Self-repairing recoverable antifouling ionic liquid hybrid fluorinated polysiloxane material as well as preparation and application thereof

Abstract

The invention discloses a preparation method of a self-repairing recoverable antifouling ionic liquid hybrid fluorinated polysiloxane material. The preparation method comprises the following steps: synthesizing a fluorinated polysiloxane prepolymer; adding ionic liquid into the fluorinated polysiloxane prepolymer, heating and stirring until a uniform prepolymer-ionic liquid mixture is formed; injecting the prepolymer-ionic liquid mixture into a mold, cooling to room temperature, and curing to obtain the self-repairing recoverable antifouling ionic liquid hybridized fluorinated polysiloxane material. The double in-situ phase change behavior of glass transition of the polysiloxane matrix and solid-liquid phase change of the ionic liquid is utilized, molecular chain movement is activated during heating to achieve self-repairing and arbitrary remodeling, the mechanical property is recovered after cooling, and rapid closed-loop recovery is achieved; according to the invention, the inherent high chemical inertness of polysiloxane is retained, and meanwhile, the required dynamic characteristics are endowed through ionic liquid hybridization.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology. More specifically, this invention relates to a self-healing, recyclable, and antifouling ionic liquid hybrid fluorinated polysiloxane material, its preparation, and its application. Background Technology

[0002] Polysiloxanes are widely used in coatings due to their low surface energy, chemical inertness, weather resistance, and biocompatibility. However, in complex and harsh operating environments, coatings are prone to damage and failure, and the extensive use of non-degradable polymers has caused serious environmental problems. Therefore, the development of polysiloxane materials with both self-healing and recyclability has become an urgent need.

[0003] Current self-healing polymers often incorporate polysiloxanes as flexible segments into carbon-based resins, or achieve repair through Si-O bond recombination under specific conditions. The former relies on polar carbon-based components, weakening the inherent hydrophobicity and chemical inertness of polysiloxanes; the latter is limited by specific chemical compositions and reaction conditions, making it difficult to achieve rapid and efficient repair while maintaining the intrinsic advantages of polysiloxanes. Similarly, polymer recycling typically relies on strategies such as thermal depolymerization, catalytic cracking, or dissolution, which suffer from problems such as complex processes, low efficiency, performance degradation, or the use of harmful solvents.

[0004] In summary, existing technologies struggle to simultaneously achieve rapid self-healing, 100% closed-loop recovery, and complete preservation of the excellent chemical stability and low surface energy properties of nonpolar polysiloxanes. Summary of the Invention

[0005] One object of the present invention is to solve at least the above-mentioned problems and / or defects, and to provide at least the advantages described below.

[0006] To achieve these objectives and other advantages of the present invention, a method for preparing a self-healing, recyclable, and antifouling ionic liquid hybrid fluorinated polysiloxane material is provided, comprising the following steps: Step 1: Synthesize fluorinated polysiloxane prepolymer; Step 2: Add ionic liquid to fluorinated polysiloxane prepolymer and heat and stir until a homogeneous prepolymer-ionic liquid mixture is formed; Step 3: Inject the prepolymer-ionic liquid mixture into the mold, cool to room temperature, and cure to obtain a self-healing, recyclable, and anti-fouling ionic liquid hybrid fluorinated polysiloxane material.

[0007] Preferably, in step one, the specific method for synthesizing the fluorinated polysiloxane prepolymer is as follows: mixing silane monomers to obtain a monomer mixture; adding dilute hydrochloric acid to the monomer mixture, stirring and reacting, cooling to room temperature, allowing it to stand and separate into layers, and then pouring off the upper aqueous phase to obtain the fluorinated polysiloxane prepolymer.

[0008] Preferably, the silane monomer includes: triethoxymethylsilane, triethoxyphenylsilane, diethoxy(methyl)phenylsilane, diethoxydimethylsilane, and 1H,1H,2H,2H-perfluorodecyltriethoxysilane.

[0009] Preferably, the molar ratio of the triethoxymethylsilane, triethoxyphenylsilane, diethoxy(methyl)phenylsilane, diethoxydimethylsilane and 1H,1H,2H,2H-perfluorodecyltriethoxysilane is 3~5:2~4:0~2:0~2:1~3.

[0010] Preferably, the pH of the dilute hydrochloric acid is 2 to 4; the amount of dilute hydrochloric acid added is 40 to 50% of the volume fraction of the monomer mixture.

[0011] Preferably, the stirring reaction is carried out at a temperature of 70-90°C for 6-10 hours.

[0012] Preferably, in step two, the ionic liquid is bis(trifluoromethanesulfonyl)imine tetrabutylammonium ([TBA][TFSI]); the amount of ionic liquid added is 15-35% of the mass of the fluorinated polysiloxane prepolymer.

[0013] Preferably, in step two, the heating and stirring temperature is 110~130℃.

[0014] Preferably, step two is replaced by: adding 1-3% by mass of reinforcing material to the ionic liquid, heating and stirring to mix evenly to obtain an ionic liquid mixture; adding 15-35% by mass of the ionic liquid mixture to the fluorinated polysiloxane prepolymer, heating and stirring until a homogeneous prepolymer-ionic liquid mixture is formed.

[0015] Preferably, the method for preparing the reinforcing material includes the following steps: S1. The nano-silica is subjected to low-temperature heat treatment to obtain activated silica; S2. Add activated silica to anhydrous ethanol and ultrasonically disperse for 20-40 min. Add polyethylene glycol 600 and ultrasonically disperse for 5-15 min. Then add heptadecafluorodecyltrimethoxysilane and adjust the pH to 3-6. Stir the reaction at 50-80℃ for 2-4 h. Centrifuge, wash, and vacuum dry to obtain modified silica A. S3. Add activated silica to anhydrous ethanol and ultrasonically disperse for 20-40 min. Add polyethylene glycol 600 and ultrasonically disperse for 5-15 min. Then add trifluoropropyltrimethoxysilane and adjust the pH to 3-6. Stir the reaction at 50-80℃ for 2-4 h. Centrifuge, wash, and vacuum dry to obtain modified silica B. S4. Mix modified silica A and modified silica B evenly to obtain the reinforcing material.

[0016] Preferably, in step S1, the specific method for low-temperature heat treatment is as follows: under a nitrogen atmosphere, the temperature is raised to 200-300°C at a heating rate of 3-7°C / min and held for 1-2 hours.

[0017] Preferably, in step S2, the mass-to-volume ratio of activated silica, polyethylene glycol 600, heptadecafluorodecyltrimethoxysilane, and anhydrous ethanol is 5-15 g: 0.3-1 g: 1-5 g: 100-300 mL.

[0018] Preferably, in step S3, the mass-to-volume ratio of activated silica, polyethylene glycol 600, trifluoropropyltrimethoxysilane, and anhydrous ethanol is 5-15 g: 0.3-1 g: 1-5 g: 100-300 mL.

[0019] Preferably, in step S4, the mass ratio of modified silica A to modified silica B is 1:1~3.

[0020] Preferably, step three is replaced by: forming the prepolymer-ionic liquid mixture onto the substrate by spin coating or blade coating, and curing it to obtain a self-healing, recyclable, and antifouling ionic liquid hybrid fluorinated polysiloxane material.

[0021] A self-healing, recyclable, and antifouling ionic liquid hybrid fluorinated polysiloxane material is prepared by the preparation method described above.

[0022] Application of a self-healing, recyclable, and antifouling ionic liquid hybrid fluorinated polysiloxane material prepared by the method described above in protective coatings.

[0023] Application of a self-healing, recyclable, and antifouling ionic liquid hybrid fluorinated polysiloxane material prepared by the method described above in antifouling coatings.

[0024] Application of a self-healing, recyclable, and antifouling ionic liquid hybrid fluorinated polysiloxane material prepared by the method described above in self-healing coatings.

[0025] Application of a self-healing, recyclable, and antifouling ionic liquid hybrid fluorinated polysiloxane material prepared by the method described above in antibacterial materials.

[0026] Preferably, the prepolymer-ionic liquid mixture obtained in step two is coated onto the substrate surface and heat-treated at 110~130°C to cure it, thereby obtaining a self-healing, recyclable, and antifouling ionic liquid hybrid fluorinated polysiloxane coating.

[0027] The present invention has at least the following beneficial effects: The present invention provides a method for preparing an ionic liquid hybrid fluorinated polysiloxane material with self-healing, closed-loop recyclability and anti-fouling functions, which solves the problem of self-healing and rapid recycling of non-polar silicone resins.

[0028] (1) Unique self-repair and recycling mechanism: Utilizing the glass transition of polysiloxane and the solid-liquid phase transition of ionic liquid, the molecular chain motion is activated during heating to achieve self-repair (efficiency up to 100%) and arbitrary reshaping. After cooling, the mechanical properties are restored, realizing rapid closed-loop recycling (completed within about 15 minutes).

[0029] (2) Excellent stability: The material retains the inherent high chemical inertness of polysiloxane, while being endowed with the required dynamic properties through ionic liquid hybridization.

[0030] (3) Green and environmentally friendly: The prepolymer is synthesized using a solvent-free aqueous phase method, which avoids the use of traditional organic solvents; the material itself is recyclable, which is in line with the concept of sustainable development.

[0031] (4) Mechanical properties: Two types of modified nano-silica were used as reinforcing materials to synergistically improve the mechanical properties of the material. First, the nano-silica was activated by low-temperature heat treatment, which facilitated subsequent modification. Then, the activated nano-silica was surface modified by heptadecafluorodecyltrimethoxysilane and trifluoropropyltrimethoxysilane, respectively, to improve interfacial compatibility and enhance the interfacial bonding force with fluorinated polysiloxanes. Experiments showed that the combination of long-chain and short-chain fluorinated silanes after modifying the nano-silica had a synergistic effect and could significantly improve the mechanical properties of the material. At the same time, polyethylene glycol was added during the modification process to improve dispersibility and promote the reaction. Then, the reinforcing material was mixed evenly with ionic liquid. The lubricating effect of the ionic liquid promoted the uniform dispersion of the reinforcing material and avoided agglomeration.

[0032] Other advantages, objectives and features of the present invention will become apparent in part from the following description, and in part from those skilled in the art through study and practice of the invention. Attached Figure Description

[0033] Figure 1 An optical photograph of the self-healing process of the FSR-L material prepared in Example 1 of this invention; Figure 2 This is a schematic diagram of the closed-loop recycling process of the FSR-L material prepared in Example 1 of the present invention; Figure 3 Infrared spectra of the FSR-L material prepared in Example 1 and the FSR material prepared in Comparative Example 1 before and after chemical stability testing; Figure 4 The FSR-L material prepared in Example 1 and the FSR material prepared in Comparative Example 1 of this invention were tested in *Pseudomonas aeruginosa* (Pseudomonas aeruginosa). Pseudomonas sp. SEM images of bacterial adhesion after immersion in bacterial solution (with steel surface as control). Detailed Implementation

[0034] The present invention will now be described in further detail with reference to the accompanying drawings, so that those skilled in the art can implement it based on the description.

[0035] It should be understood that terms such as “having,” “comprising,” and “including” as used herein do not exclude the presence or addition of one or more other elements or combinations thereof.

[0036] Example 1 A method for preparing a self-healing, recyclable, and antifouling ionic liquid hybrid fluorinated polysiloxane material includes the following steps: Step 1: Weigh and mix triethoxymethylsilane, triethoxyphenylsilane, diethoxy(methyl)phenylsilane, diethoxydimethylsilane, and 1H,1H,2H,2H-perfluorodecyltriethoxysilane in a molar ratio of 4:3:1:1:1. Add 45% by volume of dilute hydrochloric acid at pH=3 to the monomer mixture and stir vigorously at 80°C for 8 hours. After the reaction is completed, cool to room temperature, allow to stand and separate into layers, and then pour off the upper aqueous phase to obtain the fluorinated polysiloxane prepolymer. Step 2: Take a certain amount of fluorinated polysiloxane prepolymer, add 20% of its mass of bis(trifluoromethanesulfonyl)imine tetrabutylammonium ([TBA][TFSI]), and stir at 120°C until a homogeneous prepolymer-ionic liquid mixture is formed; Step 3: Pour the prepolymer-ionic liquid mixture into a polytetrafluoroethylene mold, slowly cool to room temperature, and cure to obtain a self-healing, recyclable, and anti-fouling ionic liquid hybrid fluorinated polysiloxane (FSR-L) material; Step 4: Coat a portion of the prepolymer-ionic liquid mixture onto the steel plate surface and heat-treat it at 120℃ to cure it, forming an FSR-L coating. After immersing in both glossy and matte Pseudomonas aeruginosa bacterial solutions for 30 hours, no bacteria adhered to the surface. Figure 4 As shown.

[0037] Example 2 This embodiment is basically the same as that of embodiment 1, except that in embodiment 2, the amount of [TBA][TFSI] added is 25% of the mass of the fluorinated polysiloxane prepolymer.

[0038] Example 3 This embodiment is basically the same as that of embodiment 1, except that in embodiment 3, the amount of [TBA][TFSI] added is 30% of the mass of the fluorinated polysiloxane prepolymer.

[0039] Example 4 In this embodiment, step two is replaced by: adding 2% by mass of reinforcing material to [TBA][TFSI], stirring and mixing evenly at 120°C to obtain an ionic liquid mixture; taking a certain amount of fluorinated polysiloxane prepolymer, adding 20% ​​by mass of the ionic liquid mixture, and stirring at 120°C until a homogeneous prepolymer-ionic liquid mixture is formed; the remaining steps are the same as in Example 1. The method for preparing the reinforcing material includes the following steps: S1. The nano-silica is subjected to low-temperature heat treatment. Under a nitrogen atmosphere, the temperature is increased to 250°C at a heating rate of 5°C / min and held for 1 hour to obtain activated silica. S2. Add 10g of activated silica to 200mL of anhydrous ethanol and sonicate for 30min. Add 0.5g of polyethylene glycol 600 and sonicate for 10min. Then add 2g of heptadecafluorodecyltrimethoxysilane. Adjust the pH to 5 with dilute hydrochloric acid (pH=3). Stir the reaction at 60℃ for 3h. Centrifuge, wash with anhydrous ethanol, and vacuum dry to obtain modified silica A. S3. Add 10g of activated silica to 200mL of anhydrous ethanol and sonicate for 30min. Add 0.5g of polyethylene glycol 600 and sonicate for 10min. Then add 2g of trifluoropropyltrimethoxysilane. Adjust the pH to 5 with dilute hydrochloric acid (pH=3). Stir the reaction at 60℃ for 3h. Centrifuge, wash with anhydrous ethanol, and vacuum dry to obtain modified silica B. S4. Mix modified silica A and modified silica B at a mass ratio of 1:2 to obtain the reinforcing material.

[0040] Example 5 In this embodiment, the mass ratio of modified silica A to modified silica B in the reinforcing material is 1:1, and the remaining steps are the same as in Example 4.

[0041] Example 6 In this embodiment, the mass ratio of modified silica A to modified silica B in the reinforcing material is 1:3, and the remaining steps are the same as in Example 4.

[0042] Example 7 In this embodiment, the method for preparing the reinforcing material includes the following steps: S1. The nano-silica is subjected to low-temperature heat treatment. Under a nitrogen atmosphere, the temperature is increased to 250°C at a heating rate of 5°C / min and held for 1 hour to obtain activated silica. S2. Add 10g of activated silica to 200mL of anhydrous ethanol and sonicate for 30min. Add 0.5g of polyethylene glycol 600 and sonicate for 10min. Then add 2g of heptadecafluorodecyltrimethoxysilane. Adjust the pH to 5 with dilute hydrochloric acid (pH=3). Stir the reaction at 60℃ for 3h. Centrifuge, wash with anhydrous ethanol, and vacuum dry to obtain modified silica A, i.e., the reinforcing material. The remaining steps are the same as in Example 4; Compared to Example 4, this example only uses heptadecafluorodecyltrimethoxysilane for modification.

[0043] Example 8 In this embodiment, the method for preparing the reinforcing material includes the following steps: S1. The nano-silica is subjected to low-temperature heat treatment. Under a nitrogen atmosphere, the temperature is increased to 250°C at a heating rate of 5°C / min and held for 1 hour to obtain activated silica. S2. Add 10g of activated silica to 200mL of anhydrous ethanol and sonicate for 30min. Add 0.5g of polyethylene glycol 600 and sonicate for 10min. Then add 2g of trifluoropropyltrimethoxysilane. Adjust the pH to 5 with dilute hydrochloric acid (pH=3). Stir the reaction at 60℃ for 3h. Centrifuge, wash with anhydrous ethanol, and vacuum dry to obtain modified silica B, i.e., the reinforcing material. The remaining steps are the same as in Example 4; Compared to Example 4, this example only uses trifluoropropyltrimethoxysilane for modification.

[0044] Example 9 In this embodiment, the method for preparing the reinforcing material includes the following steps: S1. Add 10g of nano-silica to 200mL of anhydrous ethanol and sonicate for 30min. Add 0.5g of polyethylene glycol 600 and sonicate for 10min. Then add 2g of heptadecafluorodecyltrimethoxysilane. Adjust the pH to 5 with dilute hydrochloric acid (pH=3). Stir the reaction at 60℃ for 3h. Centrifuge, wash with anhydrous ethanol, and vacuum dry to obtain modified silica A. S2. Add 10g of nano-silica to 200mL of anhydrous ethanol and sonicate for 30min. Add 0.5g of polyethylene glycol 600 and sonicate for 10min. Then add 2g of trifluoropropyltrimethoxysilane. Adjust the pH to 5 with dilute hydrochloric acid (pH=3). Stir the reaction at 60℃ for 3h. Centrifuge, wash with anhydrous ethanol, and vacuum dry to obtain modified silica B. S3. Mix modified silica A and modified silica B at a mass ratio of 1:2 to obtain a reinforcing material; The remaining steps are the same as in Example 4; Compared to Example 4, this example does not involve low-temperature heat treatment.

[0045] Example 10 In this embodiment, the method for preparing the reinforcing material includes the following steps: S1. The nano-silica is subjected to low-temperature heat treatment. Under a nitrogen atmosphere, the temperature is increased to 250°C at a heating rate of 5°C / min and held for 1 hour to obtain activated silica. S2. Add 10g of activated silica to 200mL of anhydrous ethanol, sonicate for 40min, then add 2g of heptadecafluorodecyltrimethoxysilane, adjust pH to 5 with dilute hydrochloric acid (pH=3), stir and react at 60℃ for 3h, centrifuge, wash with anhydrous ethanol, and vacuum dry to obtain modified silica A. S3. Add 10g of activated silica to 200mL of anhydrous ethanol, sonicate for 40min, then add 2g of trifluoropropyltrimethoxysilane, adjust pH to 5 with dilute hydrochloric acid (pH=3), stir and react at 60℃ for 3h, centrifuge, wash with anhydrous ethanol, and vacuum dry to obtain modified silica B. S4. Mix modified silica A and modified silica B at a mass ratio of 1:2 to obtain a reinforcing material. The remaining steps are the same as in Example 4; Compared to Example 4, this example does not include polyethylene glycol 600.

[0046] Example 11 In this embodiment, step two is replaced by: adding 2% by mass of nano-silica to [TBA][TFSI], stirring and mixing evenly at 120°C to obtain an ionic liquid mixture; taking a certain amount of fluorinated polysiloxane prepolymer, adding 20% ​​by mass of the ionic liquid mixture, and stirring at 120°C until a homogeneous prepolymer-ionic liquid mixture is formed; the remaining steps are the same as in Example 1. Compared to Example 4, nano-silica is directly added in this example.

[0047] Comparative Example 1 A method for preparing a fluorinated silicone resin includes the following steps: Step 1: Weigh and mix triethoxymethylsilane, triethoxyphenylsilane, diethoxy(methyl)phenylsilane, diethoxydimethylsilane, and 1H,1H,2H,2H-perfluorodecyltriethoxysilane in a molar ratio of 4:3:1:1:1. Add dilute hydrochloric acid with pH=3 to the monomer mixture and stir vigorously at 80°C for 8 hours. After the reaction is completed, cool to room temperature, allow to stand and separate into layers, and pour off the upper aqueous phase to obtain fluorinated polysiloxane prepolymer. Step 2: The fluorinated polysiloxane prepolymer is poured into a polytetrafluoroethylene mold and subjected to step-by-step thermosetting: the temperature is gradually increased from 120°C to 150°C at a heating rate of 10°C / h and held for 1 hour, and finally cured at 200°C for 2 hours to complete cross-linking and obtain cured fluorinated silicone resin (FSR). Compared to Example 1, this comparative example does not add [TBA][TFSI] ionic liquid, and directly cures the fluorinated polysiloxane prepolymer.

[0048] Performance Testing and Results Analysis Self-healing and recyclability: The FSR-L and FSR specimens obtained in the examples and comparative examples were stretched to breakage, and then the fracture surfaces were tightly fitted together and heated at 90°C for 5 minutes for repair, followed by cooling to room temperature; the broken FSR-L and FSR materials were heated and melted at 90°C and injected into a mold for cooling.

[0049] like Figure 1 As shown, the FSR-L spline prepared in Example 1 was reconnected and the seam disappeared, restoring its original shape. Figure 2 As shown, the broken FSR-L material was heated and melted at 90°C, injected into a mold and cooled, completing closed-loop recycling and reshaping. The mechanical property data of Examples 1-3 before repair, after repair, and after recycling are shown in Table 1. It can be seen that after the FSR-L in Examples 1-3 fractured, the fractured area could be quickly reconnected and restored to its original shape and mechanical properties under conditions of 90°C and 5 minutes, achieving a self-repair efficiency of 100%. After the FSR-L in Examples 1-3 fractured, it was heated and melted at 90°C, injected into a mold and cooled, achieving 100% closed-loop recycling and reshaping within 15 minutes. The FSR prepared in Comparative Example 1 could not achieve self-repair and recycling.

[0050] Table 1 Stability: Samples from Example 1 and Comparative Example 1 were immersed in hydrochloric acid (pH=1) and sodium hydroxide (pH=14) for 48 hours, respectively, or subjected to 240 hours of UV aging. Figure 3 FTIR analysis showed that the chemical structure of the FSR-L material in Example 1 did not change significantly, demonstrating its excellent chemical stability and aging resistance. In contrast, the FSR material prepared in Comparative Example 1 without the addition of an ionic liquid did not show significant structural changes, which is attributed to the excellent stability of the fluorinated polysiloxane. This indicates that the FSR-L material prepared according to this invention retains the inherent high chemical inertness of fluorinated polysiloxane while acquiring the desired dynamic properties through ionic liquid hybridization.

[0051] Antifouling performance: The FSR-L material prepared in Example 1 and the FSR material prepared in Comparative Example 1 were immersed in light- and dark-light-treated common Pseudomonas bacterial solutions for 30 hours. SEM images of bacterial adhesion on their surfaces are shown below. Figure 4 As shown, with a steel surface as a control, it can be seen that no intact cells were observed adhering to the surface of the FSR-L material; only some debris was attached. This indicates that the FSR-L material of the present invention can effectively prevent microbial adhesion and has excellent antibacterial and antifouling properties.

[0052] Tensile strength tests revealed that the tensile strength of FSR-L materials in Examples 1-3 was lower than that of FSR in Comparative Example 1, indicating that the mechanical properties of the material were reduced due to ionic liquid hybridization. To improve the mechanical properties of the material, this invention utilizes two types of modified nano-silica as reinforcing materials to synergistically enhance the mechanical properties. The tensile strengths are shown in Table 2. The tensile strengths of the FSR-L materials prepared in Examples 4-11 were all higher than those in Example 1. Meanwhile, the FSR-L materials prepared in Examples 4-11 still maintain excellent self-healing and recycling properties, stability, and antibacterial and antifouling properties: after fracture, they can recover their original shape and mechanical properties at 90°C for 5 minutes, and the self-healing efficiency can still reach 100%; after breakage, they can be heated and melted at 90°C, injected into a mold and cooled, and 100% closed-loop recycling and remolding can be achieved within 15 minutes; after immersion in hydrochloric acid (pH=1) or sodium hydroxide (pH=14) for 48 hours, or after 240 hours of ultraviolet aging, the chemical structure did not change significantly; after immersion in light / dark Pseudomonas aeruginosa bacterial solution for 30 hours, no intact cells were observed adhering to the surface of the material.

[0053] Table 2 Example 1 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Tensile strength / MPa 1.9 3.4 3.1 3.3 2.5 2.7 3.1 3.2 2.1 Although embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and embodiments. They can be applied to various fields suitable for the present invention. For those skilled in the art, other modifications can be easily made. Therefore, without departing from the general concept defined by the claims and their equivalents, the present invention is not limited to the specific details and illustrations shown and described herein.

Claims

1. A process for the preparation of a self-healing recyclable stain repellent ionic liquid hybrid fluorinated polysiloxane material, characterized in that, The method comprises the following steps: Step one, synthesizing fluorinated polysiloxane prepolymer; Step two, adding ionic liquid to the fluorinated polysiloxane prepolymer, heating and stirring to obtain a prepolymer-ionic liquid mixture; Step three, injecting the prepolymer-ionic liquid mixture into a mold, cooling to room temperature, and curing to obtain a self-repairing, recyclable, stain-resistant ionic liquid hybrid fluorinated polysiloxane material.

2. The process for preparing a self-healing recyclable stain repellent ionic liquid hybrid fluorinated polysiloxane material according to claim 1, wherein, In the step one, the specific method for synthesizing the fluorinated polysiloxane prepolymer is as follows: mixing silane monomers to obtain a monomer mixture; adding dilute hydrochloric acid to the monomer mixture, stirring and reacting, cooling to room temperature, standing and separating into layers, and then pouring off the upper aqueous phase to obtain the fluorinated polysiloxane prepolymer.

3. A process for the preparation of a self-healing recyclable stain repellent ionic liquid hybrid fluorinated polysiloxane material as claimed in claim 2, wherein, The silane monomers include triethoxymethylsilane, triethoxyphenylsilane, diethoxy(methyl)phenylsilane, diethoxydimethylsilane, and 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane.

4. A process for the preparation of a self-healing recyclable stain repellent ionic liquid hybrid fluorinated polysiloxane material as claimed in claim 3, wherein, The molar ratio of the triethoxymethylsilane, triethoxyphenylsilane, diethoxy(methyl)phenylsilane, diethoxydimethylsilane, and 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane is 3-5: 2-4: 0-2: 0-2: 1-3.

5. The process for preparing a self-healing, recyclable, stain resistant ionic liquid hybrid fluorinated polysiloxane material according to claim 2, wherein, The pH of the dilute hydrochloric acid is 2-4, and the dilute hydrochloric acid is added in an amount of 40-50% of the volume fraction of the monomer mixture.

6. The process for preparing a self-healing, recyclable, stain repellent ionic liquid hybrid fluorinated polysiloxane material according to claim 2, wherein, The stirring and reaction temperature is 70-90°C, and the time is 6-10h.

7. The process for preparing a self-healing, recyclable, stain repellent ionic liquid hybrid fluorinated polysiloxane material according to claim 1, wherein, In the step two, the ionic liquid is bis(trifluoromethylsulfonyl) imide tetrabutylammonium, and the amount of the ionic liquid added is 15-35% of the mass of the fluorinated polysiloxane prepolymer.

8. The process for preparing a self-healing, recyclable, stain repellent ionic liquid hybrid fluorinated polysiloxane material according to claim 1, wherein, In the step two, the heating and stirring temperature is 110-130°C.

9. A self-healing recyclable stain repellent ionic liquid hybrid fluorinated polysiloxane material, characterized in that, The self-repairing, recyclable, stain-resistant ionic liquid hybrid fluorinated polysiloxane material is prepared by the method of any one of claims 1-8.

10. Use of the self-repairing, recyclable, stain-resistant ionic liquid hybrid fluorinated polysiloxane material of claim 9 in a stain-resistant coating.

Images