Fluorine release agent composition with antibacterial property and preparation method thereof

Abstract

The invention discloses a fluorine release agent composition with antibacterial performance and a preparation method of the fluorine release agent composition, and belongs to the technical field of mixed coating preparation. The preparation method comprises the following steps: mixing hydrogen-containing silicone oil, a compound emulsifier, water and absolute ethyl alcohol, heating to 50-60 DEG C, and hydrolyzing for 50-80 minutes to obtain a hydrolyzed emulsion; mixing the hydrolyzed emulsion and the antibacterial extract, and reacting at 50-60 DEG C for 3-4 hours to obtain modified hydrogen-containing silicone oil; and mixing the modified hydrogen-containing silicone oil, a fluorine-containing alkyl compound and an addition catalyst, heating to 80-90 DEG C, and reacting for 7-8 hours to obtain the fluorine release agent composition. The fluorine release agent composition with low release force, good demolding effect and antibacterial property is obtained by carrying out hydrosilylation reaction on the modified hydrogen-containing silicone oil obtained by modifying the hydrogen-containing silicone oil and the fluorine-containing alkyl compound.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of mixed coating preparation, and particularly relates to a fluorine release agent composition with antibacterial property and a preparation method thereof. BACKGROUND

[0002] A fluorine release agent is a substance that is mainly used to reduce the friction and adhesion of the surface of a material, and separate two surfaces that are difficult or impossible to separate. The main components of a fluorine release agent generally include fluoropolymers (such as polytetrafluoroethylene PTFE), fluorinated hydrocarbons and other fluorine compounds. The fluorine release agent generally has good high-temperature resistance, corrosion resistance, chemical inertness and low surface energy, and based on these characteristics, the fluorine release agent is widely used in multiple fields, including: (1) plastic and rubber industry: in the production process of plastic and rubber products, the fluorine release agent is used as a release agent to reduce the adhesion between the mold and the finished product, and improve the production efficiency, and due to its excellent high-temperature resistance and chemical stability, the fluorine release agent can maintain good performance under high-temperature conditions; (2) coating and ink: in the production of coatings and inks, the fluorine release agent can be used to improve the leveling property, gloss and stain resistance of the coating, and its low surface energy property makes the coating surface easier to clean, and improves the service life and maintenance convenience of the product; (3) electronic industry: in the manufacturing process of electronic components, the fluorine release agent can be used as an anti-adhesion agent to ensure the stability of the electronic components in high-temperature and humid environments, and prevent short circuits and corrosion; (4) food processing: in food packaging and processing equipment, the fluorine release agent can effectively prevent food from adhering to the surface of the equipment, and ensure the smooth production and meet the food safety standards.

[0003] With the increasing emphasis on health and safety, the antibacterial function of the fluorine release agent has been increasingly concerned, such as food-grade coatings that are in direct contact with food in the food industry, the application of antibacterial fluorine release agent can reduce the speed of corrosion and deterioration, thereby prolonging the shelf life of food; functional coatings in the medical and pharmaceutical fields, such as certain medical devices and pharmaceutical clean areas, the application of antibacterial fluorine release agent can effectively reduce the risk of bacterial infection, and ensure the safety of patients and drugs.

[0004] There are very few reports on the coating prepared by the fluorine release agent in the antibacterial field in the prior art, and therefore, it is a technical problem to be solved to study a fluorine release agent with antibacterial function. SUMMARY

[0005] According to the deficiencies of the prior art, the modified hydrogen-containing silicone oil obtained by modifying the hydrogen-containing silicone oil and the fluorine-containing alkyl compound are obtained by a silicon-hydrogen addition reaction to obtain a fluorine release agent composition, thereby solving the technical problems in the background art. Specifically, the technical scheme of the present application includes the following contents:

[0006] One of the purposes of the present application is to provide a preparation method of fluorine release agent composition with antibacterial property, the preparation method comprising the following steps:

[0007] The hydrogen-containing silicone oil, the composite emulsifier, the water and the anhydrous ethanol are mixed and heated to 50-60 DEG C to hydrolyze for 50-80 min to obtain a hydrolyzed emulsion;

[0008] The hydrolyzed emulsion and the antibacterial extract are mixed and reacted at 50-60 DEG C for 3-4 h to obtain a modified hydrogen-containing silicone oil;

[0009] The modified hydrogen-containing silicone oil, the fluorine-containing alkyl compound and the addition catalyst are mixed and heated to 80-90 DEG C to react for 7-8 h to obtain the fluorine release agent composition.

[0010] Further, the hydrogen-containing silicone oil contains hydrogen in an amount of 0.3-0.6%.

[0011] Further, 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] Further, the weight ratio of the hydrogen-containing silicone oil: the composite emulsifier: the water: the anhydrous ethanol is 10:1-1.5:10-15:25-30.

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

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

[0015] Further, the fluorine-containing alkyl compound includes hexafluorobutyl acrylate or hexafluorobutyl methacrylate, and the fluorine-containing alkyl compound needs to contain a carbon-carbon double bond for introduction to the modified hydrogen-containing silicone oil by silicon hydrogen addition.

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

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

[0018] The second purpose of the present application is to provide a fluorine release agent composition prepared by the preparation method of the fluorine release agent composition with antibacterial property.

[0019] Compared with the prior art, the present application has the following advantages:

[0020] The present application firstly modifies the hydrogen-containing silicone oil, and then introduces the antibacterial extract into the hydrogen-containing silicone oil through condensation of the silicon hydroxyl generated by hydrolysis of the hydrogen-containing silicone oil and the hydroxyl on the antibacterial extract to obtain modified hydrogen-containing silicone oil. Then, the modified hydrogen-containing silicone oil and the fluoroalkyl compound are subjected to a silicon hydrogen addition reaction to introduce fluorine atoms into the modified hydrogen-containing silicone oil, thereby obtaining a fluorine release agent composition with low release force, good demolding effect and good antibacterial performance. DETAILED DESCRIPTION

[0021] The technical solutions of the present application will be clearly and completely described below through embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0022] Unless otherwise specified, the raw materials and reagents used in the present application below are commercially available or can be prepared by known methods.

[0023] Example 1

[0024] A preparation method of a fluorine release agent composition with antibacterial performance, specifically comprising the following processes:

[0025] 20 parts by weight of deionized water and 60 parts by weight of anhydrous ethanol were weighed and mixed in a flask, then 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) was added and mixed and stirred until uniformly dispersed. Then 20 parts by weight of hydrogen-containing silicone oil with a hydrogen content of 0.3% was added to the flask and mixed and stirred at a speed of 400 r / min for 20 min. After stirring, the flask was placed in a water bath and hydrolyzed at a temperature of 50℃ for 50 min. After the reaction was completed, the mixture was cooled to room temperature to obtain a hydrolyzed emulsion;

[0026] 4 parts by weight of the hydrolyzed emulsion and 0.4 parts by weight of chlorogenic acid were weighed and mixed to obtain a mixed solution, and the mixed solution was placed in a water bath and condensed at a temperature of 50℃ for 3 h. After the condensation was completed, the mixture was cooled to room temperature to obtain modified hydrogen-containing silicone oil;

[0027] 2 parts by weight of the modified hydrogen-containing silicone oil, 0.8 parts by weight of hexafluorobutyl acrylate and 1 part by weight of chloroplatinic acid solution (mass concentration of 50 mg / L) were weighed and added to a reaction kettle, and then nitrogen was introduced into the reaction kettle to remove the air in the kettle. Under the protection of nitrogen, the reaction kettle was heated to 80℃, and the mixture was stirred at this temperature for 7 h. After the reaction was completed, the mixture in the reaction kettle was cooled to room temperature, and the fluorine release agent composition was obtained after the mixture was treated by reduced pressure distillation.

[0028] Example 2:

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

[0030] Take 24 parts by weight of deionized water and 56 parts by weight of anhydrous ethanol mixed in a flask, then add 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) and mix and stir until evenly dispersed. Then take 20 parts by weight of hydrogen-containing silicone oil with a hydrogen content of 0.4% and add it to the flask, mix and stir at a speed of 400 r / min for 20 min. After stirring, place the flask in a water bath and hydrolyze at a temperature of 55°C for 60 min. After the reaction is complete, cool to room temperature to obtain a hydrolyzed emulsion;

[0031] Take 4 parts by weight of the hydrolyzed emulsion and 0.8 parts by weight of chlorogenic acid and mix and stir to obtain a mixture, then place the mixture in a water bath and condense at a temperature of 55°C for 3.5 h. After condensation, cool to room temperature to obtain modified hydrogen-containing silicone oil;

[0032] Take 2 parts by weight of modified hydrogen-containing silicone oil, 1 part by weight of hexafluorobutyl acrylate, and 1 part by weight of chloroplatinic acid solution (mass concentration of 50 mg / L) and add them to a reaction kettle, then introduce nitrogen into the reaction kettle to remove the air in the kettle. Under the protection of nitrogen, raise the temperature of the reaction kettle to 85°C, and stir at this temperature for 7.5 h. After the reaction is complete, cool to room temperature and remove the mixture in the reaction kettle, then treat the mixture with reduced pressure distillation to obtain a fluorine release agent composition.

[0033] Example 3:

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

[0035] Take 28 parts by weight of deionized water and 52 parts by weight of anhydrous ethanol mixed in a flask, then add 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) and mix and stir until evenly dispersed. Then take 20 parts by weight of hydrogen-containing silicone oil with a hydrogen content of 0.5% and add it to the flask, mix and stir at a speed of 400 r / min for 20 min. After stirring, place the flask in a water bath and hydrolyze at a temperature of 55°C for 70 min. After the reaction is complete, cool to room temperature to obtain a hydrolyzed emulsion;

[0036] Take 4 parts by weight of the hydrolyzed emulsion and 0.12 parts by weight of rosemary acid and mix and stir to obtain a mixture, then place the mixture in a water bath and condense at a temperature of 55°C for 3.5 h. After condensation, cool to room temperature to obtain modified hydrogen-containing silicone oil;

[0037] Take 2 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 (mass concentration of 50 mg / L) into the reaction kettle, then nitrogen is introduced into the reaction kettle to remove the air in the kettle. Under the protection of nitrogen, the reaction kettle is heated to 85℃, and the reaction is stirred at this temperature for 8h. After the reaction is completed, the mixture in the reaction kettle is cooled to room temperature, and the mixture is treated by reduced pressure distillation to obtain the fluorine release agent composition.

[0038] Example 4:

[0039] A method for preparing a fluorine release agent composition with antibacterial properties, specifically including the following processes:

[0040] Take 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. Then take 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 a speed of 400 r / min for 20 min. After stirring, place the flask in a water bath and hydrolyze at a temperature of 60℃ for 80 min. After the reaction is completed, cool to room temperature to obtain a hydrolyzed emulsion;

[0041] Take 4 parts by weight of the hydrolyzed emulsion and 0.16 parts by weight of rosemary acid and mix and stir to obtain a mixture, then place the mixture in a water bath and condense at a temperature of 60℃ for 4h. After condensation, cool to room temperature to obtain the modified hydrogen-containing silicone oil;

[0042] Take 2 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 (mass concentration of 50 mg / L) into the reaction kettle, then nitrogen is introduced into the reaction kettle to remove the air in the kettle. Under the protection of nitrogen, the reaction kettle is heated to 90℃, and the reaction is stirred at this temperature for 8h. After the reaction is completed, the mixture in the reaction kettle is cooled to room temperature, and the mixture is treated by reduced pressure distillation to obtain the fluorine release agent composition.

[0043] Comparative Example 1:

[0044] A method for preparing a fluorine release agent composition with antibacterial properties, specifically including the following processes:

[0045] Take 30 parts by weight of deionized water and 50 parts by weight of anhydrous ethanol mixed in a flask, then add 3 parts by weight of composite emulsifier (composed of Span 40, AEO-25 and Tween 80 according to the weight ratio of 0.3:1:0.2) mixed and stirred until dispersed uniformly. Then take 20 parts by weight of hydrogen-containing silicone oil with hydrogen content of 0.2% and add it to the flask, mix and stir at 400 r / min for 20 min. After stirring, place the flask in a water bath at 60℃ for 80 min. After the reaction, cool to room temperature to obtain the hydrolysis emulsion;

[0046] The rest of the process remains the same as in Example 4.

[0047] Comparative Example 2:

[0048] A method for preparing a fluorine release agent composition with antibacterial properties, specifically including the following processes:

[0049] Take 30 parts by weight of deionized water and 50 parts by weight of anhydrous ethanol mixed in a flask, then add 3 parts by weight of composite emulsifier (composed of Span 40, AEO-25 and Tween 80 according to the weight ratio of 0.3:1:0.2) mixed and stirred until dispersed uniformly. Then take 20 parts by weight of hydrogen-containing silicone oil with hydrogen content of 0.8% and add it to the flask, mix and stir at 400 r / min for 20 min. After stirring, place the flask in a water bath at 60℃ for 80 min. After the reaction, cool to room temperature to obtain the hydrolysis emulsion;

[0050] The rest of the process remains the same as in Example 4.

[0051] Comparative Example 3:

[0052] A method for preparing a fluorine release agent composition with antibacterial properties, specifically including the following processes:

[0053] Take 30 parts by weight of deionized water and 50 parts by weight of anhydrous ethanol mixed in a flask, then add 3 parts by weight of Span 40 mixed and stirred until dispersed uniformly. Then take 20 parts by weight of hydrogen-containing silicone oil with hydrogen content of 0.6% and add it to the flask, mix and stir at 400 r / min for 20 min. After stirring, place the flask in a water bath at 60℃ for 80 min. After the reaction, cool to room temperature to obtain the hydrolysis emulsion;

[0054] The rest of the process remains the same as in Example 4.

[0055] Comparative Example 4:

[0056] A method for preparing a fluorine release agent composition with antibacterial properties, specifically including the following processes:

[0057] Take 30 parts by weight of deionized water and 50 parts by weight of anhydrous ethanol mixed in a flask, then add 3 parts by weight of composite emulsifier (composed of Span 40, AEO-25 and Tween 80 according to the weight ratio of 0.5:0.5:0.5) mixed and stirred until evenly dispersed. Then take 20 parts by weight of hydrogen-containing silicone oil with hydrogen content of 0.6% and add it to the flask, mix and stir at 400 r / min for 20 min. After stirring, place the flask in a water bath and hydrolyze at 60°C for 80 min. After the reaction is completed, cool to room temperature to obtain the hydrolysis emulsion;

[0058] The rest of the process remains the same as in Example 4.

[0059] Comparative Example 5:

[0060] A method for preparing a fluorine release agent composition with antibacterial properties, specifically including the following processes:

[0061] Take 30 parts by weight of deionized water and 50 parts by weight of anhydrous ethanol mixed in a flask, then add 3 parts by weight of composite emulsifier (composed of Span 40, AEO-25 and Tween 80 according to the weight ratio of 0.3:1:0.2) mixed and stirred until evenly dispersed. Then take 20 parts by weight of hydrogen-containing silicone oil with hydrogen content of 0.6% and add it to the flask, mix and stir at 400 r / min for 20 min. After stirring, place the flask in a water bath and hydrolyze at 60°C for 80 min. After the reaction is completed, cool to room temperature to obtain the hydrolysis emulsion;

[0062] Take 4 parts by weight of hydrolysis emulsion and 0.16 parts by weight of limonene and mix to obtain a mixed solution, place the mixed solution in a water bath and condense at 60°C for 4h. After condensation, cool to room temperature to obtain modified hydrogen-containing silicone oil;

[0063] Take 2 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 (mass concentration of 50mg / L) and add them to the reaction kettle, then introduce nitrogen into the reaction kettle to remove the air in the kettle. Under the protection of nitrogen, heat the reaction kettle to 90°C, and stir at this temperature for 8h. After the reaction is completed, cool to room temperature and take out the mixed solution in the reaction kettle, and then treat the mixed solution by reduced pressure distillation to obtain the fluorine release agent composition.

[0064] Comparative Example 6:

[0065] A method for preparing a fluorine release agent composition with antibacterial properties, specifically including the following processes:

[0066] Take 30 parts by weight of deionized water and 50 parts by weight of anhydrous ethanol mixed in a flask, then add 3 parts by weight of composite emulsifier (composed of Span 40, AEO-25 and Tween 80 according to the weight ratio of 0.3:1:0.2) mixed and stirred until evenly dispersed. Then take 20 parts by weight of hydrogen-containing silicone oil with hydrogen content of 0.6% and add it to the flask, mix and stir at a speed of 400 r / min for 20 min. After stirring, place the flask in a water bath and hydrolyze at a temperature of 60℃ for 80 min. After the reaction is completed, cool to room temperature to obtain a hydrolyzed emulsion;

[0067] Take 4 parts by weight of hydrolyzed emulsion and 0.16 parts by weight of rosemary acid and mix to obtain a mixed solution. Place the mixed solution in a water bath and condense at a temperature of 60℃ for 4h. After condensation, cool to room temperature to obtain a modified hydrogen-containing silicone oil;

[0068] Take 2 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 (mass concentration of 50mg / L) and add them to the reaction kettle, then introduce nitrogen into the reaction kettle to remove the air in the kettle. Under the protection of nitrogen, heat the reaction kettle to 90℃, and stir at this temperature for 8h. After the reaction is completed, cool to room temperature and take out the mixed solution in the reaction kettle. The mixed solution is treated by reduced pressure distillation to obtain a fluorine releasing agent composition.

[0069] Comparative Example 7:

[0070] A method for preparing a fluorine releasing agent composition with antibacterial properties, specifically including the following processes:

[0071] Take 30 parts by weight of deionized water and 50 parts by weight of anhydrous ethanol mixed in a flask, then add 3 parts by weight of composite emulsifier (composed of Span 40, AEO-25 and Tween 80 according to the weight ratio of 0.3:1:0.2) mixed and stirred until evenly dispersed. Then take 20 parts by weight of hydrogen-containing silicone oil with hydrogen content of 0.6% and add it to the flask, mix and stir at a speed of 400 r / min for 20 min. After stirring, place the flask in a water bath and hydrolyze at a temperature of 60℃ for 80 min. After the reaction is completed, cool to room temperature to obtain a hydrolyzed emulsion;

[0072] Take 4 parts by weight of hydrolyzed emulsion and 0.16 parts by weight of rosemary acid and mix to obtain a mixed solution. Place the mixed solution in a water bath and condense at a temperature of 60℃ for 4h. After condensation, cool to room temperature to obtain a modified hydrogen-containing silicone oil;

[0073] 2 parts by weight of modified hydrogenated silicone oil, 1.4 parts by weight of perfluorobutylethylene, and 1.2 parts by weight of chloroplatinic acid solution (50 mg / L) were added to a reactor. Nitrogen was then introduced to expel the air from the reactor. Under nitrogen, the reactor was heated to 90°C and stirred at this temperature for 8 hours. After the reaction was complete, the mixture was cooled to room temperature and removed from the reactor. The mixture was then distilled under reduced pressure to yield a fluorine-based release agent composition.

[0074] Comparative Example 8:

[0075] A method for preparing a fluorine 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 uniformly dispersed. Then weigh 20 parts by weight of hydrogenated silicone oil with a hydrogen content of 0.6% and add it to the flask. Mix and stir at a speed of 400r / min for 20 minutes. After stirring, place the flask in a water bath and hydrolyze at a temperature of 70°C for 100 minutes. After the reaction is completed, cool to room temperature to obtain a hydrolyzed emulsion;

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

[0078] The rest of the process remains the same as in Example 4.

[0079] Release force test:

[0080] The fluorine-based release agent compositions obtained in Examples 1-4 and Comparative Examples 1-8 were mixed and dissolved in n-heptane to prepare a 5% by mass coating solution. The coating solution was then coated onto a PET film to a thickness of 10 μm and cured at 140°C for 6 minutes to produce a release film. A 20 mm × 200 mm tape was applied to the release film and manually pressed back and forth five times with a 2 kg roller. The film was then allowed to stand for 30 minutes before undergoing a 180° peel test at a peel speed of 5 mm / s. The results are shown in Table 1.

[0081] Table 1 Release force

[0082] Material source 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 fluorine release agent composition prepared in Examples 1 to 4 and Comparative Examples 1 to 8 was brushed on the surface of a mold, and brushed twice, after the first brushing, the second brushing was performed after the first brushing was completely dried, and then dried, and then the PU foaming mixture (polyester TPU and azodicarbonamide were mixed in a weight ratio of 1:0.02) was poured into the mold, and after foaming and molding at a high temperature of 220°C, it was cooled to room temperature and completely taken out, which was recorded as the first demolding, and then the PU foaming mixture was poured into the mold again, and after foaming and molding again, it was completely taken out again, which was recorded as the second demolding, and the cycle operation was repeated until it could not be taken out. The results are shown in Table 2 below.

[0085] Table 2 Demolding performance

[0086] Material source Release frequency (times) 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 fluorine release agent composition prepared in Examples 1 to 4 and Comparative Examples 1 to 8 and the sterilized LB liquid medium were mixed in a weight ratio of 1:1, and then dispersed uniformly by ultrasonic power of 300W to obtain a mixed liquid medium. The Staphylococcus aureus culture solution with an initial viable bacterial count of 1×10 9 / mL and the Escherichia coli culture solution with an initial viable bacterial count of 1×10 9 / mL were added to the mixed liquid medium (the weight ratio of culture solution to medium was 1:1), and the sterilized LB liquid medium without the fluorine release agent composition was used as a blank control, and then placed in a constant temperature incubator at 37°C and shaken at a speed of 100r / min for 24h. After the culture was completed, the residual viable bacterial count was measured, and then the antibacterial rate was obtained, the antibacterial rate = (initial viable bacterial count - residual viable bacterial count) / residual viable bacterial count of the blank group x 100%, and the results are shown in Table 3 below.

[0089] Table 3 Antibacterial effect

[0090] Material source E. coli antibacterial rate (%) S. aureus antibacterial rate (%) 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] From the above Tables 1 to 3, the following conclusions can be drawn:

[0092] (1) It can be found from Examples 1 to 4 that the fluorine release agent composition prepared by modifying the hydrogen-containing silicone oil to obtain modified hydrogen-containing silicone oil, and then reacting with fluorine-containing alkyl compounds through a silicon hydrogen addition reaction, has low release force, good demolding effect and good antibacterial performance, and has good application prospect in the fields of food and medicine.

[0093] (2) It can be found from Comparative Example 1 that when the hydrogen content of the hydrogen-containing silicone oil is low, the efficiency of the silicon hydrogen addition reaction can be reduced, and in the present system, the hydrogen-containing silicone oil is difficult to react with hexafluorobutyl methacrylate, which can result in a small amount of fluorine-containing groups in the fluorine release agent composition prepared finally, and further result in a high release force and a low number of demolding times of the release film formed by curing the coating liquid, which is not conducive to use.

[0094] (3) It can be found from Comparative Example 2 that when the hydrogen content of the hydrogen-containing silicone oil is high, the silicon hydrogen addition reaction can be intense, which can result in a small surface tension of the fluorine release agent composition prepared finally, a poor adhesion of the fluorine release agent composition to the substrate, easy to fall off, and further result in a high release force and a low number of demolding times of the release film formed by curing the coating liquid, which is not conducive to use.

[0095] (4) It can be found from Comparative Examples 3 and 4 that when a single emulsifier or other proportion of composite emulsifier is used, the fluorine release agent composition prepared has a high release force and a low number of demolding times when the release film is formed by curing the coating liquid, and the antibacterial effect is also poor, which shows that in the present system, the type and proportion of the emulsifier used have an important influence on the hydrolysis and emulsification of the modified hydrogen-containing silicone oil, and if the emulsification system is unstable, not only can the silicon hydrogen addition reaction of the modified hydrogen-containing silicone oil be weakened, but also the effect of the grafted antibacterial extract after hydrolysis can be affected, and further the release force, the number of demolding times and the antibacterial effect of the final product can be poor.

[0096] (5) It can be found from Comparative Example 5 that the fluorine release agent composition prepared has a high release force and a low number of demolding times when the release film is formed by curing the coating liquid, and the antibacterial effect is also poor, which can be because on the one hand, limonene has antibacterial activity, but due to the structure not containing hydroxyl groups, it is difficult to be introduced into the modified hydrogen-containing silicone oil by condensation with the silicon hydroxyl groups obtained by hydrolysis, and the double bond in limonene can compete with the fluorine-containing alkyl compound, which can consume the silicon hydrogen bond on the modified hydrogen-containing silicone oil, weaken the reaction of the fluorine-containing alkyl compound with the modified hydrogen-containing silicone oil, and further result in poor release force, demolding times and antibacterial effect of the release film formed by curing the coating liquid, which is not conducive to use.

[0097] (6) It can be found from Comparative Example 6 that the fluorine release agent composition prepared has a high release force and a low number of demolding times when the release film is formed by curing the coating liquid, which can be because although trifluoropropylmethylcyclotrisiloxane contains fluorine-containing groups, it does not have a double bond, which is difficult to be introduced into the modified hydrogen-containing silicone oil by silicon hydrogen addition, and further result in poor release force and demolding times of the release film formed by curing the coating liquid, which is not conducive to use.

[0098] (7) It can be found from Comparative Example 7 that the fluorine release agent composition prepared has high release force and low release frequency when the release film formed by curing the coating liquid, which may be due to the fact that the boiling point of perfluorobutyl ethylene is lower than the reaction temperature in the system, which may be due to the fact that the modification of the hydrogen-containing silicone oil and the silicon hydrogen addition reaction of perfluorobutyl ethylene is not conducive to the introduction of the modified hydrogen-containing silicone oil by silicon hydrogen addition, and the release film formed by curing the coating liquid has poor release force and release frequency, which is not conducive to use.

[0099] (8) It can be found from Comparative Example 8 that the fluorine release agent composition prepared has poor antibacterial effect when the release film formed by curing the coating liquid, which may be due to the fact that the high hydrolysis temperature and long hydrolysis time in the system easily cause the hydrogen-containing silicone oil to hydrolyze and recondense and polymerize, which makes it difficult to access the antibacterial extract rosemary acid, and the release film formed by curing the coating liquid has poor antibacterial effect.

[0100] The above examples have described the technical solutions and beneficial effects of the present application in detail. It should be understood that the above description is only a specific embodiment of the present application and is not intended to limit the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of the claimed present application.

Claims

1. A method for preparing a fluorine release agent composition having antibacterial properties, characterized in that: The preparation method comprises the following steps: The hydrogenated silicone oil, the composite emulsifier, water and anhydrous ethanol are mixed and heated to 50° C. to 60° C. and hydrolyzed for 50 min to 80 min to obtain a hydrolyzed emulsion; The hydrolyzed emulsion and the antibacterial extract are mixed and reacted at 50° C. to 60° C. for 3 h to 4 h to obtain a modified hydrogenated silicone oil; The modified hydrogen-containing silicone oil, the fluorine-containing alkyl compound and the addition catalyst are mixed and heated to 80° C. to 90° C. and reacted for 7 h to 8 h to obtain a fluorine release agent composition.

2. The method for preparing a fluorine release agent composition with antibacterial properties according to claim 1, characterized in that: The hydrogen content of the hydrogen-containing silicone oil is 0.3% to 0.6%.

3. The method for preparing a fluorine release agent composition with antibacterial properties according to claim 1, characterized in that: 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.

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

5. The method for preparing a fluorine release agent composition with antibacterial properties according to claim 1, characterized in that: The antibacterial extract includes chlorogenic acid or rosmarinic acid.

6. The method for preparing a fluorine 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.

7. The method for preparing a fluorine release agent composition with antibacterial properties according to claim 1, characterized in that: The fluorine-containing alkyl compound includes hexafluorobutyl acrylate or hexafluorobutyl methacrylate.

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

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

6.

10. A fluorine-based release agent composition prepared by the method for preparing a fluorine-based release agent composition with antibacterial properties according to any one of claims 1 to 9.