Polymer, preparation method thereof, non-stick coating and cooking utensil

Abstract

The invention discloses a polymer, a preparation method thereof, a non-stick coating, a cooking utensil and a method for preparing the cooking utensil, a main chain of the polymer comprises a silicon-oxygen bond, and two end groups of the polymer respectively comprise an active group and a low surface energy group; the low surface energy group comprises a silane group; the active groups comprise at least one of-NH2,-SH,-Cl,-Br, an epoxy group, a glycidyl group and a glycidoxy group. The polymer has a Si-O main chain, and has outstanding thermal oxidation stability, excellent moisture resistance, water resistance, rust resistance, cold resistance, corrosion resistance and the like. One end of the polymer contains silane groups, so that the coating has excellent anti-sticking performance, the other end of the polymer has active groups, and the active groups can be combined with other structures such as a bottom layer and a surface layer in a chemical bond form, so that the problem of material evaporation loss when the coating is used is avoided, and the service life of the coating is prolonged. The lasting non-stick performance of the coating is facilitated.

Description

Technical Field

[0001] The invention belongs to the technical field of materials, and in particular relates to a polymer, a preparation method thereof, a non-stick coating and a cooking utensil. Background Art

[0002] The mainstream non-stick pans on the market currently rely on spraying a non-stick coating on the surface of the substrate, relying on the coating's strong hydrophobicity and low friction coefficient to achieve non-stick food. However, existing non-stick coatings have defects such as poor adhesion to the substrate, easy to fall off after long-term use, poor toughness, easy to be corroded by acid, and poor non-stick durability.

[0003] Therefore, it is necessary to improve the non-stick coating. Summary of the invention

[0004] The present invention aims to improve at least one of the above technical problems at least to some extent.

[0005] In order to improve the above technical problems, the present invention provides a polymer, wherein the main chain of the polymer includes a silicon-oxygen bond, and the two end groups of the polymer respectively include an active group and a low surface energy group; the low surface energy group includes a silane group; the active group includes at least one of -NH2, -SH, -Cl, -Br, an epoxy group, a glycidyl group, and a glycidyloxy group. Thus, the polymer has a Si-O main chain, has outstanding thermal oxidation stability, and excellent moisture-proof, waterproof, rust-proof, cold-resistant, corrosion-resistant and other properties. One end of the polymer of the present invention contains a silane group, which has a lower surface energy and can make the coating have excellent anti-sticking properties. The other end of the polymer has active groups such as -NH2, -SH, -Cl, -Br, and a glycidyl group, which can be combined with other structures such as a bottom layer and a surface layer in the form of a chemical bond, avoiding the problem of material evaporation loss when the coating is used, which is beneficial for the coating to have a lasting non-stick property.

[0006] According to an embodiment of the present invention, the structural formula of the low surface energy group is: Wherein, n3 is an integer greater than 100.

[0007] According to an embodiment of the present invention, the structural formula of the polymer is as shown in Formula I:

[0008]

[0009] Wherein, n1 and n2 are independently selected from integers greater than 1, and R is the active group.

[0010] The present invention also provides a method for preparing the polymer described above, the method comprising: subjecting the hydroxy silicone oil shown in formula II, tetraethyl silicate, and the silane coupling agent shown in formula III to a polymerization reaction in the presence of a catalyst to obtain the polymer shown in formula I; formula II: Formula III: Wherein, R' is an alkyl group. Thus, the polymer prepared by this method has all the characteristics and advantages of the polymer described above, which will not be repeated here. In addition, this method also has the advantage of simple operation and is suitable for large-scale industrial production.

[0011] According to an embodiment of the present invention, the content of the hydroxy silicone oil is 5 to 25 parts by weight, the content of the tetraethyl silicate is 50 to 70 parts by weight, the content of the catalyst is 0.1 to 3 parts by weight, and the content of the silane coupling agent is 1 to 10 parts by weight.

[0012] According to an embodiment of the present invention, the method satisfies at least one of the following conditions: the molecular weight of the hydroxy silicone oil is 5000-10000; the silane coupling agent includes at least one of aminopropyltrimethoxysilane, aminopropyltriethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, chloropropyltrimethoxysilane, and chloropropyltriethoxysilane; the catalyst includes at least one of ethanolamine, diethanolamine, triethanolamine, triethylamine, aluminum acetylacetonate, and dibutyltin dilaurate.

[0013] According to an embodiment of the present invention, the method comprises: mixing the hydroxy silicone oil shown in formula II with tetraethyl silicate to obtain a mixture; adding a catalyst to the mixture to perform a first reaction; adding a silane coupling agent shown in formula III to the reaction system of the first reaction to perform a second reaction to obtain a polymer shown in formula I. The addition sequence of the present invention is conducive to the preparation of the polymer shown in formula I with a high yield, and avoids the problem of generating homopolymer byproducts due to uneven mixing.

[0014] According to an embodiment of the present invention, mixing hydroxy silicone oil with tetraethyl silicate comprises: stirring the mixed hydroxy silicone oil and tetraethyl silicate at a temperature of 70 to 90° C. for 10 to 30 minutes to obtain a mixture; the temperature of the first reaction is 50 to 120° C., and the time of the first reaction is 30 minutes to 4 hours; the temperature of the second reaction is 50 to 120° C., and the time of the second reaction is 30 minutes to 2 hours.

[0015] According to an embodiment of the present invention, after the second reaction is completed, the method further comprises the step of adding a film-forming aid to the polymer; the content of the film-forming aid is 1-10 parts by weight; the film-forming aid comprises at least one of propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol butyl ether, isopropyl alcohol, and isobutyl alcohol.

[0016] The present invention also provides a non-stick coating, which comprises: a bottom layer; a middle layer, the middle layer is located on the bottom layer, and the material forming the middle layer comprises the polymer described above or comprises a polymer prepared by the method described above; and a surface layer, the surface layer is located on a side of the middle layer away from the bottom layer. Therefore, the non-stick coating has all the characteristics and advantages of the polymer described above, which will not be repeated here.

[0017] According to an embodiment of the present invention, the material forming the bottom layer includes at least one of polyethersulfone, polyetheretherketone, and polyphenylene sulfide; the material forming the surface layer includes nano-silicon dioxide. Thus, the bottom layer of the present invention enables the coating to have excellent adhesion and toughness, the middle layer can firmly combine the three-layer structure and provide excellent anti-stick performance, the surface layer can enable the coating surface to have excellent hardness, and the bottom layer, the middle layer, and the surface layer cooperate with each other, so that the non-stick coating of the present invention can have excellent performance.

[0018] According to an embodiment of the present invention, the thickness of the bottom layer is 10-30 μm, the thickness of the middle layer is 15-25 μm, and the thickness of the surface layer is 10-25 μm.

[0019] The present invention also provides a cooking utensil, the cooking utensil comprising: a substrate; the non-stick coating as described above, the non-stick coating being disposed on the surface of the substrate, and the bottom layer of the non-stick coating being disposed on the substrate. Thus, the cooking utensil has all the features and advantages of the non-stick coating as described above, which will not be described in detail here.

[0020] According to an embodiment of the present invention, the material forming the substrate includes at least one of iron, aluminum, aluminum alloy, and stainless steel.

[0021] According to an embodiment of the present invention, the cooking utensil includes at least one of a wall breaking machine, a pressure cooker, an electric rice cooker, a wok, a frying pan, and a stew pot. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 is a flow chart of a method for preparing a polymer in one embodiment of the present invention;

[0023] Figure 2 is a schematic structural diagram of a non-stick coating in one embodiment of the present invention;

[0024] Figure 3 is a schematic structural diagram of a cooking utensil in one embodiment of the present invention;

[0025] Figure 4 It is a schematic structural diagram of a cooking utensil in another embodiment of the present invention.

[0026] Description of Reference Numerals

[0027] 100-non-stick coating, 110-bottom layer, 120-middle layer, 130-top layer, 200-base material. DETAILED DESCRIPTION

[0028] The scheme of the present invention will be explained below in conjunction with the embodiments. It will be appreciated by those skilled in the art that the following embodiments are only used to illustrate the present invention and should not be considered as limiting the scope of the present invention. Where specific techniques or conditions are not indicated in the embodiments, the techniques or conditions described in the literature in this area or the product specifications are used. The reagents or instruments used are not indicated by the manufacturer and are all conventional products that can be obtained commercially.

[0029] Existing cooking utensils have been widely used in non-stick coatings. The non-stick coating has the characteristics of strong hydrophobicity and low friction coefficient, which can achieve the effect of non-stick food. Cooking utensils coated with non-stick coatings have the advantage of being easy to clean, and they can be cleaned with a light wipe. For example, non-stick pans can easily fry and stir-fry food without sticking to the bottom, which can minimize the use of oil, keep the kitchen clean and less fumes, and it can also help reduce fat intake, conforming to the modern people's pursuit of low-fat and low-calorie consumption trends. Non-stick coatings include polytetrafluoroethylene coatings and ceramic non-stick coatings. The strength of polytetrafluoroethylene coatings is poor, easy to fall off and damage, and it will soften during cooking. Only wooden spatulas can be used, and hard food cannot be cooked; in addition, fluorine organic matter will decompose at high temperatures (greater than 410°C), causing the fluorine organic coating to gradually damage. After the fluorine organic matter on the inner surface of the pot is damaged, the non-stick pan will lose its non-stick function. In addition, there has always been controversy over whether polytetrafluoroethylene coated non-stick pans are harmful to human health during use, which has continuously caused disputes. In the related art, the non-stick additive of ceramic non-stick coating is usually silicone oil. During long-term use, the silicone oil is slowly evaporated and consumed. Using it at high temperature will accelerate the consumption of silicone oil, causing the ceramic non-stick coating to gradually lose its non-stick properties.

[0030] In order to improve the above technical problems, the present invention provides a polymer, wherein the main chain of the polymer includes a silicon-oxygen bond, and the two end groups of the polymer include an active group and a low surface energy group respectively; the low surface energy group includes a silane group; the active group includes at least one of -NH2, -SH, -Cl, -Br, an epoxy group, a glycidyl group, and a glycidyloxy group. That is to say, the two end groups of the polymer are different, one of the end groups of the polymer includes an active group, and the other end group of the polymer includes a low surface energy group. Since the bond angle of the Si-O bond in the main chain of the polymer is large, the polymer can have good flexibility. Moreover, the low surface energy group will migrate to the surface of the coating under heating conditions, which can make the coating have excellent anti-stick properties. The polymer of the present invention can be used as a middle layer material of a non-stick coating. The active group of the polymer can make the polymer tightly combined with other structures such as the bottom layer and the surface layer, avoiding the problem of material evaporation loss during the use of the coating, so that the non-stick coating has a lasting non-stick performance. The polymer of the present invention has high stability, high thermal oxidation stability, and will not decompose harmful substances under high temperature conditions. The polymer of the present invention will not harm human health during use, and has the advantages of high safety and environmental friendliness. In addition, the polymer of the present invention also has the advantages of excellent moisture resistance, waterproofness, rust resistance, cold resistance, corrosion resistance and the like.

[0031] According to an embodiment of the present invention, the structural formula of the low surface energy group is: Wherein, n3 is an integer greater than 100. The low surface energy group of the present invention is a long-chain silyl methyl group, which has a relatively low surface energy and can make the coating have excellent anti-sticking properties.

[0032] According to an embodiment of the present invention, the structural formula of the polymer is as shown in Formula I:

[0033]

[0034] Wherein, n1 and n2 are the same or different and are independently selected from an integer greater than 1, and R is the above-mentioned active group, specifically, R includes at least one of -NH2, -SH, -Cl, -Br, epoxy, glycidyl, and glycidyloxy. Thus, the main chain of the polymer includes Si-O bonds, which can make the polymer have good flexibility, and the polymer can be used as a middle layer material to firmly combine the bottom layer and the surface layer. Moreover, one end group of the polymer includes a low surface energy group, which can make the polymer have excellent anti-adhesive properties, and the other end group of the polymer includes an active group. Using the polymer as a middle layer material is conducive to the reaction of the polymer with the bottom layer material and the surface layer material, thereby firmly combining the middle layer with the bottom layer and the surface layer. In addition, the polymer also has the advantages of high stability, is not easy to decompose during use, will not harm human health, and has the advantages of environmental friendliness and high safety.

[0035] The polymer of the present invention can be used for non-stick coatings. Specifically, the polymer of the present invention can be used as a middle layer material of the non-stick coating to make the middle layer of the non-stick coating. Alternatively, the polymer of the present invention can also be used for high temperature resistant adhesives. Alternatively, the polymer of the present invention can also be used for fluororesin non-stick coatings to improve the bonding strength between the non-stick coating and the substrate.

[0036] The present invention also provides a method for preparing the polymer described above, the method comprising: subjecting the hydroxy silicone oil represented by formula II, tetraethyl silicate, and the silane coupling agent represented by formula III to polymerization reaction in the presence of a catalyst to obtain the polymer represented by formula I;

[0037] Formula II: Formula III: Wherein, each R' is the same or different and is independently selected from an alkyl group. Thus, the polymer prepared by this method has the same structure as the polymer described above. In addition, this method has the advantages of simple operation and low production cost.

[0038] It should be noted that the term "alkyl" should be understood to preferably mean a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 40 carbon atoms, preferably C 1-10 Alkyl. "C 1-10 “Alkyl” is to be understood as meaning preferably a linear or branched, saturated, monovalent hydrocarbon radical having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. The alkyl radical is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl etc. or their isomers. In particular, the radical has 1, 2, 3, 4, 5, 6 carbon atoms (“C 1-6 alkyl), for example methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, more particularly, the radical having 1, 2 or 3 carbon atoms (“C 1-3 alkyl"), for example methyl, ethyl, n-propyl or isopropyl.

[0039] According to an embodiment of the present invention, the content of the hydroxy silicone oil is 5 to 25 parts by weight, the content of the tetraethyl silicate is 50 to 70 parts by weight, the content of the catalyst is 0.1 to 3 parts by weight, and the content of the silane coupling agent is 1 to 10 parts by weight. Thus, when the content of each component is within the above range, it is conducive to a sufficient polymerization reaction and a high yield of the polymer shown in Formula I is obtained.

[0040] According to an embodiment of the present invention, the molecular weight of the hydroxy silicone oil is 5000 to 10000. If the molecular weight of the hydroxy silicone oil is too small, the non-stick performance of the hydroxy silicone oil is poor, which in turn makes the non-stick performance of the polymer poor. If the molecular weight of the hydroxy silicone oil is too large, the hardness of the hydroxy silicone oil will be small, which will affect the hardness of the polymer. Moreover, if the molecular weight of the hydroxy silicone oil is too large, the hydroxy silicone oil is too viscous, which will affect the flatness of the product surface when spraying to form a product.

[0041] According to some embodiments of the present invention, the silane coupling agent includes at least one of aminopropyltrimethoxysilane, aminopropyltriethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, chloropropyltrimethoxysilane, and chloropropyltriethoxysilane.

[0042] According to some embodiments of the present invention, the catalyst includes at least one of ethanolamine, diethanolamine, triethanolamine, triethylamine, aluminum acetylacetonate, and dibutyltin dilaurate.

[0043] According to an embodiment of the present invention, referring to Figure 1 , the method comprising:

[0044] S100, mixing the hydroxy silicone oil represented by formula II with tetraethyl silicate to obtain a mixture;

[0045] Through step S100, the hydroxy silicone oil and tetraethyl silicate can be mixed evenly, avoiding the occurrence of problems such as homopolymerization of monomers with higher activity and non-reaction of monomers with lower activity due to uneven mixing, which is conducive to obtaining the polymer shown in formula I in high yield.

[0046] According to an embodiment of the present invention, mixing hydroxy silicone oil with tetraethyl silicate includes: stirring the mixed hydroxy silicone oil and tetraethyl silicate at a temperature of 70 to 90° C. (e.g., 50° C., 55° C., 60° C., 65° C., 70° C., 75° C., 80° C., 85° C., 90° C.) for 10 to 30 minutes (e.g., 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes) to obtain a mixture. This facilitates uniform mixing of hydroxy silicone oil and tetraethyl silicate, so that both hydroxy silicone oil and tetraethyl silicate can participate in the subsequent polymerization reaction.

[0047] S200, adding a catalyst to the mixture to perform a first reaction;

[0048] The temperature of the first reaction is 50-120°C (e.g., 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C), and the time of the first reaction is 30min-4h (e.g., 30min, 1h, 2h, 3h, 4h). Thus, under this condition, it is beneficial for hydroxy silicone oil and tetraethyl silicate to hydrolyze.

[0049] S300, adding a silane coupling agent to the reaction system of the first reaction, performing a second reaction, and obtaining a polymer represented by formula I.

[0050] The temperature of the second reaction is 50-120°C (e.g., 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C), and the time of the second reaction is 30min-2h (e.g., 30min, 1h, 2h). This is conducive to the reaction of the hydrolyzed molecules with the silane coupling agent to generate the polymer shown in Formula I.

[0051] According to an embodiment of the present invention, after the second reaction is completed, the method further comprises the step of adding a film-forming aid to the polymer. After the film-forming aid is added to the polymer, it can be used as a coating liquid for the middle layer and sprayed to form a film to form the middle layer. By adding the film-forming aid, the leveling of the polymer is facilitated and the film formation is facilitated.

[0052] According to some embodiments of the present invention, the content of the film-forming aid is 1-10 parts by weight; if the content of the film-forming aid is too low, the content of the polymer is relatively high, which will make the leveling effect of the polymer poor; if the content of the film-forming aid is too high, the content of the polymer that plays a key role in improving the non-stick performance is relatively low, affecting the non-stick performance.

[0053] According to some embodiments of the present invention, the film-forming aid includes at least one of propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol butyl ether, isopropyl alcohol, and isobutyl alcohol. After these compounds are mixed with the polymer, they can play a role in diluting the polymer and are beneficial to the leveling and film formation of the polymer.

[0054] The method for preparing the polymer of the present invention also has the advantages of simple operation and low production cost, and is suitable for large-scale industrial production.

[0055] The present invention also provides a non-stick coating, referring to Figure 2The non-stick coating 100 includes a bottom layer 110, a middle layer 120 and a surface layer 130, wherein the middle layer 120 is located on the bottom layer 110, and the surface layer 130 is located on a side of the middle layer 120 away from the bottom layer 110. The material forming the middle layer 120 includes the polymer described above or includes a polymer prepared by the method described above. Therefore, the non-stick coating 100 has all the characteristics and advantages of the polymer described above, which will not be repeated here. One end group of the polymer forming the middle layer 120 contains a low surface energy group, which has a low surface energy. Under heating conditions, it will migrate to the surface of the middle layer 120 close to the surface layer 130, so that the non-stick coating 100 has good anti-stick properties; the middle layer 120, as a transition layer, can provide good bonding between the bottom layer 110 and the surface layer 130. Specifically, the other end group of the polymer has an active group R, which can react with the ether bond of the bottom layer 110 and the silicon dioxide of the surface layer 130, so that the bottom layer 110 and the surface layer 130 are firmly bonded together through the middle layer 120, avoiding the problem of material evaporation loss, and making the non-stick coating 100 have a lasting non-stick property. In general, the non-stick coating 100 of the present invention has good non-stick properties, is easy to clean, and the temperature distribution in the non-stick coating is relatively uniform when heated, which can prevent the problem of burning food and greatly improve the user experience.

[0056] According to an embodiment of the present invention, the material forming the bottom layer 110 includes at least one of polyethersulfone, polyetheretherketone, and polyphenylene sulfide. The above materials have the advantages of high temperature resistance, low cost and easy availability. At the same time, the above materials also have excellent adhesion to the metal substrate, which is conducive to the firm bonding of the non-stick coating to the metal substrate.

[0057] According to an embodiment of the present invention, the material forming the surface layer 130 includes nano-silicon dioxide, thereby enabling the surface of the non-stick coating to have excellent hardness.

[0058] According to an embodiment of the present invention, the thickness of the bottom layer 110 is 10 to 30 μm, for example, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm, 30 μm. Thus, the bottom layer 110 can be firmly attached to the substrate 200 and has high toughness. If the thickness of the bottom layer 110 is too small, it will affect the bonding strength between the non-stick coating 100 and the substrate 200, resulting in poor adhesion and easy damage to the coating. If the thickness of the bottom layer 110 is too large, the coating will be prone to cracking.

[0059] According to an embodiment of the present invention, the thickness of the middle layer 120 is 15 to 25 μm, for example, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, and 25 μm. In this way, the non-stick coating can have good anti-stick properties, and can ensure that the bottom layer 110 and the surface layer 130 are firmly bonded. If the thickness of the middle layer 120 is too small, the effect of improving the non-stick performance will be poor, the bonding strength of the bottom layer 110 and the surface layer 130 will be affected, the effect of bonding the bottom layer 110 and the surface layer 130 will be poor, and the service life of the non-stick coating 100 will be short. If the thickness of the middle layer 120 is too large, the coating will easily crack, detach, and other undesirable problems will occur during use.

[0060] According to an embodiment of the present invention, the thickness of the surface layer 130 is 10 to 25 μm, for example, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm. Thus, the non-stick coating can have a higher hardness. If the thickness of the surface layer 130 is too small, there will be problems such as poor corrosion resistance, easy damage to the coating, and short service life of the coating. If the thickness of the surface layer 130 is too large, there will be a problem that the coating is easy to crack, and the excessive thickness of the coating will also increase the production cost.

[0061] In general, when the thickness of the bottom layer 110, the middle layer 120, and the surface layer 130 are within the above range, the bottom layer 110, the middle layer 120, and the surface layer 130 cooperate with each other, so that the non-stick coating has better non-stick performance during long-term use. At the same time, the non-stick coating also has excellent advantages such as moisture-proof, waterproof, rust-proof, cold-resistant, and corrosion-resistant.

[0062] It should be noted that the “thickness” is the distance measured from the surface of the non-stick coating along a direction perpendicular to the surface of the non-stick coating.

[0063] The present invention also provides a cooking utensil, referring to Figure 3 and Figure 4 The cooking utensil comprises: a substrate 200 and the non-stick coating 100 described above, wherein the non-stick coating 100 is disposed on the surface of the substrate 200, and the bottom layer 110 of the non-stick coating 100 is disposed on the substrate 200. Thus, the cooking utensil has all the features and advantages of the non-stick coating described above, which will not be described in detail here. In general, the cooking utensil has a better long-term non-stick effect.

[0064] According to the specific type of cooking utensils and / or actual non-stick requirements, the non-stick coating 100 can cover a part or the entire surface of the substrate 200. For example, the non-stick coating 100 can be disposed on a part of the inner surface of the substrate 200, and the non-stick coating 100 at least covers the cooking area of ​​the cooking utensils, thereby achieving the effect of non-stick pan when cooking food. Alternatively, the non-stick coating 100 can also be further disposed on the outer surface of the substrate 200.

[0065] According to an embodiment of the present invention, the material forming the substrate 200 includes at least one of iron, aluminum, aluminum alloy, and stainless steel. These materials are cheap and easy to obtain, and can have a strong bonding force with the non-stick coating. The present invention does not limit the shape of the substrate 200, and the shape of the substrate 200 can be changed according to the purpose of the cooking utensil. For example, the shape of the substrate 200 can be a round bottom pan shape, a frying pan shape, a kettle shape, etc. In addition, the present invention does not limit the size of the substrate 200, and the size of the substrate 200 can be adjusted according to the specific needs of the cooking utensil.

[0066] According to an embodiment of the present invention, the cooking utensil includes at least one of a wall breaking machine, a pressure cooker, an electric rice cooker, a wok, a frying pan, a stew pot, a soup pot, a grill, and a bread maker.

[0067] It should be noted that, in addition to the structures described above, the cooking utensil may also include structures that a conventional cooking utensil should have. For example, the cooking utensil may also include other structures such as a handle, a pot cover, and a heating element.

[0068] According to an embodiment of the present invention, a cooking utensil can be prepared in the following manner: spraying a bottom layer material on one side of a substrate to form a bottom layer; spraying the aforementioned polymer on the side of the bottom layer away from the substrate to form a middle layer; spraying a surface layer material on the side of the middle layer away from the bottom layer to form a surface layer; heating and drying the bottom layer, the middle layer, and the surface layer, and then sintering and curing to obtain a non-stick coating; wherein the heating and drying temperature is 150°C, and the heating and drying time is 10 minutes; the sintering and curing temperature is 300°C, and the sintering and curing time is 10 minutes. During the sintering and curing process, the polymer can react with the groups in the bottom layer material and the surface layer material at high temperature, so that the bottom layer and the surface layer can be firmly combined.

[0069] The present invention is described below with reference to specific embodiments. It should be noted that these embodiments are merely illustrative and do not limit the present invention in any way.

[0070] Example 1

[0071] Preparation of polymer

[0072] Add 10 g of hydroxy silicone oil (molecular weight 7000) and 50 g of tetraethyl silicate into a flask, stir at 70°C for 30 min, then add 0.1 g of dibutyltin dilaurate, stir and react at 70°C for 2 h, then add 5 g of mercaptopropyltriethoxysilane, stir and react at 70°C for 1 h to obtain a polymer, add 8 g of propylene glycol monomethyl ether to the polymer to obtain a silicone coating.

[0073] Preparing non-stick coatings

[0074] The substrate of the cooking utensil was preheated to 50-60° C., and then a polyethersulfone emulsion was sprayed on the substrate to form a bottom layer with a thickness of 20 μm. Subsequently, the organic silicon coating prepared in Example 1 was sprayed on the bottom layer to form a middle layer with a thickness of 15 μm. Subsequently, nano-silicon dioxide was sprayed on the middle layer to form a surface layer with a thickness of 15 μm. After the surface layer was sprayed, it was baked at 150° C. for 10 min, and then the temperature was raised to 300° C. and baked for 15 min to obtain a cooking utensil with a non-stick coating.

[0075] Example 2

[0076] Preparation of polymer

[0077] Add 10 g of hydroxy silicone oil (molecular weight 7000) and 50 g of tetraethyl silicate into a flask, stir at 70°C for 30 min, then add 0.1 g of dibutyltin dilaurate, stir and react at 70°C for 2 h, then add 1 g of aminopropyltriethoxysilane, stir and react at 70°C for 1 h to obtain a polymer, add 8 g of propylene glycol monomethyl ether to the polymer to obtain a silicone coating.

[0078] Preparing non-stick coatings

[0079] The substrate of the cooking utensil was preheated to 50-60° C., and then a polyethersulfone emulsion was sprayed on the substrate to form a bottom layer with a thickness of 20 μm. Subsequently, the organic silicon coating prepared in Example 2 was sprayed on the bottom layer to form a middle layer with a thickness of 15 μm. Subsequently, nano-silicon dioxide was sprayed on the middle layer to form a surface layer with a thickness of 15 μm. After the surface layer was sprayed, it was baked at 150° C. for 10 min, and then the temperature was increased to 300° C. and baked for 15 min to obtain a cooking utensil with a non-stick coating.

[0080] Example 3

[0081] Preparation of polymer

[0082] Add 10 g of hydroxy silicone oil (molecular weight 7000) and 50 g of tetraethyl silicate into a flask, stir at 70°C for 30 min, then add 0.1 g of dibutyltin dilaurate, stir and react at 70°C for 2 h, then add 5 g of glycidyloxypropyltriethoxysilane, stir and react at 70°C for 1 h to obtain a polymer, add 8 g of propylene glycol monomethyl ether to the polymer to obtain a silicone coating.

[0083] Preparing non-stick coatings

[0084] The substrate of the cooking utensil was preheated to 50-60° C., and then a polyethersulfone emulsion was sprayed on the substrate to form a bottom layer with a thickness of 20 μm. Subsequently, the silicone coating prepared in Example 3 was sprayed on the bottom layer to form a middle layer with a thickness of 15 μm. Subsequently, nano-silicon dioxide was sprayed on the middle layer to form a surface layer with a thickness of 15 μm. After the surface layer was sprayed, it was baked at 150° C. for 10 min, and then the temperature was raised to 300° C. and baked for 15 min to obtain a non-stick coating.

[0085] Example 4

[0086] Preparation of polymer

[0087] Add 10 g of hydroxy silicone oil (molecular weight 9000) and 50 g of tetraethyl silicate into a flask, stir at 70°C for 30 min, then add 0.1 g of dibutyltin dilaurate, stir and react at 70°C for 2 h, then add 5 g of glycidyloxypropyltriethoxysilane, stir and react at 70°C for 1 h to obtain a polymer, add 8 g of propylene glycol monomethyl ether to the polymer to obtain a silicone coating.

[0088] Preparing non-stick coatings

[0089] The substrate of the cooking utensil was preheated to 50-60° C., and then a polyethersulfone emulsion was sprayed on the substrate to form a bottom layer with a thickness of 20 μm. Subsequently, the silicone coating prepared in Example 4 was sprayed on the bottom layer to form a middle layer with a thickness of 15 μm. Subsequently, nano-silicon dioxide was sprayed on the middle layer to form a surface layer with a thickness of 15 μm. After the surface layer was sprayed, it was baked at 150° C. for 10 min, and then the temperature was raised to 300° C. and baked for 15 min to obtain a cooking utensil with a non-stick coating.

[0090] Comparative Example 1

[0091] Preparation of polymer

[0092] 10 g of hydroxy silicone oil (molecular weight 5000) and 50 g of tetraethyl silicate were added to a flask, stirred at 70° C. for 30 min, and then 0.1 g of dibutyltin dilaurate was added, stirred and reacted at 70° C. for 2 h to obtain a polymer. 8 g of propylene glycol monomethyl ether was added to the polymer to obtain a silicone coating.

[0093] Preparing non-stick coatings

[0094] The substrate of the cooking utensil is preheated to 50-60° C., and then a polyethersulfone emulsion is sprayed on the substrate to form a bottom layer with a thickness of 20 μm. Subsequently, the silicone coating prepared in Comparative Example 1 is sprayed on the bottom layer to form a middle layer with a thickness of 15 μm. Subsequently, nano-silicon dioxide is sprayed on the middle layer to form a surface layer with a thickness of 15 μm. After the surface layer is sprayed, it is baked at 150° C. for 10 min, and then the temperature is increased to 300° C. and baked for 15 min to obtain a cooking utensil with a non-stick coating.

[0095] Comparative Example 2

[0096] Preparation of polymer

[0097] Add 10 g of hydroxy silicone oil (molecular weight 2000) and 50 g of tetraethyl silicate into a flask, stir at 70°C for 30 min, then add 0.1 g of dibutyltin dilaurate, stir and react at 70°C for 2 h, then add 5 g of glycidyloxypropyltriethoxysilane, stir and react at 70°C for 1 h to obtain a polymer, add 8 g of propylene glycol monomethyl ether to the polymer to obtain a silicone coating.

[0098] Preparing non-stick coatings

[0099] The substrate of the cooking utensil is preheated to 50-60°C, and then a polyethersulfone emulsion is sprayed on the substrate to form a bottom layer with a thickness of 20 μm. Subsequently, the silicone coating prepared in Comparative Example 2 is sprayed on the bottom layer to form a middle layer with a thickness of 15 μm. Subsequently, nano-silicon dioxide is sprayed on the middle layer to form a surface layer with a thickness of 15 μm. After the surface layer is sprayed, it is baked at 150°C for 10 min, and then the temperature is increased to 300°C and baked for 15 min to obtain a cooking utensil with a non-stick coating.

[0100] The non-stick coatings in Examples 1-4 and Comparative Examples 1-2 were subjected to the following performance tests:

[0101] 1. Boil salt water test

[0102] The test method is as follows: put an equal amount of 5% salt water by mass into the cooking utensils of Examples 1-4 and Comparative Examples 1-2, boil the salt water for 8 hours and then keep it warm for 16 hours, which is regarded as one cycle. Observe and record the number of cycles required for the non-stick coating of each cooking utensil to start bubbling or falling off.

[0103] 2. High temperature resistance test

[0104] Experimental method: The cooking utensils of Examples 1-4 and Comparative Examples 1-2 were placed under a heating condition of 400°C for 4 hours, and after cooling, 250g of rice (brand: Golden Dragon Fish) was added, and the rice was cooked at a power of 500W. After cooking, it was observed and recorded whether the rice could be poured directly from the cooking utensils without any rice residue.

[0105] 3. Wear resistance test

[0106] Test method: Use detergent to prepare 5% concentration of washing water, 3M (7447C) scouring pad, load 2.5kg, swing left and right as one stroke, replace the scouring pad every 250 strokes, check whether the non-stick coating is exposed to the substrate every 250 strokes, if the substrate is exposed, terminate the test; if the substrate is not exposed, continue the wear resistance test, record the number of strokes that meet the wear resistance requirements, which is the number of wear resistance tests.

[0107] The test results are shown in Table 1.

[0108] Table 1

[0109]

[0110] The two end groups of the polymers prepared in Examples 1-4 include active groups and low surface energy groups, respectively. In Comparative Example 1, no silane coupling agent was added during the preparation of the polymer, and the prepared polymer had no active groups. In the step of preparing the polymer in Comparative Example 2, the molecular weight of the hydroxy silicone oil was too small. As shown in Table 1, the number of cycles, high temperature resistance, and wear resistance of the cooking utensils in Examples 1-4 in the boiling salt water test were better than those of the cooking utensils in Comparative Examples 1-2, indicating that the non-stick coating prepared by the method of the present invention has lasting non-stickiness, high temperature resistance, and strong wear resistance. That is to say, when the main chain of the polymer forming the middle layer of the non-stick coating includes a silicon-oxygen bond, the two end groups of the polymer include active groups and low surface energy groups, respectively, and the low surface energy groups include silane groups, and the active groups include at least one of -NH2, -SH2, -Cl, -Br, epoxy, glycidyl, and glycidyloxy, it is beneficial for the non-stick coating to have lasting non-stickiness, high temperature resistance, and strong wear resistance.

[0111] The embodiments of the present invention are described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, and these simple modifications all belong to the protection scope of the present invention. It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction.

[0112] In the description of the present invention, it is to be understood that the terms “center”, “longitudinal”, “lateral”, “length”, “width”, “thickness”, “up”, “down”, “front”, “back”, “left”, “right”, “vertical”, “horizontal”, “top”, “bottom”, “inside”, “outside”, “clockwise”, “counterclockwise”, “axial”, “radial”, “circumferential”, etc., indicating orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the referred device or element must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as limiting the present invention.

[0113] It should be noted that in this specification, the terms "first" and "second" are only used for description, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. The orientation or position relationship indicated by the terms "upper" and "lower" is based on the orientation or position relationship shown in the drawings, which is only for the convenience of describing the present invention and does not require that the present invention must be constructed and operated in a specific orientation, and cannot be understood as limiting the present invention. In the present invention, unless otherwise clearly specified and limited, the first feature "upper" or "lower" of the second feature may be that the first and second features are in direct contact, or the first and second features are in indirect contact through an intermediate medium. Moreover, the first feature "above", "above" and "above" of the second feature may be that the first feature is directly above or obliquely above the second feature, or simply indicates that the first feature is higher in level than the second feature. The first feature "below", "below" and "below" of the second feature may be that the first feature is directly below or obliquely below the second feature, or simply indicates that the first feature is lower in level than the second feature. In the description of the present invention, the meaning of "multiple" is two or more, unless otherwise clearly and specifically limited. In the present invention, unless otherwise clearly specified and limited, the terms "installed", "connected", "connected", "fixed" and the like should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0114] In the description of this specification, the description with reference to the terms "one embodiment", "some specific embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. Different embodiments or examples described in this specification and features of different embodiments or examples may be combined and combined by those skilled in the art without contradiction.

[0115] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations of the present invention. A person skilled in the art may change, modify, replace and vary the above embodiments within the scope of the present invention.

Claims

1. A polymer, characterized in that The main chain of the polymer includes a silicon-oxygen bond, and the two end groups of the polymer include an active group and a low surface energy group respectively; The low surface energy groups include silane groups; The active groups include at least one of -NH2, -SH, -Cl, -Br, epoxy, glycidyl, and glycidyloxy.

2. The polymer according to claim 1, characterized in that The structural formula of the low surface energy group is: Wherein, n3 is an integer greater than 100.

3. The polymer according to claim 2, characterized in that The structural formula of the polymer is shown in Formula I: Wherein, n1 and n2 are independently selected from integers greater than 1, and R is the active group.

4. A method for preparing a polymer according to any one of claims 1 to 3, characterized in that: The method comprises: subjecting hydroxy silicone oil represented by formula II, tetraethyl silicate and a silane coupling agent represented by formula III to polymerization reaction in the presence of a catalyst to obtain a polymer represented by formula I; Formula II: Formula III: Wherein, R' is an alkyl group.

5. The method according to claim 4, characterized in that The content of the hydroxy silicone oil is 5 to 25 parts by weight, the content of the tetraethyl silicate is 50 to 70 parts by weight, the content of the catalyst is 0.1 to 3 parts by weight, and the content of the silane coupling agent is 1 to 10 parts by weight.

6. The method according to claim 4, characterized in that The method satisfies at least one of the following conditions: The molecular weight of the hydroxy silicone oil is 5000 to 10000; The silane coupling agent includes at least one of aminopropyltrimethoxysilane, aminopropyltriethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, chloropropyltrimethoxysilane and chloropropyltriethoxysilane; The catalyst includes at least one of ethanolamine, diethanolamine, triethanolamine, triethylamine, aluminum acetylacetonate, and dibutyltin dilaurate.

7. The method according to claim 4, characterized in that The method comprises: mixing the hydroxy silicone oil represented by formula II with tetraethyl silicate to obtain a mixture; adding a catalyst to the mixture to carry out a first reaction; A silane coupling agent represented by formula III is added to the reaction system of the first reaction to carry out a second reaction to obtain a polymer represented by formula I.

8. The method according to claim 7, characterized in that Mixing the hydroxy silicone oil with tetraethyl silicate comprises: stirring the mixed hydroxy silicone oil and tetraethyl silicate at a temperature of 70 to 90° C. for 10 to 30 minutes to obtain a mixture; The temperature of the first reaction is 50-120°C, and the time of the first reaction is 30min-4h; The temperature of the second reaction is 50-120° C., and the time of the second reaction is 30 min-2 h.

9. The method according to claim 7, characterized in that: After the second reaction is completed, the method further comprises the step of adding a film-forming aid to the polymer; The content of the film-forming aid is 1-10 parts by weight; The film-forming aid includes at least one of propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol butyl ether, isopropyl alcohol and isobutyl alcohol.

10. A non-stick coating, characterized in that: The non-stick coating comprises: bottom layer; A middle layer, the middle layer is located on the bottom layer, and the material forming the middle layer includes the polymer according to any one of claims 1 to 3 or includes a polymer prepared by the method according to any one of claims 4 to 9; The surface layer is located on a side of the middle layer away from the bottom layer.

11. The non-stick coating according to claim 10, characterized in that The material forming the bottom layer includes at least one of polyethersulfone, polyetheretherketone and polyphenylene sulfide; The material forming the surface layer includes nano silicon dioxide.

12. The non-stick coating according to claim 10, characterized in that The thickness of the bottom layer is 10 to 30 μm, the thickness of the middle layer is 15 to 25 μm, and the thickness of the surface layer is 10 to 25 μm.

13. A cooking utensil, characterized in that: The cooking appliance comprises: Base material; The non-stick coating according to any one of claims 10 to 12, wherein the non-stick coating is disposed on the surface of the substrate, and the bottom layer of the non-stick coating is disposed on the substrate.

14. The cooking appliance according to claim 13, characterized in that The material forming the substrate includes at least one of iron, aluminum, aluminum alloy, and stainless steel; The cooking utensil comprises at least one of a wall breaking machine, a pressure cooker, an electric rice cooker, a wok, a frying pan, and a stew pot.

Images