A fluorine releasing agent composition having antibacterial properties and a method for preparing the same

Abstract

The application discloses a fluorine release agent composition with antibacterial performance and a preparation method thereof, and belongs to the technical field of mixed coating preparation. The preparation method comprises the following steps: mixing hydrogen-containing silicone oil, a composite emulsifier, water and anhydrous ethanol, and then hydrolyzing at 50 DEG C-60 DEG C for 50 min-80 min to obtain a hydrolysis emulsion; mixing the hydrolysis emulsion and an antibacterial extract, and then reacting at 50 DEG C-60 DEG C for 3 h-4 h to obtain modified hydrogen-containing silicone oil; mixing the modified hydrogen-containing silicone oil, a fluorine-containing alkyl compound and an addition catalyst, and then heating to 80 DEG C-90 DEG C to react for 7 h-8 h to obtain the fluorine release agent composition. The modified hydrogen-containing silicone oil obtained by modifying the hydrogen-containing silicone oil and the fluorine-containing alkyl compound are reacted through a silicon hydrogen addition reaction, and the fluorine release agent composition with low release force, good demolding effect and antibacterial performance is obtained.

Description

Technical Field

[0001] This invention belongs to the field of mixed coating preparation technology, specifically relating to a fluorinated release agent composition with antibacterial properties and its preparation method. Background Technology

[0002] Fluorinated release agents are substances primarily used to reduce friction and adhesion between material surfaces, separating two surfaces that are difficult or impossible to separate. The main components of fluorinated release agents generally include fluoropolymers (such as polytetrafluoroethylene PTFE), fluorinated hydrocarbons, and other fluorinated compounds. Fluorinated release agents typically possess good properties such as high temperature resistance, corrosion resistance, chemical inertness, and low surface energy. Based on these properties, fluorinated release agents are widely used in multiple fields, including: (1) Plastics and rubber industry: In the production process of plastics and rubber products, fluorinated release agents are used as mold release agents to reduce adhesion between the mold and the finished product, thereby improving production efficiency. Due to their excellent high temperature resistance and chemical stability, fluorinated release agents can maintain good performance under high temperature conditions; (2) Coatings and inks: In the production of coatings and inks, fluorinated release agents can be used to improve the leveling, gloss, and stain resistance of the coating. Their low surface energy properties make the coating surface easier to clean, improving the product's service life and maintenance convenience; (3) Electronics industry: In the manufacturing process of electronic components, fluorinated release agents can be used as anti-sticking agents to ensure the stability of electronic components in high temperature and humid environments, preventing short circuits and corrosion; (4) Food processing: In food packaging and processing equipment, fluorinated release agents can effectively prevent food from sticking to the equipment surface, ensuring smooth production and meeting food safety standards.

[0003] With increasing emphasis on health and safety, the antibacterial function of fluorinated release agents is receiving growing attention. For example, in the food industry, the application of antibacterial fluorinated release agents in food-grade coatings that come into direct contact with food can reduce the rate of corrosion and spoilage, thereby extending the shelf life of food. In the medical and pharmaceutical fields, such as in certain medical devices and pharmaceutical clean areas, the application of antibacterial fluorinated release agents can effectively reduce the risk of bacterial infection and ensure the safety of patients and medicines.

[0004] There are very few reports in the existing technology on coatings prepared with fluorinated release agents in the field of antibacterial properties. Therefore, researching a fluorinated release agent with antibacterial effects is a technical problem that urgently needs to be solved. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention utilizes a modified hydrogen-containing silicone oil obtained by modifying hydrogen-containing silicone oil and a fluorinated alkyl compound through a hydrosilylation reaction to obtain a fluorinated release agent composition, thereby solving the technical problems mentioned in the background art. Specifically, the technical solution of this invention includes the following:

[0006] One objective of this invention is to provide a method for preparing a fluorinated release agent composition with antibacterial properties, the preparation method comprising the following steps:

[0007] Hydrogen-containing silicone oil, composite emulsifier, water and anhydrous ethanol are mixed and heated to 50℃~60℃ for 50min~80min to hydrolyze and obtain hydrolyzed emulsion;

[0008] Modified hydrogen-containing silicone oil was obtained by mixing hydrolyzed emulsion and antibacterial extract and reacting at 50℃~60℃ for 3h~4h.

[0009] A fluorinated release agent composition is obtained by mixing modified hydrogen-containing silicone oil, fluorinated alkyl compound and addition catalyst and heating to 80℃~90℃ for 7h~8h.

[0010] Furthermore, the hydrogen content of the hydrogen-containing silicone oil is 0.3% to 0.6%.

[0011] Furthermore, the composite emulsifier is composed of Span 40, AEO-25 and Tween 80 in a weight ratio of 0.2-0.3:1:0.1-0.2.

[0012] Furthermore, the weight ratio of the hydrogen-containing silicone oil, composite emulsifier, water, and anhydrous ethanol is 10:1-1.5:10-15:25-30.

[0013] Furthermore, the antibacterial extract includes chlorogenic acid or rosmarinic acid, and the antibacterial extract needs to contain a hydroxyl structure for condensation with silanol groups in the hydrolyzed emulsion.

[0014] Furthermore, the weight ratio of the hydrolyzed emulsion to the antibacterial extract is 1:0.1 to 0.4.

[0015] Furthermore, the fluorinated alkyl compound includes hexafluorobutyl acrylate or hexafluorobutyl methacrylate, and the fluorinated alkyl compound needs to contain a carbon-carbon double bond for introduction into the modified hydrogen-containing silicone oil via hydrosilylation.

[0016] Furthermore, the addition catalyst comprises a chloroplatinic acid solution with a mass concentration of 50 mg / L.

[0017] Furthermore, the weight ratio of the modified hydrogen-containing silicone oil, the fluorinated alkyl compound, and the addition catalyst is 1:0.4-0.7:0.5-0.6.

[0018] A second objective of this invention is to provide a fluorinated release agent composition prepared by a method for preparing a fluorinated release agent composition with antibacterial properties.

[0019] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0020] This invention first modifies hydrogen-containing silicone oil by condensing the silanol groups generated after hydrolysis of the hydrogen-containing silicone oil with the hydroxyl groups on an antibacterial extract to form siloxane bonds, thereby introducing the antibacterial extract into the hydrogen-containing silicone oil to obtain modified hydrogen-containing silicone oil. Next, the modified hydrogen-containing silicone oil and a fluorinated alkyl compound are subjected to a hydrosilylation reaction to introduce fluorine atoms into the modified hydrogen-containing silicone oil, resulting in a fluorinated release agent composition with low release force, good demolding effect, and good antibacterial properties. Detailed Implementation

[0021] The technical solution of the present invention will be clearly and completely described below through embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0022] Unless otherwise stated, all raw materials and reagents used in this invention are commercially available or can be prepared by known methods.

[0023] Example 1:

[0024] A method for preparing a fluorinated release agent composition with antibacterial properties, specifically comprising the following steps:

[0025] Weigh 20 parts by weight of deionized water and 60 parts by weight of anhydrous ethanol and mix them in a flask. Then add 2 parts by weight of a composite emulsifier (composed of Span 40, AEO-25, and Tween 80 in a weight ratio of 0.2:1:0.1) and mix and stir until evenly dispersed. Next, weigh 20 parts by weight of hydrogen-containing silicone oil with a hydrogen content of 0.3% and add it to the flask. Mix and stir at 400 rpm for 20 min. After stirring, place the flask in a water bath and hydrolyze it at 50°C for 50 min. After the reaction is complete, cool to room temperature to obtain the hydrolyzed emulsion.

[0026] Four parts by weight of hydrolyzed emulsion and 0.4 parts by weight of chlorogenic acid were weighed and mixed to obtain a mixture. The mixture was placed in a water bath and condensed at 50°C for 3 hours. After condensation, it was cooled to room temperature to obtain modified hydrogen-containing silicone oil.

[0027] Two parts by weight of modified hydrogen-containing silicone oil, 0.8 parts by weight of hexafluorobutyl acrylate, and 1 part by weight of chloroplatinic acid solution (50 mg / L) were weighed and added to a reaction vessel. Nitrogen gas was then introduced into the reaction vessel to purge the air inside. Under nitrogen protection, the reaction vessel was heated to 80°C and stirred for 7 hours. After the reaction was completed, the mixture was cooled to room temperature and removed from the reaction vessel. The mixture was then subjected to vacuum distillation to obtain the fluorinated release agent composition.

[0028] Example 2:

[0029] A method for preparing a fluorinated release agent composition with antibacterial properties, specifically comprising the following steps:

[0030] 24 parts by weight of deionized water and 56 parts by weight of anhydrous ethanol were weighed and mixed in a flask. Then, 2.4 parts by weight of a composite emulsifier (composed of Span 40, AEO-25, and Tween 80 in a weight ratio of 0.2:1:0.15) were added and mixed until uniformly dispersed. Next, 20 parts by weight of hydrogen-containing silicone oil with a hydrogen content of 0.4% were weighed and added to the flask, and the mixture was stirred at 400 rpm for 20 minutes. After stirring, the flask was placed in a water bath and hydrolyzed at 55°C for 60 minutes. After the reaction was complete, the mixture was cooled to room temperature to obtain the hydrolyzed emulsion.

[0031] Four parts by weight of hydrolyzed emulsion and 0.8 parts by weight of chlorogenic acid were weighed and mixed to obtain a mixture. The mixture was placed in a water bath and condensed at 55°C for 3.5 hours. After condensation, the mixture was cooled to room temperature to obtain modified hydrogen-containing silicone oil.

[0032] Two parts by weight of modified hydrogen-containing silicone oil, one part by weight of hexafluorobutyl acrylate, and one part by weight of chloroplatinic acid solution (50 mg / L) were weighed and added to a reaction vessel. Nitrogen gas was then introduced into the reaction vessel to purge the air inside. Under nitrogen protection, the reaction vessel was heated to 85°C and stirred for 7.5 hours. After the reaction was completed, the mixture was cooled to room temperature and removed from the reaction vessel. The mixture was then subjected to vacuum distillation to obtain the fluorinated release agent composition.

[0033] Example 3:

[0034] A method for preparing a fluorinated release agent composition with antibacterial properties, specifically comprising the following steps:

[0035] 28 parts by weight of deionized water and 52 parts by weight of anhydrous ethanol were weighed and mixed in a flask. Then, 2.8 parts by weight of a composite emulsifier (composed of Span 40, AEO-25, and Tween 80 in a weight ratio of 0.3:1:0.15) were added and stirred until uniformly dispersed. Next, 20 parts by weight of hydrogen-containing silicone oil with a hydrogen content of 0.5% were weighed and added to the flask, and the mixture was stirred at 400 rpm for 20 minutes. After stirring, the flask was placed in a water bath and hydrolyzed at 55°C for 70 minutes. After the reaction was complete, the mixture was cooled to room temperature to obtain the hydrolyzed emulsion.

[0036] Four parts by weight of hydrolyzed emulsion and 0.12 parts by weight of rosmarinic acid were weighed and mixed to obtain a mixture. The mixture was placed in a water bath and condensed at 55°C for 3.5 hours. After condensation, it was cooled to room temperature to obtain modified hydrogen-containing silicone oil.

[0037] Two parts by weight of modified hydrogen-containing silicone oil, 1.2 parts by weight of hexafluorobutyl methacrylate, and 1.2 parts by weight of chloroplatinic acid solution (50 mg / L) were weighed and added to a reaction vessel. Nitrogen gas was then introduced into the reaction vessel to purge the air inside. Under nitrogen protection, the reaction vessel was heated to 85°C and stirred for 8 hours. After the reaction was completed, the mixture was cooled to room temperature and removed from the reaction vessel. The mixture was then subjected to vacuum distillation to obtain the fluorinated release agent composition.

[0038] Example 4:

[0039] A method for preparing a fluorinated release agent composition with antibacterial properties, specifically comprising the following steps:

[0040] Weigh 30 parts by weight of deionized water and 50 parts by weight of anhydrous ethanol and mix them in a flask. Then add 3 parts by weight of a composite emulsifier (composed of Span 40, AEO-25, and Tween 80 in a weight ratio of 0.3:1:0.2) and mix and stir until evenly dispersed. Next, weigh 20 parts by weight of hydrogen-containing silicone oil with a hydrogen content of 0.6% and add it to the flask. Mix and stir at 400 rpm for 20 min. After stirring, place the flask in a water bath and hydrolyze it at 60°C for 80 min. After the reaction is complete, cool to room temperature to obtain the hydrolyzed emulsion.

[0041] Four parts by weight of hydrolyzed emulsion and 0.16 parts by weight of rosmarinic acid were weighed and mixed to obtain a mixture. The mixture was placed in a water bath and condensed at 60°C for 4 hours. After condensation, it was cooled to room temperature to obtain modified hydrogen-containing silicone oil.

[0042] Two parts by weight of modified hydrogen-containing silicone oil, 1.4 parts by weight of hexafluorobutyl methacrylate, and 1.2 parts by weight of chloroplatinic acid solution (50 mg / L) were weighed and added to a reaction vessel. Nitrogen gas was then introduced into the reaction vessel to purge the air inside. Under nitrogen protection, the reaction vessel was heated to 90°C and stirred for 8 hours. After the reaction was completed, the mixture was cooled to room temperature and removed from the reaction vessel. The mixture was then subjected to vacuum distillation to obtain the fluorinated release agent composition.

[0043] Comparative Example 1:

[0044] A method for preparing a fluorinated release agent composition with antibacterial properties, specifically comprising the following steps:

[0045] Weigh 30 parts by weight of deionized water and 50 parts by weight of anhydrous ethanol and mix them in a flask. Then add 3 parts by weight of a composite emulsifier (composed of Span 40, AEO-25, and Tween 80 in a weight ratio of 0.3:1:0.2) and mix and stir until evenly dispersed. Next, weigh 20 parts by weight of hydrogen-containing silicone oil with a hydrogen content of 0.2% and add it to the flask. Mix and stir at 400 rpm for 20 min. After stirring, place the flask in a water bath and hydrolyze it at 60°C for 80 min. After the reaction is complete, cool to room temperature to obtain the hydrolyzed emulsion.

[0046] The remaining process is consistent with Example 4.

[0047] Comparative Example 2:

[0048] A method for preparing a fluorinated release agent composition with antibacterial properties, specifically comprising the following steps:

[0049] Weigh 30 parts by weight of deionized water and 50 parts by weight of anhydrous ethanol and mix them in a flask. Then add 3 parts by weight of a composite emulsifier (composed of Span 40, AEO-25, and Tween 80 in a weight ratio of 0.3:1:0.2) and mix and stir until evenly dispersed. Next, weigh 20 parts by weight of hydrogen-containing silicone oil with a hydrogen content of 0.8% and add it to the flask. Mix and stir at 400 rpm for 20 min. After stirring, place the flask in a water bath and hydrolyze it at 60°C for 80 min. After the reaction is complete, cool to room temperature to obtain the hydrolyzed emulsion.

[0050] The remaining process is consistent with Example 4.

[0051] Comparative Example 3:

[0052] A method for preparing a fluorinated release agent composition with antibacterial properties, specifically comprising the following steps:

[0053] Weigh 30 parts by weight of deionized water and 50 parts by weight of anhydrous ethanol and mix them in a flask. Then add 3 parts by weight of Span 40 and stir until evenly dispersed. Next, weigh 20 parts by weight of hydrogen-containing silicone oil with a hydrogen content of 0.6% and add it to the flask. Mix and stir at 400 rpm for 20 min. After stirring, place the flask in a water bath and hydrolyze it at 60°C for 80 min. After the reaction is complete, cool to room temperature to obtain the hydrolyzed emulsion.

[0054] The remaining process is consistent with Example 4.

[0055] Comparative Example 4:

[0056] A method for preparing a fluorinated release agent composition with antibacterial properties, specifically comprising the following steps:

[0057] Weigh 30 parts by weight of deionized water and 50 parts by weight of anhydrous ethanol and mix them in a flask. Then add 3 parts by weight of a composite emulsifier (composed of Span 40, AEO-25, and Tween 80 in a weight ratio of 0.5:0.5:0.5) and mix and stir until evenly dispersed. Next, weigh 20 parts by weight of hydrogen-containing silicone oil with a hydrogen content of 0.6% and add it to the flask. Mix and stir at 400 rpm for 20 min. After stirring, place the flask in a water bath and hydrolyze it at 60°C for 80 min. After the reaction is complete, cool to room temperature to obtain the hydrolyzed emulsion.

[0058] The remaining process is consistent with Example 4.

[0059] Comparative Example 5:

[0060] A method for preparing a fluorinated release agent composition with antibacterial properties, specifically comprising the following steps:

[0061] Weigh 30 parts by weight of deionized water and 50 parts by weight of anhydrous ethanol and mix them in a flask. Then add 3 parts by weight of a composite emulsifier (composed of Span 40, AEO-25, and Tween 80 in a weight ratio of 0.3:1:0.2) and mix and stir until evenly dispersed. Next, weigh 20 parts by weight of hydrogen-containing silicone oil with a hydrogen content of 0.6% and add it to the flask. Mix and stir at 400 rpm for 20 min. After stirring, place the flask in a water bath and hydrolyze it at 60°C for 80 min. After the reaction is complete, cool to room temperature to obtain the hydrolyzed emulsion.

[0062] Four parts by weight of hydrolyzed emulsion and 0.16 parts by weight of limonene were weighed and mixed to obtain a mixture. The mixture was placed in a water bath and condensed at 60°C for 4 hours. After condensation, it was cooled to room temperature to obtain modified hydrogen-containing silicone oil.

[0063] Two parts by weight of modified hydrogen-containing silicone oil, 1.4 parts by weight of hexafluorobutyl methacrylate, and 1.2 parts by weight of chloroplatinic acid solution (50 mg / L) were weighed and added to a reaction vessel. Nitrogen gas was then introduced into the reaction vessel to purge the air inside. Under nitrogen protection, the reaction vessel was heated to 90°C and stirred for 8 hours. After the reaction was completed, the mixture was cooled to room temperature and removed from the reaction vessel. The mixture was then subjected to vacuum distillation to obtain the fluorinated release agent composition.

[0064] Comparative Example 6:

[0065] A method for preparing a fluorinated release agent composition with antibacterial properties, specifically comprising the following steps:

[0066] Weigh 30 parts by weight of deionized water and 50 parts by weight of anhydrous ethanol and mix them in a flask. Then add 3 parts by weight of a composite emulsifier (composed of Span 40, AEO-25, and Tween 80 in a weight ratio of 0.3:1:0.2) and mix and stir until evenly dispersed. Next, weigh 20 parts by weight of hydrogen-containing silicone oil with a hydrogen content of 0.6% and add it to the flask. Mix and stir at 400 rpm for 20 min. After stirring, place the flask in a water bath and hydrolyze it at 60°C for 80 min. After the reaction is complete, cool to room temperature to obtain the hydrolyzed emulsion.

[0067] Four parts by weight of hydrolyzed emulsion and 0.16 parts by weight of rosmarinic acid were weighed and mixed to obtain a mixture. The mixture was placed in a water bath and condensed at 60°C for 4 hours. After condensation, it was cooled to room temperature to obtain modified hydrogen-containing silicone oil.

[0068] Two parts by weight of modified hydrogen-containing silicone oil, 1.4 parts by weight of trifluoropropylmethylcyclotrisiloxane, and 1.2 parts by weight of chloroplatinic acid solution (50 mg / L) were weighed and added to a reaction vessel. Nitrogen gas was then introduced into the reaction vessel to purge the air inside. Under nitrogen protection, the reaction vessel was heated to 90°C and stirred for 8 hours. After the reaction was completed, the mixture was cooled to room temperature and removed from the reaction vessel. The mixture was then subjected to vacuum distillation to obtain the fluorinated release agent composition.

[0069] Comparative Example 7:

[0070] A method for preparing a fluorinated release agent composition with antibacterial properties, specifically comprising the following steps:

[0071] Weigh 30 parts by weight of deionized water and 50 parts by weight of anhydrous ethanol and mix them in a flask. Then add 3 parts by weight of a composite emulsifier (composed of Span 40, AEO-25, and Tween 80 in a weight ratio of 0.3:1:0.2) and mix and stir until evenly dispersed. Next, weigh 20 parts by weight of hydrogen-containing silicone oil with a hydrogen content of 0.6% and add it to the flask. Mix and stir at 400 rpm for 20 min. After stirring, place the flask in a water bath and hydrolyze it at 60°C for 80 min. After the reaction is complete, cool to room temperature to obtain the hydrolyzed emulsion.

[0072] Four parts by weight of hydrolyzed emulsion and 0.16 parts by weight of rosmarinic acid were weighed and mixed to obtain a mixture. The mixture was placed in a water bath and condensed at 60°C for 4 hours. After condensation, it was cooled to room temperature to obtain modified hydrogen-containing silicone oil.

[0073] Two parts by weight of modified hydrogen-containing silicone oil, 1.4 parts by weight of perfluorobutylethylene, and 1.2 parts by weight of chloroplatinic acid solution (50 mg / L) were weighed and added to a reaction vessel. Nitrogen gas was then introduced into the reaction vessel to purge the air inside. Under nitrogen protection, the reaction vessel was heated to 90°C and stirred for 8 hours. After the reaction was completed, the mixture was cooled to room temperature and removed from the reaction vessel. The mixture was then subjected to vacuum distillation to obtain the fluorinated release agent composition.

[0074] Comparative Example 8:

[0075] A method for preparing a fluorinated release agent composition with antibacterial properties, specifically comprising the following steps:

[0076] Weigh 30 parts by weight of deionized water and 50 parts by weight of anhydrous ethanol and mix them in a flask. Then add 3 parts by weight of a composite emulsifier (composed of Span 40, AEO-25, and Tween 80 in a weight ratio of 0.3:1:0.2) and mix and stir until evenly dispersed. Next, weigh 20 parts by weight of hydrogen-containing silicone oil with a hydrogen content of 0.6% and add it to the flask. Mix and stir at 400 rpm for 20 min. After stirring, place the flask in a water bath and hydrolyze it at 70°C for 100 min. After the reaction is complete, cool to room temperature to obtain the hydrolyzed emulsion.

[0077] Four parts by weight of hydrolyzed emulsion and 0.16 parts by weight of rosmarinic acid were weighed and mixed to obtain a mixture. The mixture was placed in a water bath and condensed at 60°C for 4 hours. After condensation, it was cooled to room temperature to obtain modified hydrogen-containing silicone oil.

[0078] The remaining process is consistent with Example 4.

[0079] Release force test:

[0080] The fluorinated release agent compositions obtained in Examples 1-4 and Comparative Examples 1-8 were mixed and dissolved in n-heptane as a solvent to prepare a 5% (w / w) coating solution. The coating solution was then applied to a PET film with a thickness controlled at 10 μm, and cured at 140°C for 6 minutes to obtain a release film. 20 mm × 200 mm adhesive tape was applied to the release film, and a 2 kg roller was used to manually press it back and forth 5 times. After standing for 30 minutes, a 180° peel test was performed at a peeling speed of 5 mm / s. The results are shown in Table 1 below.

[0081] Table 1 Release Force Magnitude

[0082] Source of materials Release force (g / 25mm) Example 1 3.17 Example 2 3.12 Example 3 3.05 Example 4 3.08 Comparative Example 1 4.45 Comparative Example 2 4.41 Comparative Example 3 4.22 Comparative Example 4 4.08 Comparative Example 5 5.21 Comparative Example 6 5.18 Comparative Example 7 4.27 Comparative Example 8 3.13

[0083] Demolding performance test:

[0084] The fluorinated release agent compositions prepared in Examples 1-4 and Comparative Examples 1-8 were brushed onto the mold surface in two coats. After the first coat was completely dry, the second coat was applied. After drying, the PU foam mixture (polyester TPU and azodicarbonamide mixed in a weight ratio of 1:0.02) was poured into the mold. After high-temperature foaming at 220°C, the mold was cooled to room temperature and completely removed, which was recorded as demolding 1. Then, the PU foam mixture was poured back into the mold, and after foaming and molding again, it was completely removed again, which was recorded as demolding 2. This process was repeated until the mold could no longer be removed. The results are shown in Table 2 below.

[0085] Table 2 Demolding performance

[0086] Source of materials Number of demolding cycles Example 1 8 Example 2 9 Example 3 10 Example 4 10 Comparative Example 1 3 Comparative Example 2 3 Comparative Example 3 4 Comparative Example 4 5 Comparative Example 5 1 Comparative Example 6 1 Comparative Example 7 4 Comparative Example 8 9

[0087] Antibacterial performance test:

[0088] The fluorinated release agent compositions obtained in Examples 1-4 and Comparative Examples 1-8 were mixed with sterilized LB liquid culture medium at a weight ratio of 1:1 and then dispersed uniformly by ultrasonication at 300W to obtain a mixed liquid culture medium. The initial viable count was 1×10⁻⁶. 9 Staphylococcus aureus culture medium with CFU / mL and an initial viable count of 1×10⁻⁶ 9 E. coli culture medium of 1 / mL was added to a mixed liquid culture medium (culture medium: culture medium weight ratio of 1:1). Sterilized LB liquid medium without fluorine release agent was used as a blank control. The media were placed in a constant temperature incubator at 37℃ and shaken at 100 rpm for 24 h. After incubation, the media were removed, and the number of remaining viable bacteria was measured to obtain the antibacterial rate. Antibacterial rate = (initial viable bacteria count - remaining viable bacteria count) / remaining viable bacteria count of the blank group × 100%. The results are shown in Table 3 below.

[0089] Table 3 Antibacterial effect

[0090] Source of materials Antibacterial rate of Escherichia coli (%) Antibacterial rate against Staphylococcus aureus (%) Example 1 81.3 83.5 Example 2 83.1 84.6 Example 3 84.5 85.4 Example 4 83.4 86.8 Comparative Example 1 76.8 74.5 Comparative Example 2 77.1 73.2 Comparative Example 3 29.8 27.6 Comparative Example 4 33.1 31.4 Comparative Example 5 23.7 20.8 Comparative Example 6 75.3 70.8 Comparative Example 7 74.4 68.8 Comparative Example 8 42.7 38.5

[0091] The following conclusions can be drawn from Tables 1-3 above:

[0092] (1) As can be seen from Examples 1 to 4, the present invention obtains a modified hydrogen-containing silicone oil by modifying hydrogen-containing silicone oil, and then reacts it with a fluorinated alkyl compound through a hydrosilylation reaction to obtain a fluorinated release agent composition. This composition has low release force, good demolding effect and good antibacterial properties, and has good application prospects in the food and pharmaceutical fields.

[0093] (2) Comparative Example 1 shows that when the hydrogen content of the hydrogen-containing silicone oil is low, the efficiency of the hydrosilylation reaction may be reduced. In this system, the reaction between the hydrogen-containing silicone oil and hexafluorobutyl methacrylate is more difficult, which may result in fewer fluorinated groups in the final fluorinated release agent composition. Consequently, the release force of the release film formed by curing the coating liquid is higher, the number of demolding times is lower, and it is not conducive to use.

[0094] (3) Comparative Example 2 shows that when the hydrogen content of the hydrogen-containing silicone oil is high, the hydrosilylation reaction may be more intense, which may result in the surface tension of the final fluorinated release agent composition being too low. When the surface tension is too low, the adhesion between the fluorinated release agent composition and the substrate becomes poor and it is easy to fall off. This may result in the release force of the release film formed by the curing of the coating liquid being high and the number of demolding times being low, which is not conducive to use.

[0095] (4) Comparative Examples 3 and 4 show that when using a single emulsifier or other composite emulsifiers in different proportions, the fluorinated release agent composition prepared exhibits higher release force and fewer demolding times when the coating liquid is cured to form a release film. It also shows poor antibacterial effect. This indicates that in this system, the type and proportion of emulsifier have a significant impact on the modified hydrogen-containing silicone oil prepared by hydrolysis emulsification. If the emulsion system is unstable, it may not only weaken the hydrosilylation reaction of the modified hydrogen-containing silicone oil, but may also lead to the effect of grafting antibacterial extract after hydrolysis, resulting in poor release force, demolding times and antibacterial effect.

[0096] (5) Comparative Example 5 shows that the prepared fluorinated release agent composition has a high release force and a low number of demolding times when it is prepared into a release film formed by curing the coating liquid, and the antibacterial effect is also poor. This may be because, on the one hand, although limonene has antibacterial activity, it does not contain hydroxyl groups in its structure, so it is difficult to introduce it into the modified hydrogen-containing silicone oil by condensation with the silanol groups obtained by hydrolysis. Furthermore, the double bond in limonene may compete with the fluorinated alkyl compound, which may consume the silane-hydrogen bond on the modified hydrogen-containing silicone oil, weakening the reaction between the fluorinated alkyl compound and the modified hydrogen-containing silicone oil. As a result, the release force, demolding times and antibacterial effect of the release film formed by curing the coating liquid are all poor, which is not conducive to its use.

[0097] (6) Comparative Example 6 shows that the prepared fluorinated release agent composition has a high release force and a low number of demolding times when it is prepared into a release film formed by curing the coating liquid. This may be because although trifluoropropylmethylcyclotrisiloxane contains fluorinated groups, it does not have double bonds and is difficult to introduce into the modified hydrogen-containing silicone oil through hydrosilylation. As a result, the release force and number of demolding times of the release film formed by curing the coating liquid are poor, which is not conducive to its use.

[0098] (7) Comparative Example 7 shows that the prepared fluorinated release agent composition has a higher release force and a lower number of demolding times when it is prepared into a release film formed by curing the coating liquid. This may be because the boiling point of perfluorobutylethylene in this system is lower than the reaction temperature. It may vaporize and be unfavorable to the hydrosilylation reaction between the modified hydrogen-containing silicone oil and perfluorobutylethylene. It is difficult to introduce it into the modified hydrogen-containing silicone oil through hydrosilylation, which leads to poor release force and demolding times of the release film formed by curing the coating liquid, which is not conducive to its use.

[0099] (8) Comparative Example 8 shows that the prepared fluorinated release agent composition has poor antibacterial effect when it is prepared into a release film formed by curing the coating liquid. This may be because in this system, the higher hydrolysis temperature and longer hydrolysis time make it easy for the hydrogen-containing silicone oil to re-condense and polymerize while hydrolyzing, making it difficult to incorporate the antibacterial extract rosmarinic acid, thus resulting in poor antibacterial effect of the release film formed by curing the coating liquid.

[0100] The embodiments described above provide a detailed explanation of the technical solutions and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Various changes and modifications can be made to the present invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed.

Claims

1. A method for preparing a fluorinated release agent composition with antibacterial properties, characterized in that, The preparation method includes the following steps: Hydrogen-containing silicone oil, composite emulsifier, water and anhydrous ethanol are mixed and heated to 50℃~60℃ for 50min~80min to hydrolyze and obtain hydrolyzed emulsion; Modified hydrogen-containing silicone oil was obtained by mixing hydrolyzed emulsion and antibacterial extract and reacting at 50℃~60℃ for 3h~4h. A fluorinated release agent composition is obtained by mixing modified hydrogen-containing silicone oil, fluorinated alkyl compound and addition catalyst and heating to 80℃~90℃ for 7h~8h. The hydrogen content of the hydrogen-containing silicone oil is 0.3% to 0.6%; The antibacterial extract is chlorogenic acid or rosmarinic acid; The fluorinated alkyl compound is hexafluorobutyl acrylate or hexafluorobutyl methacrylate; The composite emulsifier is composed of Span 40, AEO-25 and Tween 80 in a weight ratio of 0.2~0.3:1:0.1~0.

2.

2. The method for preparing a fluorinated release agent composition with antibacterial properties according to claim 1, characterized in that, The hydrogen-containing silicone oil: composite emulsifier: The weight ratio of water to anhydrous ethanol is 10:1~1.5:10~15:25~30.

3. The method for preparing a fluorinated release agent composition with antibacterial properties according to claim 1, characterized in that, The weight ratio of the hydrolyzed emulsion to the antibacterial extract is 1:0.1~0.

4.

4. The method for preparing a fluorinated release agent composition with antibacterial properties according to claim 1, characterized in that, The addition catalyst comprises a chloroplatinic acid solution with a mass concentration of 50 mg / L.

5. The method for preparing a fluorinated release agent composition with antibacterial properties according to claim 1, characterized in that, The weight ratio of the modified hydrogen-containing silicone oil, fluorinated alkyl compound, and addition catalyst is 1:0.4~0.7:0.5~0.

6.

6. A fluorinated release agent composition prepared by the method for preparing a fluorinated release agent composition with antibacterial properties as described in any one of claims 1 to 5.