Application of perfluoro-substituted decene-co-vinylamine polymer in PMMA (polymethyl methacrylate) surface treatment

Abstract

The invention discloses an application of a perfluoro-substituted decene-co-vinylamine polymer in PMMA (polymethyl methacrylate) surface treatment. When the polymethyl methacrylate is used as a PMMA (polymethyl methacrylate) surface modifier, the surface hydrophobicity of an organic glass plate can be effectively improved, and the plate is endowed with excellent anti-fouling performance. Researches show that the hydrophobic layer constructed by using the perfluoro-substituted decene-co-vinylamine copolymer not only can maintain good optical transmittance of the PMMA plate, but also can ensure uniform distribution and long-term stability of the assembly layer.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials and surface modification, and specifically relates to application of a perfluorosubstituted decene-co-vinylamine polymer in PMMA surface treatment. Background Art

[0002] Polymethyl methacrylate (PMMA) is a widely used light-transmitting polymer material. By modifying the surface of PMMA polymer material with some surface modifiers with special properties, some functional transparent polymer materials can be obtained.

[0003] Generally speaking, using silane coupling agents as surface modifiers to modify the surface of materials will significantly improve certain properties of the materials. For example, using silane coupling agents to modify the surface of commercial carbon black can improve its dispersibility in rubber blends; using silane coupling agents to modify SiO2 nanoparticles modified with TiO2 nanocomposites can improve the inkjet performance of blue light-cured inks; Go Yanan et al. modified PVDF membranes with hydrophobic octadecylsilane to improve their anti-wetting properties; Peter Rodič et al. used chemical etching methods to graft n-octyltrimethoxysilane and perfluorooctyltrimethoxysilane on the surface to prepare (super) hydrophobic aluminum surfaces, enhance their corrosion resistance, and obtain a material surface with self-cleaning and anti-icing capabilities; Wang Qi et al. grafted fluoroalkyl silanes onto the surface of porous glass to give it ultra-high hydrophobicity and high visible light transmittance.

[0004] Although silane coupling agents have certain chemical activity, their molecular weight is relatively low and they may not be able to maintain stability and durability in certain application scenarios. Macromolecular modifiers, on the other hand, have higher molecular weights and can form more complex and stable chemical structures. This structural feature enables macromolecular modifiers to play a more lasting and stable role in material modification. Summary of the invention

[0005] The purpose of the present invention is to provide an application of a perfluorosubstituted decene-co-vinylamine polymer in the surface treatment of PMMA. The present invention uses a copolymer containing a perfluoroalkyl chain to construct a uniform and stable hydrophobic layer on the surface of a plexiglass plate (PMMA), which not only maintains the good optical transparency of PMMA, but also improves the surface hydrophobicity of the PMMA plate and gives it excellent anti-fouling performance.

[0006] In order to achieve the above-mentioned invention object, the present invention adopts the following technical solutions: Application of perfluorosubstituted decene-co-vinylamine polymers in PMMA surface treatment.

[0007] The method for modifying the surface of a PMMA plate using a perfluoro-substituted decene-co-vinylamine copolymer comprises the following steps: 1) Remove the protective film on the outer layer of the PMMA plate, wash away the organic matter adsorbed on the surface with detergent, rinse with deionized water, obtain a PMMA plate with a thickness of 1 mm, and cut it into small pieces; 2) The small pieces obtained in step 1) are placed in a sodium hydroxide solution with a mass fraction of 10% to 20% and a temperature of 65 to 75°C for pretreatment for 25 to 35 minutes, and then washed in pure water at the same temperature for 20 to 40 seconds; 3) Dissolve 0.01-0.06 g of perfluoro-substituted decene-co-vinylamine copolymer in ethanol solution to obtain a perfluoro-substituted decene-co-vinylamine copolymer mixed solution; suspend the small piece pretreated in step 2) in the above mixed solution, rotate and modify, take out and wash with pure water for 50-70 seconds, and dry naturally.

[0008] Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention uses a copolymer containing a perfluoroalkyl chain as a PMMA surface modifier to improve the surface hydrophobicity of the organic glass sheet and give it excellent anti-fouling performance.

[0009] , UV-visible spectrophotometer and water contact angle test characterized the construction of hydrophobic layer by perfluoro-substituted decene-co-vinylamine copolymer, which maintained the original high transparency of PMMA and imparted hydrophobic properties.

[0010] , Through comparison, it is found that the visible light transmittance of the PMMA plate modified with silane coupling agent is significantly reduced, and the coating is unevenly distributed, with local accumulation. In addition, its stability is poor. In contrast, the hydrophobic layer constructed with perfluorosubstituted decene-co-vinylamine copolymer can not only maintain good optical transmittance, but also ensure the uniform distribution of the assembly layer and long-term stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] In order to more clearly illustrate the technical solution of the present invention, the following is a brief introduction to the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without paying any creative work.

[0012] Figure 1 The infrared and Raman test images of the hydrophobic layer constructed by using the perfluoro-substituted decene-co-vinylamine copolymer of the present invention and the comparative example; Figure 2 The contact angle and surface free energy test diagram of the hydrophobic layer constructed by using the perfluoro-substituted decene-co-vinylamine copolymer of the present invention; Figure 3SEM images of the hydrophobic layer constructed by perfluoro-substituted decene-co-vinylamine copolymers in the present invention: (a) PMMA; (b) PMMA-OH; (c) PMMA-OH-O1; (d) PMMA-OH-O2; (e) PMMA-OH-P1; (f) PMMA-OH-P2; Figure 4 The UV-Vis absorption spectrum and surface resistivity test graph of the hydrophobic layer constructed by using the perfluoro-substituted decene-co-vinylamine copolymer in the present invention; Figure 5 This is a test diagram of the contact angle change after sewage treatment using a hydrophobic layer constructed using a perfluoro-substituted decene-co-vinylamine copolymer in the present invention; Figure 6 This is a test chart of haze change after sewage treatment using a hydrophobic layer constructed using a perfluoro-substituted decene-co-vinylamine copolymer in the present invention: M0: PMMA; M1-M3: PMMA plates modified with coupling agents; M4: PMMA plates modified with a perfluoro-substituted decene-co-vinylamine copolymer. DETAILED DESCRIPTION

[0013] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described below in conjunction with specific embodiments. However, the following embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present invention.

[0014] It should be noted that the preparation method of the perfluoro-substituted decene-co-vinylamine copolymer in the present invention can be found in CN115116842 A. The perfluoro-substituted decene-co-vinylamine copolymers in the following embodiments of the present invention are prepared by the method of Example 1 of CN115116842 A.

[0015] Example 1 The method of modifying the surface of a PMMA plate using a perfluoro-substituted decene-co-vinylamine copolymer in this embodiment comprises the following steps: 1) Remove the protective film on the outer layer of the PMMA plate, wash away the organic matter adsorbed on the surface with detergent, rinse with deionized water, and obtain a PMMA plate with a thickness of 1 mm, which is cut into small pieces of 1 cm × 1 cm; 2) The small piece obtained in step 1) was placed in a 70°C, 15% by mass sodium hydroxide solution for pretreatment for 30 minutes, and then taken out and washed in pure water at the same temperature for 30 seconds; 3) Dissolve 0.06 g of perfluoro-substituted decene-co-vinylamine copolymer in ethanol solution to obtain a perfluoro-substituted decene-co-vinylamine copolymer mixed solution; suspend the small piece pretreated in step 2) in the above mixed solution, rotate and modify, take out and wash with pure water for 60 seconds, and dry naturally.

[0016] Example 2 The method of modifying the surface of a PMMA plate using a perfluoro-substituted decene-co-vinylamine copolymer in this embodiment comprises the following steps: 1) Remove the protective film on the outer layer of the PMMA plate, wash away the organic matter adsorbed on the surface with detergent, rinse with deionized water, and obtain a PMMA plate with a thickness of 1 mm, which is cut into small pieces of 1 cm × 1 cm; 2) The small piece obtained in step 1) was placed in a 70°C, 15% by mass sodium hydroxide solution for pretreatment for 30 minutes, and then taken out and washed in pure water at the same temperature for 30 seconds; 3) Dissolve 0.02 g of perfluoro-substituted decene-co-vinylamine copolymer in ethanol solution to obtain a perfluoro-substituted decene-co-vinylamine copolymer mixed solution; suspend the small piece pretreated in step 2) in the above mixed solution, rotate and modify, take out and wash with pure water for 60 seconds, and dry naturally.

[0017] Example 3 The method of modifying the surface of a PMMA plate using a perfluoro-substituted decene-co-vinylamine copolymer in this embodiment comprises the following steps: 1) Remove the protective film on the outer layer of the PMMA plate, wash away the organic matter adsorbed on the surface with detergent, rinse with deionized water, and obtain a PMMA plate with a thickness of 1 mm, which is cut into small pieces of 1 cm × 1 cm; 2) The small piece obtained in step 1) was placed in a 70°C, 15% by mass sodium hydroxide solution for pretreatment for 30 minutes, and then taken out and washed in pure water at the same temperature for 30 seconds; 3) Dissolve 0.01 g of perfluoro-substituted decene-co-vinylamine copolymer in ethanol solution to obtain a perfluoro-substituted decene-co-vinylamine copolymer mixed solution; suspend the small piece pretreated in step 2) in the above mixed solution, rotate and modify, take out and wash with pure water for 60 seconds, and dry naturally.

[0018] Example 4 The method of modifying the surface of a PMMA plate using a perfluoro-substituted decene-co-vinylamine copolymer in this embodiment comprises the following steps: 1) Remove the protective film on the outer layer of the PMMA plate, wash away the organic matter adsorbed on the surface with detergent, rinse with deionized water, and obtain a PMMA plate with a thickness of 1 mm, which is cut into small pieces of 1 cm × 1 cm; 2) The small piece obtained in step 1) was placed in a 10% sodium hydroxide solution at 65°C for 25 minutes for pretreatment, and then washed in pure water at the same temperature for 20 seconds; 3) Dissolve 0.03 g of perfluoro-substituted decene-co-vinylamine copolymer in ethanol solution to obtain a perfluoro-substituted decene-co-vinylamine copolymer mixed solution; suspend the small piece pretreated in step 2) in the above mixed solution, rotate and modify, take out and wash with pure water for 50 seconds, and dry naturally.

[0019] Example 5 The method of modifying the surface of a PMMA plate using a perfluoro-substituted decene-co-vinylamine copolymer in this embodiment comprises the following steps: 1) Remove the protective film on the outer layer of the PMMA plate, wash away the organic matter adsorbed on the surface with detergent, rinse with deionized water, and obtain a PMMA plate with a thickness of 1 mm, which is cut into small pieces of 1 cm × 1 cm; 2) The small piece obtained in step 1) was placed in a 75°C, 20% by mass sodium hydroxide solution for pretreatment for 35 min, and then taken out and washed in pure water at the same temperature for 40 s; 3) Dissolve 0.05 g of perfluoro-substituted decene-co-vinylamine copolymer in ethanol solution to obtain a perfluoro-substituted decene-co-vinylamine copolymer mixed solution; suspend the small piece pretreated in step 2) in the above mixed solution, rotate and modify, take out and wash with pure water for 70 seconds, and dry naturally.

[0020] Comparative Example 1 This comparative example 1 is the same as example 1, except that in step 3), 0.06 g of a perfluoro-substituted decene-co-vinylamine copolymer is dissolved in an ethanol solution to obtain a perfluoro-substituted decene-co-vinylamine copolymer mixed solution, which is replaced by a mixed solution obtained by dissolving 0.06 g of octadecyltrimethoxysilane in 20 g of cyclohexane.

[0021] Comparative Example 2 This comparative example 2 is the same as example 1, except that in step 3), 0.06 g of perfluoro-substituted decene-co-vinylamine copolymer is dissolved in ethanol solution to obtain a perfluoro-substituted decene-co-vinylamine copolymer mixed solution, which is replaced by a mixed solution obtained by dissolving 0.06 g of octyltrimethoxysilane in 20 g of cyclohexane.

[0022] Comparative Example 3 This comparative example 3 is the same as example 1, except that in step 3), 0.06 g of perfluoro-substituted decene-co-vinylamine copolymer is dissolved in ethanol solution to obtain a perfluoro-substituted decene-co-vinylamine copolymer mixed solution, which is replaced by a mixed solution obtained by dissolving 0.06 g of perfluoro-substituted octyltrimethoxysilane in 20 g of cyclohexane.

[0023] Performance Testing In order to illustrate the effect of the present invention, the surface-modified PMMA plate materials obtained in Example 1 and Comparative Examples 1 to 3 were subjected to infrared, Raman, contact angle, surface free energy, SEM electron microscopy, UV-Vis absorption spectrum, surface resistivity and other tests. For ease of explanation, octadecyltrimethoxysilane dissolved in cyclohexane is recorded as O1; octyltrimethoxysilane dissolved in cyclohexane is recorded as O2; perfluoro-substituted octyltrimethoxysilane dissolved in cyclohexane is recorded as P1; perfluoro-substituted decene-vinylamine copolymer dissolved in ethanol solution is recorded as P2. The PMMA plates obtained in Example 1 and Comparative Examples 1 to 3 are recorded as PMMA-OH-P2, PMMA-OH-O1, PMMA-OH-O2, and PMMA-OH-P1, respectively. See the specific test results. Figure 1 to Figure 6 .

[0024] Figure 1 The infrared and Raman test images of the hydrophobic layer constructed by the perfluoro-substituted decene-co-vinylamine copolymer of the present invention and the comparative example. Figure 1 It can be seen that the coupling agent and the perfluoro-substituted decene-co-vinylamine copolymer (P2) were successfully modified.

[0025] Figure 2 The contact angle and surface free energy test diagram of the hydrophobic layer constructed using perfluorosubstituted decene-co-vinylamine copolymer. Figure 2 It can be seen that when the concentration of the modifier is increased to a certain level, the contact angle and surface free energy of the hydrophobic layer constructed by P2 remain stable compared to the hydrophobic layer constructed by the coupling agent, which provides a relatively broad and stable modification space for the use of the modifier and greatly facilitates the precise control of processing conditions.

[0026] Figure 3 This is a SEM image of a hydrophobic layer constructed using a perfluorosubstituted decene-co-vinylamine copolymer. Figure 3 It can be seen that a certain degree of accumulation occurs on the surface of the PMMA plate modified with silane coupling agent. This accumulation phenomenon may not only have an adverse effect on the stability of the hydrophobic effect, but also increase the roughness of the PMMA surface, thereby increasing the possibility of light scattering, resulting in a decrease in the transparency of PMMA. In contrast, the surface of the PMMA plate modified with P2 appears relatively smooth, forming a dense and uniform organic hydrophobic layer.

[0027] Figure 4 The UV-Vis absorption spectrum and surface resistivity test diagram of the hydrophobic layer constructed using perfluorosubstituted decene-co-vinylamine copolymer. Figure 4 It can be seen that the transmittance of the PMMA plate modified by the coupling agent is reduced to varying degrees, and P2 is not easy to accumulate on the surface of the organic glass plate, so the PMMA plate modified by P2 has a higher transmittance. The surface resistivity of the organic glass plate is 5.09×10 11 Ω, and with the increase of P2 content, the active sites on the surface of the organic glass plate tend to be saturated, resulting in a stable surface resistivity. As the surface resistivity of the modified organic glass plate increases, its conductivity will also decrease, and the electrostatic adsorption will decrease, so that the adsorption of some fine dust on the surface of the material is weakened, which can also play a certain degree of anti-fouling effect.

[0028] Figure 5 This is a test diagram of the change in contact angle of sewage treatment using a hydrophobic layer constructed using a perfluorosubstituted decene-co-vinylamine copolymer. Figure 5 It can be seen that as the number of sewage treatments increases, the hydrophobic layer constructed by the silane coupling agent is destroyed. The hydrophobic layer constructed by the perfluorosubstituted decene-co-vinylamine copolymer has high stability and density, and can effectively resist the penetration and damage of water.

[0029] Figure 6 The haze change test diagram of the hydrophobic layer constructed by perfluoro-substituted decene-co-vinylamine copolymer after sewage treatment: M0: PMMA; M1-M3: PMMA plate modified by coupling agent; M4: PMMA plate modified by perfluoro-substituted decene-co-vinylamine copolymer. Figure 6 It can be seen that the haze of the original plexiglass plate M0 changes greatly after sewage treatment, while the plexiglass plate modified with perfluoro-substituted decene-co-vinylamine copolymer has a relatively small haze change due to its lower surface energy and conductivity, and the degree of surface contamination by sewage is less.

Claims

1. Application of perfluorosubstituted decene-co-vinylamine polymer in PMMA surface treatment.

2. A method for modifying the surface of a PMMA plate using a perfluoro-substituted decene-co-vinylamine copolymer, characterized in that: The following steps are involved: 1) Remove the protective film on the outer layer of the PMMA plate, wash away the organic matter adsorbed on the surface with detergent, rinse with deionized water, obtain a PMMA plate with a thickness of 1 mm, and cut into small pieces; 2) The small pieces obtained in step 1) are placed in a sodium hydroxide solution with a mass fraction of 10% to 20% and a temperature of 65 to 75°C for pretreatment for 25 to 35 minutes, and then washed in pure water at the same temperature for 20 to 40 seconds; 3) Dissolve 0.01-0.06 g of perfluoro-substituted decene-co-vinylamine copolymer in ethanol solution to obtain a perfluoro-substituted decene-co-vinylamine copolymer mixed solution; suspend the small piece pretreated in step 2) in the above mixed solution, rotate and modify, take out and wash with pure water for 50-70 seconds, and dry naturally.

Images