Preparation method of lotus-shaped nano antimony trioxide doped methyl methacrylate polymer film

Abstract

The invention discloses a preparation method of a lotus-shaped nano antimony trioxide doped methyl methacrylate polymer film, which comprises the following steps: firstly, preparing a lotus-shaped nano antimony trioxide material, and then taking the prepared lotus-shaped nano antimony trioxide material as a dopant of the methyl methacrylate polymer film to prepare the lotus-shaped nano antimony trioxide doped methyl methacrylate polymer film. And thermally polymerizing a layer of polymer film on the metal substrate. The film layer prepared by the method has high corrosion potential, low corrosion current and large impedance, which indicates that the film layer has good corrosion resistance. The coating can be applied to anticorrosion engineering of surfaces of electrical equipment such as air conditioners, electric water heaters, air conditioners and refrigerators and metal parts of mechanical equipment such as tractors and cranes.

Description

Technical Field

[0001] This invention relates to the field of anti-corrosion polymer films, and in particular to a method for preparing a lotus-shaped nano-antimony trioxide-doped methyl methacrylate polymer film. Background Technology

[0002] To improve the corrosion resistance of metal components, a traditional method involves mixing heavy metals such as hexavalent chromium and lead tetroxide with a polymer film, followed by thermal polymerization onto the metal substrate surface. However, hexavalent chromium and lead tetroxide are toxic, and the EU RoHS regulation (Restriction of Hazardous Substances Directive) prohibits their use in the electrical and electronics industries. While polymer films without hexavalent chromium and lead tetroxide are non-toxic, their corrosion resistance is poor, leading to persistent corrosion problems, especially in harsh environments. The inventor's earlier Chinese patents, "A method for preparing a rosin-based and acrylamide thermally polymerized anticorrosive film with high pitting potential" (Patent No.: CN201910627322.1), "A method for preparing a rosin-based thermally polymerized anticorrosive film doped with nickel oxide nanoparticles with high pitting potential" (Patent No.: CN 201910627317.0), and "A method for preparing a rosin-based thermally polymerized anticorrosive film doped with cobalt oxide nanoparticles with high pitting potential" (Patent No.: CN201910627320.2), while showing good results, still have limited effectiveness in harsh environments. Furthermore, although there are methods for synthesizing flower-shaped nano-antimony trioxide, the synthesized petals are too thick, have a small specific surface area, and a small contact area with organic coatings, resulting in low performance and insignificant effects. Improving the specific surface area of ​​the material has been a long-standing challenge for those skilled in the art. Therefore, researching a method for preparing thin, lotus-shaped antimony trioxide nanoparticles, and then doping them into a methyl methacrylate polymer film to create a high-performance coating, is of great significance. Summary of the Invention

[0003] The technical problem to be solved by the present invention is to provide a method for preparing a lotus-shaped nano-antimony trioxide-doped methyl methacrylate polymer film that is easy to manufacture.

[0004] To solve the above-mentioned technical problems, the present invention adopts the following technical solution: firstly, lotus-shaped nano-antimony trioxide material is synthesized, and the prepared lotus-shaped nano-antimony trioxide material is used as a dopant, methyl methacrylate as a monomer, and glycerol as a crosslinking agent. Then, a layer of lotus-shaped nano-antimony trioxide-doped methyl methacrylate polymer film is thermally polymerized on the surface of the metal part.

[0005] The above-mentioned method for preparing a lotus-shaped nano-antimony trioxide-doped methyl methacrylate polymer film involves using lotus-shaped nano-antimony trioxide material as a dopant, methyl methacrylate as a monomer, and glycerol as a crosslinking agent. The metal component is immersed in the solution, and then thermal polymerization is carried out on the surface of the metal component to obtain the film.

[0006] The preparation method of the above-mentioned lotus-shaped antimony trioxide-doped methyl methacrylate polymer film includes the following steps: <1> Synthesis of lotus-shaped antimony trioxide nanomaterials: 0.15 g antimony trichloride, 25 g ethanol, 25 g ethylenediamine, 0.02 g poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol), and 200 ml benzyl alcohol were added to a beaker and stirred for 30 minutes. The mixture was then transferred to a 500 mL stainless steel autoclave lined with polytetrafluoroethylene, sealed, and placed in an oven at 180°C for 12 h. The precipitate was washed three times with ethanol and deionized water, collected by centrifugation, and then vacuum dried at 120°C for 12 hours to obtain the final product. <2> Add 20-50 g of isopropanol, 0.25 g of initiator azobisisobutyronitrile, and 20-50 g of crosslinking agent glycerol sequentially to 100 g-200 g of methyl methacrylate, then add the following steps: <1> The lotus-shaped nano-antimony trioxide material was prepared by adding 0.20 g to 0.80 g of each substance and stirring for 2 min, followed by stirring for another 25 min. <3> Preparation of polymer film: Immersion of clean, smooth metal parts into the step <2> The mixture is heated for 10 minutes, and then the part is removed and placed in a drying oven at 90 °C for 200 min for thermal polymerization to obtain the final product.

[0007] Experiments have shown that using low-carbon steel electrodes... as base The prepared lotus-shaped nano-antimony trioxide material was used as a dopant, methyl methacrylate as a monomer, azobisisobutyronitrile as an initiator, and glycerol as a crosslinking agent. It was then thermally polymerized onto a 1 cm diameter low-carbon steel electrode surface. Electrochemical workstation tests showed that the corrosion current of the polymer film doped with the lotus-shaped nano-antimony trioxide material was significantly reduced, while its corrosion potential was increased, exceeding that of the undoped methyl methacrylate polymer film by 200 mV. AC impedance analysis showed that the impedance of the undoped methyl methacrylate polymer film was 50 kohm·cm⁻¹. 2 The impedance of the polymer film layer with lotus-shaped antimony trioxide nanomaterials as dopants is 1000 kohm·cm. 2Around 100°C, the impedance increased significantly. Tinplate sheets coated with lotus-shaped nano-antimony trioxide material as a dopant prepared by this method showed almost no corrosion after immersion in a 3.5% sodium chloride solution for 60 days; however, coatings without the lotus-shaped nano-antimony trioxide material as a dopant showed severe corrosion after immersion in a 3.5% sodium chloride solution for 60 days, exhibiting blistering and peeling. The coating prepared by this method using lotus-shaped nano-antimony trioxide material as a dopant surpasses the performance of current methyl methacrylate polymer film coatings and is easier to prepare. In particular, the lotus-shaped nano-antimony trioxide material synthesized by this method significantly improves the corrosion resistance of the coating. Attached Figure Description

[0008] Figure 1 This is a transmission electron microscope (TEM) image of the prepared lotus-shaped antimony trioxide nanomaterial.

[0009] Figure 2 The polarization curves of the methyl methacrylate polymer film prepared by the method of preparing a lotus-shaped nano-antimony trioxide doped methyl methacrylate polymer film in Example 1 are shown: Curve a is the polymer film without lotus-shaped nano-antimony trioxide dopant, and curve b is the polymer film with lotus-shaped nano-antimony trioxide dopant.

[0010] Figure 3 The AC impedance diagram of the film prepared by the method of preparing lotus-shaped antimony trioxide doped methyl methacrylate polymer film in Example 1 is shown below: Curve a is the polymer film without lotus-shaped antimony trioxide dopant, and curve b is the polymer film with lotus-shaped antimony trioxide dopant.

[0011] Figure 4 This is a corrosion photograph of the polymer film layer without lotus-shaped nano-antimony trioxide dopant in Example 1, after being immersed in a 3.5% sodium chloride solution for 60 days.

[0012] Figure 5 Corrosion photograph of the polymer film containing lotus-shaped nano-antimony trioxide dopant in Example 1 after immersion in 3.5% sodium chloride solution for 60 days. Detailed Implementation Example

[0014] I. Pretreatment of electrodes and tinplate sheets The electrodes (Q235 low-carbon steel electrodes (1 cm in diameter) and tinplate sheets (12 cm × 5 cm × 1 mm) were polished sequentially with 280-grit and 600-grit sandpaper, respectively. Then, they were ultrasonically cleaned in 5% hydrochloric acid for 1 min, ultrasonically cleaned in deionized water for 5 min, and finally ultrasonically cleaned in anhydrous ethanol for 5 min before drying for later use.

[0015] II. Preparation of Lotus-shaped Antimony Trioxide Nanomaterials and Polymer Films <1> Synthesis of lotus-shaped antimony trioxide nanomaterials: 0.15 g antimony trichloride, 25 g ethanol, 25 g ethylenediamine, 0.02 g poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol), and 200 ml benzyl alcohol were added to a beaker and stirred for 30 minutes. The mixture was then transferred to a 500 mL stainless steel autoclave lined with polytetrafluoroethylene, sealed, and placed in an oven at 180°C for 12 h. The precipitate was washed three times with ethanol and deionized water, collected by centrifugation, and then vacuum dried at 120°C for 12 hours to obtain the final product. <2> Add 20 g of isopropanol, 0.25 g of initiator azobisisobutyronitrile, and 20 g of crosslinking agent glycerol sequentially to 100 g of methyl methacrylate, then add the following steps: <1> The lotus-shaped nano-antimony trioxide material was prepared by adding one substance at a time and stirring for 2 minutes, followed by stirring for another 25 minutes. <3> Preparation of polymer film: Immersion of clean, smooth metal parts into the step <2> The mixture is heated for 10 minutes, and then the part is removed and placed in a drying oven at 90 °C for 200 min for thermal polymerization to obtain the final product.

[0016] <4> Preparation of polymeric films without lotus-shaped antimony trioxide nanomaterials: The preparation of methyl methacrylate polymeric films without lotus-shaped antimony trioxide nanomaterials involves the following processes and steps, except for the absence of lotus-shaped antimony trioxide nanomaterials. <2> , <3> The same result is obtained, i.e., a polymer film layer without lotus-shaped nano-antimony trioxide material dopants.

[0017] III. Corrosion Resistance Test of Polymer Layer <1> Electrochemical testing: Electrochemical polarization curves and AC impedance measurements were performed on the polymer film layers without and containing lotus-shaped nano-antimony trioxide material in a 3.5% sodium chloride solution. Corrosion current, corrosion potential, and impedance were compared. It was found that the corrosion current of the film layer containing lotus-shaped nano-antimony trioxide material was significantly reduced, and its corrosion potential increased by more than 200 mV compared to the polymer film layer without the lotus-shaped nano-antimony trioxide material. Figure 2 (As shown); the impedance of the polymer film coating without lotus-shaped nano-antimony trioxide material is 50 kohm·cm. 2 The impedance of the film containing lotus-shaped antimony trioxide nanomaterials is approximately 1000 kohm·cm. 2 Around, the impedance increases significantly (e.g. Figure 3 (As shown).

[0018] <2> The prepared polymer film layers without lotus-shaped nano-antimony trioxide material and the polymer film layers containing lotus-shaped nano-antimony trioxide material were immersed in a 3.5% sodium chloride solution for 60 days. It was found that the polymer film layer without lotus-shaped nano-antimony trioxide material showed severe corrosion, with blistering and peeling phenomena (such as...). Figure 4 As shown); the polymer film containing lotus-shaped nano-antimony trioxide material exhibits almost no corrosion (as shown). Figure 5 (As shown).

[0019] Therefore, the method for preparing a lotus-shaped nano-antimony trioxide-doped methyl methacrylate polymer film according to the present invention produces a film layer with low corrosion current, high corrosion potential, and large impedance, exhibiting strong resistance to salt water corrosion and good anti-corrosion performance. In particular, the lotus-shaped nano-antimony trioxide material synthesized by this method significantly improves the anti-corrosion performance of the coating.

Claims

1. A method for preparing a lotus-shaped nano-antimony trioxide-doped methyl methacrylate polymer film, characterized in that, Lotus-shaped nano-antimony trioxide material was used as a dopant for methyl methacrylate polymer film, methyl methacrylate was used as monomer and glycerol was used as crosslinking agent, and then a polymer film was thermally polymerized on a metal substrate. The specific steps are as follows: <1> Synthesis of lotus-shaped antimony trioxide nanomaterials: 0.15 g antimony trichloride, 25 g ethanol, 25 g ethylenediamine, 0.02 g poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol), and 200 ml benzyl alcohol were added to a beaker and stirred for 30 minutes. The mixture was then transferred to a 500 mL stainless steel autoclave lined with polytetrafluoroethylene, sealed, and placed in an oven at 180°C for 12 h. The precipitate was washed three times with ethanol and deionized water, collected by centrifugation, and then vacuum dried at 120°C for 12 hours to obtain the final product. <2> Add 20-50 g of isopropanol, 0.25 g of initiator azobisisobutyronitrile, and 20-50 g of crosslinking agent glycerol sequentially to 100 g-200 g of methyl methacrylate, then add the following steps: <1> The lotus-shaped nano-antimony trioxide material was prepared at a ratio of 0.20 g to 0.80 g. Each substance was added and stirred for 2 min, and then stirred for another 25 min to obtain the final product. <3> Preparation of polymer film: Immersion of clean, smooth metal parts into the step <2> The mixture is heated for 10 minutes, and then the part is removed and placed in a drying oven at 90 °C for 200 min for thermal polymerization to obtain the final product.

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