A silicone non-stick material, method of manufacture and use

Abstract

The application discloses a preparation method and application of a silicone non-stick coating. The non-stick coating is composed of 55-65 parts of a fluorine-modified silicone composition, 15-25 parts of hydrophobically modified nanoparticles, 0.03-0.05 parts of a platinum catalyst, 0.01-0.03 parts of a platinum catalyst inhibitor and 15-30 parts of a solvent. The non-stick coating has suitable curing conditions, long non-stick performance and is suitable for being used as an inner coating of a non-stick cooking utensil.

Description

Technical fields:

[0001] This invention relates to the field of coating technology, and in particular to a method for preparing and applying an organosilicon non-stick material. Background technology:

[0002] Non-stick coatings have low surface energy and a low coefficient of friction, enabling them to resist sticky substances and easily remove them after adhesion. Therefore, they are widely used in cookware, automotive, construction, telecommunications, and chemical industries. Currently, non-stick coatings for cookware primarily use polytetrafluoroethylene (PTFE) as the base resin. Although PTFE outperforms other resins in non-stick coatings, its high price, poor processing properties, insolubility in common solvents, and high volatile content limit its application in non-stick coatings.

[0003] Organosilicon resins are polymers with Si-O-Si linkages forming the main chain. They possess low surface energy, second only to fluoropolymers, and exhibit good biocompatibility, making them suitable for preparing non-stick coatings for cookware. In the field of non-stick cookware coatings, organosilicon resins are often used in conjunction with polyester modification because polyesters have a full, glossy finish and excellent solvent resistance, which can compensate for the shortcomings of organosilicon resins in these aspects. Patent CN102977352A discloses a high-temperature resistant non-stick coating for pans made of polyester-modified organosilicon resin. It can cure without isocyanate, is easy to apply, and has good high-temperature resistance; however, its non-stick effect is poor, limiting its use to the outer coating of non-stick pans. Patent CN103205203A discloses a non-stick coating made of nano-SiO2 hybrid polyester-modified organosilicon. The addition of nanoparticles improves the non-stick performance of the organosilicon-modified polyester; however, because the base resin used is still organosilicon-modified polyester, the non-stick performance rapidly decreases once the nanoparticles are worn away. Although patent CN105504294A prepared a fluorine-modified silicone resin as the base resin for a non-stick coating, its paint film is brittle, its non-stick properties are unstable, and it requires etching of the cookware with a strong acid solvent to achieve the desired result. Therefore, achieving long-lasting non-stick properties in cookware coatings is an urgent problem to be solved. Summary of the Invention:

[0004] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0005] On one hand, the present invention provides an organosilicon non-stick coating, which comprises, by weight: 55-65 parts of fluorine-modified organosilicon composition, 15-25 parts of hydrophobic modified nanoparticles, 0.03-0.05 parts of platinum catalyst, 0.01-0.03 parts of platinum catalyst inhibitor, and 15-30 parts of solvent A.

[0006] In this invention, the fluorinated modified organosilicon composition is composed of a hydrogen-containing silicone resin, a fluorinated side-hydrogen vinyl silicone oil, and perfluoroethylene, in a mass ratio of 1:0.5-1.5:0.4-0.9, preferably 1:1:0.7.

[0007] The hydrogen-containing silicone resin is one or both of the silicone resins shown in Formula I and Formula II. When there are two, the ratio is 1:0.3-1.2, preferably 1:1-1.2.

[0008] Formula I: [R 1 SiO 3 / 2 ] a [R 2 SiO 3 / 2 ] b [R 3 SiO 3 / 2 ] c

[0009] In formula I, R 1 It is hydrogen; R 2 It is phenyl; R 3 It is a monovalent hydrocarbon group of C1 to C6, preferably R. 3 It is one of methyl, ethyl, and propyl; a = 0.3–0.7, b = 0.3–0.7, c = 0–0.3, and a+b+c = 1;

[0010] Formula II: [RSiO 1 / 2 ] a [SiO2] b

[0011] In Formula II, R is one or more of hydrogen, phenyl, and C1-C6 monovalent hydrocarbon groups, preferably methyl, ethyl, or propyl; a = 0.5-0.8, b = 0.2-0.5, and a+b = 1;

[0012] Furthermore, the hydrogen-containing silicone resin represented by Formula I is obtained by hydrolysis and condensation polymerization of hydrogen-containing silane, phenyl silane, and silane containing a monovalent hydrocarbon group in the presence of an acidic catalyst and water. Preferably, the molar proportions of the three are: 30-70% hydrogen-containing silane, 30-70% phenyl silane, and 0-30% monovalent hydrocarbon silane, with the total molar amount of the three being 100%.

[0013] Preferably, the hydrogen-containing silane is one or more of trimethoxysilane, triethoxysilane, tripropoxysilane, and triacetoxysilane, more preferably triethoxysilane; preferably, the phenyl-containing silane is selected from one or more of phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, and phenyltriacetoxysilane, more preferably phenyltriethoxysilane; preferably, the silane containing a monovalent hydrocarbon group is selected from one or more of methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, and hexyltrimethoxysilane, more preferably methyltriethoxysilane;

[0014] Preferably, the acidic catalyst is at least one selected from hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and trifluoroacetic acid; more preferably, it is trifluoromethanesulfonic acid.

[0015] Preferably, the amount of acidic catalyst used is 100 to 1000 ppm of the total mass of the hydrogen-containing silane.

[0016] Furthermore, in the hydrolysis-condensation reaction, the amount of water used is 1.0 to 1.6 times the total molar amount of the hydrogen-containing silane;

[0017] Furthermore, the hydrolysis-condensation reaction conditions are: reaction temperature of 40–70℃ and reaction time of 1–3 h.

[0018] Furthermore, after the hydrolysis and polycondensation reaction of the present invention is completed, the following process is also included: first, the low-boiling substances are removed by evaporation, then an organic solvent is added and refluxed to remove water, then a neutralizing agent is added to neutralize the acidic catalyst, impurities are removed by filtration, and the organic solvent is removed by vacuum distillation to obtain the hydrogen-containing silicone resin shown in Formula I.

[0019] Furthermore, the hydrogen-containing silicone resin represented by Formula II is prepared by the equilibrium reaction of water, tetraethyl orthosilicate, and disiloxane in an acidic medium and anhydrous ethanol;

[0020] Preferably, the disiloxane has the general formula R 1 a R 2 b R 3 c Si2O, where R 1 For hydrogen, R 2 It is a phenyl group, R 3It is a monovalent hydrocarbon group of C1 to C6, preferably methyl, ethyl, or propyl, a+b+c = 6, 0 ≤ a, b, c ≤ 6, preferably 0.2

[0021] Preferably, the acidic medium is formic acid, acetic acid, oxalic acid, tartaric acid, benzoic acid, p-benzenesulfonic acid, or salicylic acid; more preferably, the acidic medium is acetic acid.

[0022] Preferably, the proportions of water and anhydrous ethanol used in the equilibrium reaction to the total mass of tetraethyl orthosilicate and disiloxane in the system are 21%–40% and 12%–18%, respectively.

[0023] Preferably, the molar ratio of disiloxane to tetraethyl orthosilicate is 0.5–0.6:1; and the amount of acidic medium accounts for 0.5–0.8% of the total weight of the reactants in the reaction system.

[0024] Furthermore, the equilibrium reaction involves adding water, an acidic medium, anhydrous ethanol, and disiloxane to the reactor, while simultaneously adding tetraethyl orthosilicate dropwise with stirring. The dropwise addition time is controlled within 1.5–2 hours, and the reaction system temperature is controlled at 20°C. After the dropwise addition is complete, the mixture is slowly heated to 50–60°C and reacted for 2.5–4 hours.

[0025] Further, after the equilibrium reaction is completed, the oil phase is first separated with toluene, washed with water until neutral and dried; after the oil phase is filtered, the solvent and small molecule substances are removed by vacuum distillation to obtain the hydrogen-containing silicone resin shown in Formula II.

[0026] Preferably, the drying agent used in the above equilibrium reaction is one or more of calcium carbonate, anhydrous calcium chloride, anhydrous magnesium sulfate, and anhydrous copper sulfate; more preferably, the drying agent is anhydrous calcium chloride.

[0027] In this invention, the structural formula of the fluorinated side-hydrogen vinyl silicone oil is as follows:

[0028] CH2=CHSiO[R 1 R 2 SiO] a [R 1 HSiO] b [R 1 2SiO] c OSiCH=CH2, where R 1 It is a C1-C6 monovalent hydrocarbon group, preferably methyl, ethyl, or propyl, R 2 ​The expression is CH2CH2CF3, a:b:c = 2.67-4:13-15:1.

[0029] The fluorinated side-hydrogen vinyl silicone oil is obtained by ring-opening polymerization of trifluoropropyltrimethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, and tetramethyldivinyldisiloxane under the action of macroporous cationic strong acid resin and Speier Pt catalyst.

[0030] Furthermore, the reaction involves the following molar ratio of compounds: trifluoropropyltrimethylcyclotrisiloxane: tetramethylcyclotetrasiloxane: tetramethyldivinyldisiloxane = 2-3: 13-15: 1.

[0031] Furthermore, the reaction temperature is 45-60℃ and the time is 5.5-6.5h.

[0032] Furthermore, after the ring-opening polymerization is completed, the catalyst is removed by filtration, and low-boiling substances are removed by vacuum distillation for 3 hours to obtain the liquid, which is the fluorinated side-hydrogen vinyl silicone oil.

[0033] The perfluoroethylene is selected from carbon atoms with numbers C4-C6. 14 The preferred perfluoroalkyl ethylene is perfluorodecyl ethylene.

[0034] Furthermore, the hydrophobically modified nanoparticles are obtained by hydrophobically modifying nanoparticles.

[0035] Preferably, the nanoparticles are one or more of SiO2, TiO2, diatomaceous earth, bentonite, and calcined kaolin.

[0036] Preferably, the nanoparticles are a combination of nanoparticles with a particle size of 20-30 nm and nanoparticles with a particle size of 30-80 nm, in a ratio of 1 to 3:1; more preferably, they are 20-30 nm SiO2 and 30-80 nm TiO2.

[0037] Furthermore, the hydrophobic modification is obtained by adding the nanoparticles to a hydrophobic modifier and stirring.

[0038] Furthermore, the hydrophobic modifier is a mixed solution of a common silane coupling agent, a perfluorosilane coupling agent, and an ester solvent, in a mass ratio of 1:1-2:6-8;

[0039] Furthermore, the common silane coupling agent is one of vinyltriethoxysilane, glycidyl ether propyltrimethoxysilane, (methacryloyloxy)propyltrimethoxysilane, or mercaptopropyltriethoxysilane;

[0040] Furthermore, the perfluorosilane coupling agent is one of dodecafluoroheptylpropyltrimethoxysilane, tridecafluorooctyltriethoxysilane, and perfluorodecyltriethoxysilane;

[0041] Further, the ester solvent is a mixed solution of butyl acetate, propylene glycol methyl ether acetate and ethyl acetate, wherein the weight ratio of butyl acetate, propylene glycol methyl ether acetate and ethyl acetate is 1:(1.5-2):(1.5-2).

[0042] Furthermore, the stirring process is carried out at a speed of 500-1000 rpm for a duration of 30-60 min.

[0043] In this invention, solvent A is selected from one or more of toluene, xylene, and propylene glycol monomethyl ether acetate.

[0044] In another aspect, the present invention also provides a method for preparing an organosilicon non-stick coating, the method comprising:

[0045] The hydrogen-containing silicone resin, fluorinated side-hydrogen vinyl silicone oil, perfluorinated vinyl, platinum catalyst, platinum catalyst inhibitor, and hydrophobically modified nanoparticles are stirred at 500-1000 rpm for 30-60 min, then sprayed onto a substrate under a pressure of 0.3-0.7 MPa, and cured at 140-160℃ for 0.5-2 h to obtain the final product.

[0046] The beneficial effects of this invention are as follows:

[0047] This invention prepares a non-stick coating with fluorinated modified silicone resin as the main resin. Under suitable curing conditions, it exhibits long-lasting non-stick properties, making it suitable for use as the inner coating of non-stick cookware. Compared with existing patented technologies, the curing method is gentler, processability is better, cost is lower, and non-stick performance is superior. It also eliminates the need for etching the cookware, making it more practical. Typically, using pure organosilicon as the base resin results in a poor balance between hardness and flexibility, leading to a generally brittle coating film. This invention achieves a balance between the toughness and hardness of the silicone resin by controlling the proportions of hydrogen-containing MQ resin, hydrogen-containing T resin, vinyl silicone oil, and perfluorinated vinyl. Furthermore, by introducing different fluorine functional groups into the resin and silicone oil, this invention significantly improves the non-stick properties of the silicone resin. The addition of hydrophobic nanoparticles not only strengthens the coating but also further enhances the non-stick properties of the silicone resin. Detailed implementation method:

[0048] The present invention will be further illustrated below with specific embodiments. These embodiments are merely illustrative and do not limit the scope of the invention.

[0049] Raw materials and sources:

[0050] Perfluoroethylene, perfluorosilane coupling agent, and platinum catalyst were purchased from Aladdin Reagent (Shanghai) Co., Ltd., and macroporous strong acid cation exchange resin (HND-580) was purchased from Jiangyin Nanda Synthetic Chemical Co., Ltd. Speier catalyst (KP30) was purchased from Shanghai Neutron Star Chemical Technology Co., Ltd. Aluminum plates were used as the test substrate.

[0051] Unless otherwise specified, all other raw materials were obtained through commercial purchases.

[0052] Main testing methods:

[0053] Contact angle test: 5 μL of deionized water and n-hexadecane were respectively pipetted onto the sample surface, and the contact angle was calculated by taking pictures using an optical microscope.

[0054] Non-stickiness test: Place the cleaned sample on an electric stove and heat it at 150℃~180℃. Crack an egg onto the sample and wait for it to solidify. Then, use a non-metallic spatula to lift the egg. Excellent: No adhesion at the center or edges, easily slides off. Good: Slight adhesion at the edges, easily slides off. Medium: Stable adhesion at the edges, easily slides off at the center. Poor: Requires considerable force to slide off. Very poor: Egg cannot slide off.

[0055] Non-stick durability: According to GB / T1768-1979, the non-stick properties were tested after grinding with a 250g weight for 50, 100, and 200 revolutions respectively.

[0056] Flexibility test: Refer to GB / T1731-1993.

[0057] Hardness test: Refer to GB / T 6739-2006.

[0058] Temperature resistance test: If the coating does not lose its gloss, change color, peel off, or crack after being placed at 280℃ for 3 hours, it is considered good; otherwise, it is considered poor.

[0059] Adhesion test: Refer to GB / T 9286-1998.

[0060] Preparation Example 1 (Preparation of Hydrogen-Containing Silicone Resin I)

[0061] (1) 328 g (2 mol) of triethoxysilane, 360 g (1.5 mol) of phenyltriethoxysilane, and 267 g (1.5 mol) of methyltriethoxysilane were added to a 2 L reaction vessel. 0.5 g of trifluoromethanesulfonic acid was added, and 130 g (7.2 mol) of deionized water was gradually added dropwise under a N2 atmosphere. The reaction temperature was controlled at 40–70 °C, and the reaction time was 3 h. After the reaction was completed, the temperature was raised to 85 °C for 2 h to remove low-boiling substances. Then, 1 mol of toluene was added and refluxed to remove water. Then, 50 g of calcium carbonate was added to neutralize the acidic catalyst. The solid particles were filtered, and the toluene solvent was removed by distillation at a negative pressure of 20 mbar for 1 h to obtain the hydrogen-containing silicone resin IA shown in Formula I.

[0062] (2) 246 g (1.5 mol) of triethoxysilane and 840 g (3.5 mol) of phenyltriethoxysilane were added to a 2 L reaction vessel. 0.6 g of trifluoromethanesulfonic acid was added, and 130 g (7.2 mol) of deionized water was gradually added dropwise under a N2 atmosphere. The reaction temperature was controlled at 40–70 °C, and the reaction time was 3 h. After the reaction was completed, the temperature was raised to 85 °C for 2 h to remove low-boiling substances. Then, 1 mol of toluene was added and refluxed to remove water. Then, 50 g of calcium carbonate was added to neutralize the acidic catalyst. The solid particles were filtered, and the organic solvent was removed by distillation at a negative pressure of 20 mbar for 1 h to obtain the hydrogen-containing silicone resin IB shown in Formula I.

[0063] (3) 574 g (3.5 mol) of triethoxysilane, 120 g (0.5 mol) of phenyltriethoxysilane, and 178 g (1 mol) of methyltriethoxysilane were added to a 2 L reaction vessel. 0.5 g of trifluoromethanesulfonic acid was added, and 144 g (8 mol) of deionized water was gradually added dropwise under a N2 atmosphere. The reaction temperature was controlled at 40–70 °C, and the reaction time was 3 h. After the reaction was completed, the temperature was raised to 85 °C for 2 h to remove low-boiling substances. Then, 1 mol of toluene was added and refluxed to remove water. Then, 50 g of calcium carbonate was added to neutralize the acidic catalyst. The solid particles were filtered, and the toluene solvent was removed by distillation at a negative pressure of 20 mbar for 1 h to obtain the hydrogen-containing silicone resin IC shown in Formula I.

[0064] Preparation Example 2 (Preparation of Hydrogen-Containing Silicone Resin II)

[0065] (1) In a 2L four-necked flask, 9.75g (0.125mol) of disiloxane, 287.0g (0.75mol) of tetraphenyldisiloxane, 100.5g (0.75mol) of tetramethyldisiloxane, 120g of water, 3.8g of acetic acid, and 60g of anhydrous ethanol were added dropwise to a reactor. The addition time was controlled within 1 hour, and the system temperature was controlled at 20℃. After the addition was completed, the mixture was slowly heated to 50℃ and reacted for 3 hours. After the reaction was completed, 130g of toluene was added, and the mixture was allowed to stand for separation. The upper oil phase was taken, washed with deionized water until neutral, and dried with anhydrous calcium chloride until clear and transparent. Finally, the system was filtered and the solvent and small molecules were removed under vacuum at 80℃ for 1 hour to obtain the hydrogen-containing silicone resin IIA shown in Formula II.

[0066] (2) In a 2L four-necked flask, add 9.75g (0.125mol) disiloxane, 5.75g (0.025mol) diphenyldisiloxane, 382.6g (1mol) tetraphenyldisiloxane, and 100.5g (0.75mol) tetramethyldisiloxane. Add 500g of tetraethyl orthosilicate dropwise to the reactor over a period of 1 hour, maintaining the system temperature at 20°C. After the addition is complete, slowly heat to 50°C and react for 3 hours. After the reaction is complete, add 130g of toluene and stir thoroughly. Allow the mixture to stand and separate into layers. Take the upper oil phase, wash with deionized water until neutral, and dry with anhydrous calcium chloride until clear and transparent. Finally, filter the system and remove the solvent and small molecules under vacuum at 80°C for 1 hour to obtain the hydrogen-containing silicone resin IIB shown in Formula II.

[0067] (3) In a 2L four-necked flask, 9.75g (0.125mol) of disiloxane, 287.0g (0.75mol) of tetraphenyldisiloxane, 134g (1mol) of tetramethyldisiloxane, 120g of water, 3.8g of acetic acid, and 60g of anhydrous ethanol were added dropwise to a reactor. The addition time was controlled within 1 hour, and the system temperature was controlled at 20℃. After the addition was complete, the mixture was slowly heated to 50℃ and reacted for 3 hours. After the reaction was complete, 130g of toluene was added, and the mixture was allowed to stand for separation. The upper oil phase was taken, washed with deionized water until neutral, and dried with anhydrous calcium chloride until clear and transparent. Finally, the system was filtered and subjected to vacuum at 80℃ for 1 hour to remove the solvent and small molecules, yielding the hydrogen-containing silicone resin IIC as shown in Formula II.

[0068] Preparation Example 3 (Preparation of Fluorinated Side-Hydrogen Vinyl Silicone Oil)

[0069] (1) Add 43.29 g tetramethylcyclotetrasiloxane (0.18 mol), 16.87 g trifluoropropyltrimethylcyclotrisiloxane (0.036 mol), and 2.48 g (0.012 mol) methyldivinyldisiloxane to the reactor. Heat to 45 °C in an oil bath and stir for 10 min to mix thoroughly. Add 3.062 g macroporous strong acid cation exchange resin (HND-580) and polymerize for 6.5 h. After the reaction is complete, filter to remove the catalyst, and distill under reduced pressure at 80 °C for 3 h to remove low-boiling substances to obtain fluorinated side-hydrogen vinyl silicone oil A.

[0070] (2) Add 50.51 g tetramethylcyclotetrasiloxane (0.21 mol), 17.57 g trifluoropropyltrimethylcyclotrisiloxane (0.0375 mol), and 3.1 g (0.015 mol) methyldivinyldisiloxane to the reactor. Heat in an oil bath to 45°C and stir for 10 min to mix thoroughly. Add 3.062 g macroporous strong acid cation exchange resin (HND-580) and heat to 55°C for 6 h for polymerization. After the reaction is complete, filter to remove the catalyst, and distill under reduced pressure at 80°C for 3 h to remove low-boiling substances, obtaining fluorinated side-hydrogen vinyl silicone oil B.

[0071] (3) Add 37.52 g tetramethylcyclotetrasiloxane (0.156 mol), 11.25 g trifluoropropyltrimethylcyclotrisiloxane (0.024 mol), and 2.48 g (0.012 mol) methyldivinyldisiloxane to the reactor. Heat in an oil bath to 45°C and stir for 10 min to mix thoroughly. Add 3.062 g macroporous strong acid cation exchange resin (HND-580) and heat to 65°C for 5.5 h for polymerization. After the reaction is complete, filter to remove the catalyst, and distill under reduced pressure at 80°C for 3 h to remove low-boiling substances, obtaining fluorinated side-hydrogen vinyl silicone oil C.

[0072] Example 1

[0073] Preparation of hydrophobically modified nanoparticles: 10g of SiO2 nanoparticles with a particle size of 20-30nm and 25g of diatomaceous earth nanoparticles with a particle size of 30-80nm were added to a mixed solution of 15g glycidyl ether propyltrimethoxysilane, 15g perfluorodecyltriethoxysilane, 26g butyl acetate, 26g propylene glycol methyl ether acetate, and 39g ethyl acetate. The mixture was stirred at 800rpm for 60min to obtain hydrophobically modified nanoparticles.

[0074] Preparation of the non-stick coating: 11 parts of hydrogen-containing silicone resin IA, 11 parts of hydrogen-containing silicone resin IIA, 34 parts of fluorinated side-hydrogen vinyl silicone oil C, 9 parts of perfluorotetradecene, 15 parts of hydrophobically modified nanoparticles, 0.05 parts of platinum catalyst, 0.03 parts of platinum catalyst inhibitor, 15 parts of toluene, and 5 parts of propylene glycol monomethyl ether acetate were added to a reactor. After stirring at 1000 rpm for 30 min, the coating was sprayed onto a substrate under a pressure of 0.7 MPa and cured at 150℃ for 2 h to obtain sample 1. The application performance of sample 1 is detailed in Table 1.

[0075] Example 2

[0076] Preparation of hydrophobically modified nanoparticles: 10g of bentonite nanoparticles with a particle size of 20-30nm and 25g of TiO2 nanoparticles with a particle size of 30-80nm were added to a mixed solution of 10g vinyltriethoxysilane, 20g perfluorodecyltriethoxysilane, 16g butyl acetate, 23g propylene glycol methyl ether acetate, and 31g ethyl acetate. The mixture was stirred at 800rpm for 60min to obtain hydrophobically modified nanoparticles.

[0077] Preparation of the non-stick coating: 14 parts of hydrogen-containing silicone resin IB, 7 parts of hydrogen-containing silicone resin IIB, 22 parts of fluorinated side-hydrogen vinyl silicone oil A, 17 parts of perfluorodecylethylene, 25 parts of hydrophobically modified nanoparticles, 0.04 parts of platinum catalyst, 0.02 parts of platinum catalyst inhibitor, and 15 parts of toluene were added to a reactor. After stirring at 1000 rpm for 45 min, the coating was sprayed onto a substrate under a pressure of 0.6 MPa and cured at 160℃ for 0.5 h to obtain sample 2. The application performance of sample 2 is detailed in Table 1.

[0078] Example 3

[0079] Preparation of hydrophobically modified nanoparticles: 10g of SiO2 nanoparticles with a particle size of 20-30nm and 25g of calcined kaolin nanoparticles with a particle size of 30-80nm were added to a mixed solution of 10g mercaptopropyltriethoxysilane, 20g perfluorodecyltriethoxysilane, 13g butyl acetate, 25g propylene glycol methyl ether acetate, and 25g ethyl acetate. The mixture was stirred at 800rpm for 60min to obtain hydrophobically modified nanoparticles.

[0080] Preparation of the non-stick coating: 10 parts of hydrogen-containing silicone resin IC, 12 parts of hydrogen-containing silicone resin IIC, 22 parts of fluorinated side-hydrogenated vinyl silicone oil B, 16 parts of perfluorodecylethylene, 20 parts of hydrophobically modified nanoparticles, 0.04 parts of platinum catalyst, 0.02 parts of platinum catalyst inhibitor, 15 parts of toluene, and 5 parts of propylene glycol monomethyl ether acetate were added to a reactor. After stirring at 800 rpm for 50 min, the coating was sprayed onto a substrate under a pressure of 0.4 MPa and cured at 160℃ for 1 h to obtain sample 3. The application performance of sample 3 is detailed in Table 1.

[0081] Example 4

[0082] Preparation of hydrophobically modified nanoparticles: 10g of diatomaceous earth nanoparticles with a particle size of 20-30nm and 25g of TiO2 nanoparticles with a particle size of 30-80nm were added to a mixed solution of 10g vinyltriethoxysilane, 20g perfluorodecyltriethoxysilane, 20g butyl acetate, 40g propylene glycol methyl ether acetate, and 40g ethyl acetate. The mixture was stirred at 800rpm for 60min to obtain hydrophobically modified nanoparticles.

[0083] Preparation of the non-stick coating: 17 parts of hydrogen-containing silicone resin IA, 6 parts of hydrogen-containing silicone resin IIB, 21 parts of fluorinated side-hydrogen vinyl silicone oil A, 16 parts of perfluorooctylethylene, 20 parts of hydrophobically modified nanoparticles, 0.04 parts of platinum catalyst, 0.02 parts of platinum catalyst inhibitor, 15 parts of toluene, and 5 parts of propylene glycol monomethyl ether acetate were added to a reactor. After stirring at 800 rpm for 50 min, the coating was sprayed onto a substrate under a pressure of 0.4 MPa and cured at 140℃ for 1.5 h to obtain sample 4. The application performance of sample 4 is detailed in Table 1.

[0084] Example 5

[0085] Preparation of hydrophobically modified nanoparticles: 10g of SiO2 nanoparticles with a particle size of 20-30nm and 25g of TiO2 nanoparticles with a particle size of 30-80nm were added to a mixed solution of 15g (methacryloyloxy)propyltrimethoxysilane, 15g dodecafluoroheptylpropyltrimethoxysilane, 23g butyl acetate, 45g propylene glycol methyl ether acetate, and 45g ethyl acetate. The mixture was stirred at 800rpm for 60min to obtain hydrophobically modified nanoparticles.

[0086] Preparation of the non-stick coating: 11 parts of hydrogen-containing silicone resin IA, 11 parts of hydrogen-containing silicone resin IIA, 22 parts of fluorinated side-hydrogenated vinyl silicone oil C, 16 parts of perfluoroheptylethylene, 20 parts of hydrophobically modified nanoparticles, 0.04 parts of platinum catalyst, 0.02 parts of platinum catalyst inhibitor, 15 parts of toluene, and 5 parts of propylene glycol monomethyl ether acetate were added to a reactor. After stirring at 800 rpm for 50 min, the coating was sprayed onto a substrate under a pressure of 0.4 MPa and cured at 150 °C for 1 h to obtain sample 5. The application performance of sample 5 is detailed in Table 1.

[0087] Example 6

[0088] Preparation of hydrophobically modified nanoparticles: 10g of SiO2 nanoparticles with a particle size of 20-30nm and 25g of TiO2 nanoparticles with a particle size of 30-80nm were added to a mixed solution of 10g of vinyltriethoxysilane, 20g of perfluorodecyltriethoxysilane, 18g of butyl acetate, 35g of propylene glycol methyl ether acetate, and 35g of ethyl acetate. The mixture was stirred at 800rpm for 60min to obtain hydrophobically modified nanoparticles.

[0089] Preparation of the non-stick coating: 13 parts of hydrogen-containing silicone resin IB, 16 parts of hydrogen-containing silicone resin IIC, 14 parts of fluorinated side-hydrogenated vinyl silicone oil A, 11 parts of perfluorotridecene, 15 parts of hydrophobically modified nanoparticles, 0.03 parts of platinum catalyst, 0.01 parts of platinum catalyst inhibitor, 25 parts of xylene, and 5 parts of propylene glycol monomethyl ether acetate were added to a reactor. After stirring at 500 rpm for 60 min, the coating was sprayed onto a substrate under a pressure of 0.3 MPa and cured at 140℃ for 2 h to obtain sample 6. The application performance of sample 6 is detailed in Table 1.

[0090] Example 7

[0091] Preparation of hydrophobically modified nanoparticles: 10g of SiO2 nanoparticles with a particle size of 20-30nm and 25g of TiO2 nanoparticles with a particle size of 30-80nm were added to a mixed solution of 10g of vinyltriethoxysilane, 20g of perfluorodecyltriethoxysilane, 18g of butyl acetate, 35g of propylene glycol methyl ether acetate, and 35g of ethyl acetate. The mixture was stirred at 800rpm for 60min to obtain hydrophobically modified nanoparticles.

[0092] Preparation of the non-stick coating: 15 parts of hydrogen-containing silicone resin IC, 5 parts of hydrogen-containing silicone resin IIB, 21 parts of fluorinated side-hydrogen vinyl silicone oil B, 19 parts of perfluorononylethylene, 20 parts of hydrophobically modified nanoparticles, 0.03 parts of platinum catalyst, 0.01 parts of platinum catalyst inhibitor, 15 parts of xylene, and 5 parts of propylene glycol monomethyl ether acetate were added to a reactor. After stirring at 800 rpm for 50 min, the coating was sprayed onto a substrate under a pressure of 0.4 MPa and cured at 150 °C for 1 h to obtain sample 7. The application performance of sample 7 is detailed in Table 1.

[0093] Example 8

[0094] Preparation of hydrophobically modified nanoparticles: 10g of SiO2 nanoparticles with a particle size of 20-30nm and 25g of SiO2 nanoparticles with a particle size of 30-80nm were added to a mixed solution of 15g vinyltriethoxysilane, 15g perfluorodecyltriethoxysilane, 23g butyl acetate, 45g propylene glycol methyl ether acetate, and 45g ethyl acetate. The mixture was stirred at 800rpm for 60min to obtain hydrophobically modified nanoparticles.

[0095] Preparation of the non-stick coating: 10 parts of hydrogen-containing silicone resin IC, 12 parts of hydrogen-containing silicone resin IIC, 22 parts of fluorinated side-hydrogen vinyl silicone oil B, 16 parts of perfluorotetradecene, 20 parts of hydrophobically modified nanoparticles, 0.04 parts of platinum catalyst, 0.02 parts of platinum catalyst inhibitor, 15 parts of toluene, and 5 parts of propylene glycol monomethyl ether acetate were added to a reactor. After stirring at 800 rpm for 50 min, the coating was sprayed onto a substrate under a pressure of 0.4 MPa and cured at 150 °C for 1 h to obtain sample 8. The application performance of sample 8 is detailed in Table 1.

[0096] Comparative Example 1

[0097] Preparation of hydrophobically modified nanoparticles: 10g of SiO2 nanoparticles with a particle size of 20-30nm and 25g of calcined kaolin nanoparticles with a particle size of 30-80nm were added to a mixed solution of 10g mercaptopropyltriethoxysilane, 20g perfluorodecyltriethoxysilane, 13g butyl acetate, 25g propylene glycol methyl ether acetate, and 25g ethyl acetate. The mixture was stirred at 800rpm for 60min to obtain hydrophobically modified nanoparticles.

[0098] Preparation of the non-stick coating: 22 parts of hydrogen-containing silicone resin IC, 22 parts of fluorinated side-hydrogen vinyl silicone oil B, 16 parts of perfluorodecylethylene, 20 parts of hydrophobically modified nanoparticles, 0.04 parts of platinum catalyst, 0.02 parts of platinum catalyst inhibitor, 15 parts of toluene, and 5 parts of propylene glycol monomethyl ether acetate were added to a reactor. After stirring at 800 rpm for 50 min, the coating was sprayed onto a substrate under a pressure of 0.4 MPa and cured at 160 °C for 1 h to obtain control sample 1. The application performance of control sample 1 is detailed in Table 2.

[0099] Comparative Example 2

[0100] Preparation of hydrophobically modified nanoparticles: 10g of SiO2 nanoparticles with a particle size of 20-30nm and 25g of calcined kaolin nanoparticles with a particle size of 30-80nm were added to a mixed solution of 10g mercaptopropyltriethoxysilane, 20g perfluorodecyltriethoxysilane, 13g butyl acetate, 25g propylene glycol methyl ether acetate, and 25g ethyl acetate. The mixture was stirred at 800rpm for 60min to obtain hydrophobically modified nanoparticles.

[0101] Preparation of the non-stick coating: 22 parts of hydrogen-containing silicone resin IIC, 22 parts of fluorinated side-hydrogenated vinyl silicone oil B, 16 parts of perfluorodecylethylene, 20 parts of hydrophobically modified nanoparticles, 0.04 parts of platinum catalyst, 0.02 parts of platinum catalyst inhibitor, 15 parts of toluene, and 5 parts of propylene glycol monomethyl ether acetate were added to a reactor. After stirring at 800 rpm for 50 min, the coating was sprayed onto a substrate under a pressure of 0.4 MPa and cured at 160 °C for 1 h to obtain control sample 2. The application performance of control sample 2 is detailed in Table 2.

[0102] Comparative Example 3

[0103] Preparation of hydrophobically modified nanoparticles: 10g of SiO2 nanoparticles with a particle size of 20-30nm and 25g of calcined kaolin nanoparticles with a particle size of 30-80nm were added to a mixed solution of 10g mercaptopropyltriethoxysilane, 20g perfluorodecyltriethoxysilane, 13g butyl acetate, 25g propylene glycol methyl ether acetate, and 25g ethyl acetate. The mixture was stirred at 800rpm for 60min to obtain hydrophobically modified nanoparticles.

[0104] Preparation of the non-stick coating: 10 parts of hydrogen-containing silicone resin IC, 12 parts of hydrogen-containing silicone resin IIC, 38 parts of perfluorodecylethylene, 20 parts of hydrophobically modified nanoparticles, 0.04 parts of platinum catalyst, 0.02 parts of platinum catalyst inhibitor, 15 parts of toluene, and 5 parts of propylene glycol monomethyl ether acetate were added to a reactor. After stirring at 800 rpm for 50 min, the coating was sprayed onto a substrate under a pressure of 0.4 MPa and cured at 160℃ for 1 h to obtain comparative sample 3. The application performance of comparative sample 3 is detailed in Table 2.

[0105] Table 1 Performance Comparison of Examples

[0106]

[0107] Table 2 Comparison of Comparative Performance

[0108]

[0109] Table 3 Comparison of Existing Technical Performance

[0110]

[0111] The above description is only a preferred embodiment of the present invention. It should be noted that those skilled in the art can make several improvements and additions without departing from the method of the present invention, and these improvements and additions should also be considered within the scope of protection of the present invention.

Claims

1. An organosilicon non-stick coating, comprising, by weight: 55-65 parts of a fluorinated organosilicon composition, 15-25 parts of hydrophobically modified nanoparticles, 0.03-0.05 parts of a platinum catalyst, 0.01-0.03 parts of a platinum catalyst inhibitor, and 15-30 parts of solvent A, wherein the fluorinated organosilicon composition is composed of a hydrogen-containing silicone resin, a fluorinated side-hydrogen vinyl silicone oil, and perfluoroethylene, in a mass ratio of 1:0.5-1.5:0.4-0.

9.

2. The silicone non-stick coating as described in claim 1, characterized in that, The hydrogen-containing silicone resin is one or both of the silicone resins shown in Formula I and Formula II. Formula I: [R 1 SiO 3 / 2 a [R 2 SiO 3 / 2 b [R 3 SiO 3 / 2 c ​​​ In formula I, R 1 It is hydrogen; R 2 It is phenyl; R 3 It is a monovalent hydrocarbon group of C1 to C6; a = 0.3 to 0.7, b = 0.3 to 0.7, c = 0 to 0.3, and a + b + c = 1; Formula II: [RSiO 1 / 2 ] a [SiO2] b In Formula II, R is one or more of hydrogen, phenyl, and C1-C6 monovalent hydrocarbon groups; a = 0.5-0.8, b = 0.2-0.5, and a+b = 1.

3. The silicone non-stick coating as described in claim 2, characterized in that, In formula I, R 3 It is one of methyl, ethyl, or propyl; in Formula II, the monovalent hydrocarbon group of C1 to C6 is methyl, ethyl, or propyl.

4. The silicone non-stick coating as described in any one of claims 1-3, characterized in that, The structural formula of the fluorinated side-hydrogen vinyl silicone oil is as follows: CH2=CHSiO[R 1 R 2 SiO] a [R 1 HSiO] b [R 1 2SiO] c OSiCH=CH2, where R 1 R is a monovalent hydrocarbon group of C1 to C6. 2 The expression is CH2CH2CF3, a:b:c = 2.67-4:13-15:

1.

5. The silicone non-stick coating as described in claim 4, characterized in that, R 1 It can be methyl, ethyl, or propyl.

6. The silicone non-stick coating according to any one of claims 1-3, characterized in that, The perfluoroethylene is selected from carbon atoms with numbers C4-C6. 14 Perfluoroalkyl ethylene.

7. The silicone non-stick coating as described in claim 6, characterized in that, The perfluoroethylene is perfluorodecylethylene.

8. The silicone non-stick coating according to any one of claims 1-3, characterized in that, The hydrophobically modified nanoparticles are obtained by adding nanoparticles to a hydrophobic modifier and stirring; the nanoparticles are one or more of SiO2, TiO2, diatomaceous earth, bentonite, and calcined kaolin; and / or the hydrophobic modifier is a mixed solution of a common silane coupling agent, a perfluorosilane coupling agent, and an ester solvent, in a mass ratio of 1:1-2:6-8.

9. The silicone non-stick coating as described in claim 8, characterized in that, The common silane coupling agent is one of vinyltriethoxysilane, glycidyl ether propyltrimethoxysilane, methacryloxypropyltrimethoxysilane, or mercaptopropyltriethoxysilane.

10. The silicone non-stick coating as described in claim 8, characterized in that, The perfluorosilane coupling agent is one of dodecafluoroheptylpropyltrimethoxysilane, tridecafluorooctyltriethoxysilane, and perfluorodecyltriethoxysilane.

11. The silicone non-stick coating as described in claim 8, characterized in that, The ester solvent is a mixed solution of butyl acetate, propylene glycol methyl ether acetate and ethyl acetate, with a weight ratio of butyl acetate, propylene glycol methyl ether acetate and ethyl acetate of 1:(1.5-2):(1.5-2).

12. The silicone non-stick coating according to any one of claims 1-3, characterized in that, Solvent A is selected from one or more of toluene, xylene, and propylene glycol monomethyl ether acetate.

13. The method for preparing the organosilicon non-stick coating according to any one of claims 1-12, characterized in that, Include: The hydrogen-containing silicone resin, fluorinated side-hydrogen vinyl silicone oil, perfluorinated vinyl, platinum catalyst, platinum catalyst inhibitor, and hydrophobically modified nanoparticles are stirred at 500-1000 rpm for 30-60 min, then sprayed onto a substrate under a pressure of 0.3-0.7 MPa, and cured at 140-160℃ for 0.5-2 h to obtain the final product.

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