Preparation and application of fluorine-containing acrylate resin
Fluorinated acrylate resins were prepared by copolymerizing methyl methacrylate with fluorinated comonomers, which solved the problems of PMMA's easy solubility and strong water absorption, improved the hydrophobicity and toughness of the material, and expanded its application range.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- HENAN UNIVERSITY
- Filing Date
- 2026-03-13
- Publication Date
- 2026-06-09
AI Technical Summary
Existing PMMA materials are easily soluble in polar solvents and have high water absorption, as well as insufficient toughness, which limits their application in coatings and other fields.
A terpolymer was used to copolymerize methyl methacrylate monomer and fluorinated comonomer to introduce fluorine atoms to reduce surface energy, thereby preparing a fluorinated acrylate resin, which was then used to prepare a film by bulk polymerization.
It significantly improves the hydrophobicity and solvent resistance of PMMA, while also enhancing the material's toughness and light transmittance, thus broadening its applications in transparent protective and optical films.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of polymers and relates to the field of polymethyl methacrylate (PMMA) preparation technology, specifically to a fluorinated acrylate resin and the preparation method and application of the PMMA film. Background Technology
[0002] This section provides background information relevant to this application, which does not necessarily constitute prior art.
[0003] Polymethyl methacrylate (PMMA), commonly known as plexiglass, is a typical amorphous thermoplastic transparent polymer material. It is typically synthesized through free radical polymerization, anionic polymerization, or coordination polymerization. It possesses advantages such as high light transmittance (>92%), light weight, good weather resistance, easy processing, and low cost, and is widely used in aerospace, architectural lighting, optical lenses, display light guides, and biomedical fields. However, existing PMMA technologies face the following technical challenges: 1. The polar ester groups (-COOCH3) on the side chains of PMMA make it easy for PMMA to be solvated by polar solvents such as acetone, ethyl acetate, dichloromethane, tetrahydrofuran (THF), and N,N-dimethylformamide (DMF) through dipole-dipole interactions. This causes the molecular chains to detangle and dissolve rapidly, resulting in strong water absorption and limiting its application in coatings and other fields.
[0004] 2. The steric hindrance effect of α-methyl groups on the main chain of PMMA and the weak inter-chain forces of the amorphous structure give it the advantages of high modulus and high strength, but its low toughness limits the application range of PMMA.
[0005] To improve the performance of PMMA, existing research includes copolymerization, blending, and surface modification. Among these, introducing fluorinated monomers for copolymerization is an effective strategy. Fluorine atoms possess characteristics such as high electronegativity, small atomic radius, high CF bond energy, and low surface energy. Copolymerizing fluorinated acrylate monomers with MMA can introduce fluorine atoms into the polymer backbone or side chains, thereby significantly reducing the surface energy of the material and endowing it with excellent hydrophobicity, oleophobicity, chemical stability, and stain resistance. Simultaneously, the introduction of fluorinated segments may also affect the aggregated structure of the material, thereby improving its toughness and solvent resistance.
[0006] Therefore, synthesizing PMMA that is both solvent-resistant and hydrophobic remains a significant challenge. This invention provides a simple, mild, and highly hydrophobic fluorinated acrylate resin and its film preparation method to address the technical problems of poor water absorption and solvent resistance in traditional PMMA, thus broadening its applications in transparent protective films, optical films, and hydrophobic functional materials. Summary of the Invention
[0007] To achieve the above objectives, the present invention adopts the following technical solution: The present invention provides a fluorinated acrylate resin, the film comprising the polymerization reaction product of the following components: (a) Methyl methacrylate monomer (MMA); (b) Second monomer; (c) Fluorinated comonomers; (d) Initiator; Based on the total weight of components (a), (b), and (c), the amount of MMA used is 70%-100%, for example, 70%, 72%, 75%, 78%, 80%, 82%, 85%, 87%, 90%, 92%, 95%, 98%, or 100%, the amount of the second monomer used is 0-10%, for example, 2%, 5%, 8%, or 10%, and the amount of the fluorinated comonomer used is 0-20%, for example, 3%, 5%, 8%, 13%, 15%, 18%, or 20%.
[0008] Based on the total weight of components (a), (b), and (c), the amount of the initiator is 0.1%-1%, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1%.
[0009] The second monomer includes at least one of butyl methacrylate (BMA), butyl acrylate (BA), acrylic acid (AA), and methacrylic acid (MAA).
[0010] The fluorinated comonomers mentioned therein include at least one of 2,2,3,3-tetrafluoropropyl acrylate, trifluoroethyl methacrylate (TFEMA), trifluoroethyl acrylate (TFEA), hexafluorobutyl methacrylate (HFBM), hexafluorobutyl acrylate (HFBA), dodecylfluoroheptyl methacrylate (DFHM), and dodecylfluoroheptyl acrylate (DFHA).
[0011] Preferably, the initiator is 1,1-di-tert-butylazobisisobutyronitrile.
[0012] This invention provides a fluorinated acrylate resin that combines high toughness, high light transmittance, and excellent solvent resistance.
[0013] On the other hand, the present invention also provides a method for preparing fluorinated acrylate resin and film, comprising the following steps: Step 1: Add methyl methacrylate monomer, second monomer, fluorinated comonomer and initiator to the reactor and mix them. Stir the reaction under nitrogen protection. After the viscosity of the system increases, put it into an ice bath to quench the reaction. Step 2: The obtained fluorinated acrylate solution is precipitated with hexane and dissolved with acetone. The precipitation and dissolution are repeated 3 times. The obtained product is placed in a vacuum drying oven for drying treatment to obtain the fluorinated acrylate copolymer. Step 3: Dissolve the copolymer in toluene / tetrahydrofuran solvent to prepare a 20wt% solution, cast it into a wet film by casting, and dry the wet film to obtain a fluorinated acrylate film.
[0014] In step one, the bulk polymerization reaction is carried out at a temperature of 80-100℃, for example, 80℃, 90℃, 95℃, or 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, or 160℃. The bulk polymerization reaction is conducted under a protective atmosphere, preferably nitrogen. During high-temperature polymerization, a stamping process is required. The conversion rate of the bulk polymerization reaction reaches approximately 30%-60%.
[0015] In step two, the drying time in the vacuum drying oven shall not be less than 6 hours, for example, 4 hours, 6 hours, 9 hours, 12 hours or 15 hours, preferably 8-12 hours.
[0016] In step three, the thickness of the wet membrane is 50-200 μm, for example, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm or 200 μm.
[0017] In step three, according to the method described in claim 3, the obtained wet film is dried sequentially in three temperature ranges: the first temperature range is between 40-60℃ for 10-30 hours, such as 40℃ for 16 hours, 50℃ for 12 hours; the second temperature range is between 70-100℃ for 30 minutes to 4 hours, such as 75℃ for 3 hours, 80℃ for 2 hours; and the third temperature range is between 90-130℃ for 30 minutes to 4 hours, such as 100℃ for 2 hours, 120℃ for 1 hour.
[0018] Compared with the prior art, the present invention has the following beneficial effects: 1. The PMMA film provided by this invention is a ternary copolymer with methyl methacrylate (MMA) as the main monomer, a second monomer introduced, and a fluorinated comonomer added. Because fluorine atoms have high electronegativity, small atomic radius, and high CF bond energy, the surface energy of the copolymer is significantly reduced. This greatly improves hydrophobicity and solvent resistance while maintaining the light transmittance of the PMMA film, and also improves the material's toughness.
[0019] 2. The method for preparing the fluorinated acrylate resin provided by this invention employs bulk polymerization, which is solvent-free, environmentally friendly, and energy-efficient. The fluorinated acrylate resin prepared by this invention exhibits high solvent resistance and hydrophobicity, along with good light transmittance (not less than 92%), and excellent mechanical strength. Detailed Implementation
[0020] It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. To better illustrate the effects of the process of the present invention, specific examples are provided below.
[0021] [Examples 1-4] Example 1 77.6 g MMA, 19.4 g BMA, 3 g HFBMA, and 0.1 g AIBN initiator were added to a reaction vessel. Nitrogen was continuously purged through the vessel to remove oxygen, and the mixture was stirred. The reaction was carried out in an oil bath at 70°C for 30 min, followed by ice bath quenching. The resulting mixture was precipitated with n-hexane, and 100 g of comonomers (MMA, BMA, and HFBMA were added according to the experimental ratio) were added. 0.1 g (0.1 wt%) of AIBN was added. The reaction was stirred in an oil bath at 70°C under nitrogen atmosphere for 30 min, followed by ice bath quenching. The mixture was then dissolved in acetone, and the precipitation and dissolution were repeated three times. The mixture was then vacuum dried at 50°C to obtain a fluorinated acrylate copolymer. The obtained fluorinated product was dissolved in a toluene / tetrahydrofuran mixed solvent to prepare a 20 wt% solution, stirred for 24 h, and ultrasonically degassed for 15 min. The solution was cast onto a clean glass plate, and a film was scraped to control the wet film thickness to approximately 800 μm. The film was then subjected to repeated reactions at 50°C / 24 h and 90°C / 1 h. Drying at 120℃ for 2 hours yields a transparent film with a thickness of 100–120 μm.
[0022] Example 2 76g MMA, 19g BMA, 5g HFBMA, and 0.1g AIBN initiator were added to a reaction vessel. Nitrogen was continuously purged through the vessel to remove oxygen, and the mixture was stirred. The reaction was carried out in an oil bath at 70°C for 30 min, followed by ice bath quenching. The resulting mixture was precipitated with n-hexane, and 100g of comonomers (MMA, BMA, and HFBMA were added according to the experimental ratio) were added. 0.1g (0.1 wt%) of AIBN was added. The reaction was stirred in an oil bath at 70°C under nitrogen atmosphere for 30 min, followed by ice bath quenching. The mixture was then dissolved in acetone, and the precipitation and dissolution were repeated three times. The mixture was then vacuum dried at 50°C to obtain a fluorinated acrylate copolymer. The obtained fluorinated product was dissolved in a toluene / tetrahydrofuran mixed solvent to prepare a 20 wt% solution, stirred for 24 h, and ultrasonically degassed for 15 min. The solution was cast onto a clean glass plate, and a film was scraped to control the wet film thickness to approximately 800 μm. The film was then subjected to repeated temperature changes: 50°C / 24 h, 90°C / 1 h, and 120°C / 2 h. After drying for h, a transparent film with a thickness of 100–120 μm is obtained.
[0023] Example 3 72g MMA, 18g BMA, 10g HFBMA, and 0.1g AIBN initiator were added to a reaction vessel. Nitrogen was continuously purged through the vessel to remove oxygen, and the mixture was stirred. The reaction was carried out in an oil bath at 70°C for 30 min, followed by ice bath quenching. The resulting mixture was precipitated with n-hexane, and 100g of comonomers (MMA, BMA, and HFBMA were added according to the experimental proportions) were added. 0.1g (0.1 wt%) of AIBN was added. The reaction was stirred in an oil bath at 70°C under a nitrogen atmosphere for 30 min, followed by ice bath quenching. The mixture was then dissolved in acetone, and the precipitation and dissolution were repeated three times. The mixture was then vacuum dried at 50°C to obtain a fluorinated acrylate copolymer. The obtained fluorinated product was dissolved in a toluene / tetrahydrofuran mixed solvent to prepare a 20 wt% solution, stirred for 24 h, and ultrasonically degassed for 15 min. The solution was cast onto a clean glass plate, and a film was scraped to control the wet film thickness to approximately 800 μm. The film was then subjected to repeated temperature changes: 50°C / 24 h, 90°C / 1 h, and 120°C / 2 h. After drying for h, a transparent film with a thickness of 100–120 μm is obtained.
[0024] Example 4 68 g MMA, 17 g BMA, 15 g HFBMA, and 0.1 g AIBN initiator were added to a reaction vessel. Nitrogen was continuously purged through the vessel to remove oxygen, and the mixture was stirred. The reaction was carried out in an oil bath at 70°C for 30 min, followed by ice bath quenching. The resulting mixture was precipitated with hexane, and 100 g of comonomers (MMA, BMA, and HFBMA were added according to the experimental ratio) were added. 0.1 g (0.1 wt%) of AIBN was added. The reaction was stirred in an oil bath at 70°C under nitrogen atmosphere for 30 min, followed by ice bath quenching. The mixture was then dissolved in acetone, and the precipitation and dissolution were repeated three times. The mixture was then vacuum dried at 50°C to obtain a fluorinated acrylate copolymer. The obtained fluorinated product was dissolved in a toluene / tetrahydrofuran mixed solvent to prepare a 20 wt% solution, stirred for 24 h, and ultrasonically degassed for 15 min. The solution was cast onto a clean glass plate, and a film was scraped to control the wet film thickness to approximately 800 μm. The film was then subjected to repeated temperature changes: 50°C / 24 h, 90°C / 1 h, and 120°C / 2 h. After drying for h, a transparent film with a thickness of 100–120 μm is obtained.
[0025] [Comparative Examples 1-2] Comparative Example 1 Compared with Example 1, the difference is that BMA and HFBMA are not added, otherwise it is the same as Example 1.
[0026] Comparative Example 2 Compared with Example 1, the difference is that HFBMA is not added, otherwise it is the same as Example 1.
[0027] [Comparison Test] The PMMA membranes provided in Examples 1-6 and the PMMA membranes provided in Comparative Examples 1-2 were tested as follows: Elongation at break, tensile strength and tensile modulus: tested according to GB / T1040.2-2022; Contact angle testing shall be performed in accordance with GB / T 30693-2014.
[0028] The test results are shown in Table 1.
[0029] Table 1
[0030] As shown in Table 1 above, the experimental results revealed that pure PMMA films exhibit high tensile strength, but their elongation at break is only 2%–5%, demonstrating significant brittleness. The introduction of BMA monomer slightly improved the film's toughness, but it still suffers from excessive rigidity and insufficient flexibility. The fluorinated acrylate film prepared using the method of this invention shows a significantly higher elongation at break and enhanced toughness compared to pure PMMA, without a significant decrease in tensile strength, resulting in more balanced overall mechanical properties. The water contact angle of pure PMMA film is 74.3°. After introducing BMA monomer, the water contact angle increases to 79.8°, improving hydrophobicity and reducing the film's surface energy, thus enhancing its hydrophobicity. The introduction of the fluorinated monomer HFBMA further improves the film's hydrophobicity, and the water contact angle increases monotonically with increasing fluorinated monomer content. Compared to pure PMMA film, the maximum improvement is about 14.5°, and compared to fluorine-free PMB film, the improvement is about 9°. This is because the introduction of fluorine atoms reduces the surface energy of the resin. During the film formation process, fluorine spontaneously migrates to the film surface, which improves the hydrophobicity of the film. As the HFBMA content increases, the film flexibility continues to improve, and brittleness is effectively suppressed. This shows that the present invention has successfully solved the technical problems of poor toughness and easy breakage of PMMA through copolymerization of fluorinated acrylate.
[0031] Table 2
[0032] To evaluate the solvent resistance of the films, tensile tests were conducted after immersing the films in ethanol for 5 minutes and 24 hours. The tensile strength retention rate was calculated, and the results are shown in Table 2. After immersion for 5 minutes, the retention rates of Comparative Examples 1 and 2 decreased significantly, while the retention rate of the fluorinated resin was relatively high. After immersion for 24 hours, the strength of all films decreased significantly. Fluorinated copolymerization reduces ethanol penetration and plasticizing effect, therefore, fluorinated copolymers can effectively improve the solvent resistance of polymers.
[0033] To keep the description concise, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.
[0034] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.
Claims
1. A fluorinated acrylate resin, characterized in that, The fluorinated acrylate resin comprises the polymerization product of the following components: (a) Methyl methacrylate monomer; (b) Second monomer; (c) Fluorinated comonomers; (d) Initiator; Based on the total weight of components (a), (b), and (c), the amount of methyl methacrylate monomer is 70%-100%, the amount of the second monomer is 0-10%, and the amount of the fluorinated comonomer is 0-20%. Based on the total weight of components (a), (b), and (c), the amount of the initiator is 0.1%-1%; The second monomer includes at least one of butyl methacrylate, butyl acrylate, acrylic acid, methacrylic acid, and methyl acrylate; The fluorinated comonomer includes at least one of 2,2,3,3-tetrafluoropropyl acrylate, trifluoroethyl methacrylate (TFEMA), trifluoroethyl acrylate (TFEA), hexafluorobutyl methacrylate (HFBM), hexafluorobutyl acrylate (HFBA), dodecylfluoroheptyl methacrylate (DFHM), and dodecylfluoroheptyl acrylate (DFHA).
2. The fluorinated acrylate resin according to claim 1, characterized in that, The initiator includes at least one of azo initiators and organic peroxide initiators.
3. A method for preparing the fluorinated acrylate resin according to claim 1 or 2, characterized in that, Includes the following steps: Step 1: Add methyl methacrylate monomer, second monomer, fluorinated comonomer and initiator to the reactor and mix and react. Stir the reaction under nitrogen protection. After the viscosity of the system increases, devolatilize and granulate it. Step 2: The obtained fluorinated acrylate resin is precipitated with hexane and dissolved in acetone. The precipitation and dissolution are repeated 3 times. The resulting product is then placed in a vacuum drying oven for drying to obtain the fluorinated acrylate copolymer. Step 3: Dissolve the copolymer in toluene / tetrahydrofuran solvent to prepare a 20 wt% solution, cast it into a wet film by casting, and dry the wet film to obtain a fluorinated acrylate film.
4. The method according to claim 3, characterized in that, The bulk polymerization reaction is carried out at a temperature of 80-160°C under a protective atmosphere.
5. The method according to claim 3, characterized in that, The quenching process involves granulation after high-temperature devolatilization in the reactor.
6. The method according to claim 3, characterized in that, The resulting wet film was dried sequentially at three temperature ranges: the first range was between 40-60℃ for 10-30 hours; the second range was between 70-100℃ for 30 minutes to 4 hours; and the third range was between 90-130℃ for 30 minutes to 4 hours.
7. The method according to claim 3, characterized in that, The thickness of the wet film is 50-200 μm.