that In step A2, the photoinitiator is any one of 2,2-diethoxy-1-acetophenone, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone, 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone, and 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone.
5. The method for preparing a poly(hydroxyethyl methacrylate) porous material according to claim 1, It is characterized in that In step A2, the wavelength of ultraviolet light is 365nm and the intensity is 80mW / cm -2 .
6. The method for preparing a poly(hydroxyethyl methacrylate) porous material according to claim 1, It is characterized in that In step A3, the usage ratio of polyhydroxyethyl methacrylate, methyltrimethoxysilane and deionized water is 0.6-1.2 g: 0.6-1.2 g: 0.8-1.4 mL.
7. Application of the poly(hydroxyethyl methacrylate) porous material prepared by the preparation method according to any one of claims 1 to 6 in the field of self-cleaning materials.