A kind of organic silicon coating and its preparation method and application

Abstract

The present invention discloses an organosilicon coating and a preparation method and application thereof, belonging to the technical field of coatings. The organosilicon coating provided by the present invention comprises the following preparation raw materials: polyether polyol diglycidyl ether, epoxy-containing silane coupling agent, amino silicone oil, and catecholamine. Based on the ring-opening addition reaction characteristics between amino and epoxy groups and the condensation reaction characteristics between silane molecules containing hydrolyzable groups, the present invention successfully applies organosilicon components with low surface energy to coatings. The present invention combines the advantages of each raw material to obtain a system containing ether bonds, hydroxyl groups, catechol groups, polysiloxane segments and other groups. Through the interaction of each group, an organosilicon coating with high hardness, good adhesion, and significant anti-corrosion and anti-fouling effects is obtained, which has a wide range of applications in the field of material protection.

Description

Technical Field

[0001] The invention belongs to the technical field of coatings, and in particular relates to an organosilicon coating and a preparation method and application thereof. Background Art

[0002] In the field of material protection, it is a common method to use coating as protective material, but the protective effect of existing protective coatings is not ideal, and there is still room for improvement in its anti-corrosion performance, anti-fouling performance, hydrophobicity, adhesion performance and hardness. Taking metal materials as an example, they are widely used in various places in daily life because of their good mechanical strength, electrical conductivity, thermal conductivity and processability. However, the chemical stability of most commonly used metals is not high, and they are often corroded by salt spray and rainwater in practical applications, resulting in their mechanical strength and structure being destroyed during long-term application, which not only brings huge economic losses, but also increases safety hazards. In the field of metal material protection, although the electrochemical anti-corrosion method of external power supply or active metal can be used to effectively protect metal materials from corrosion, it is difficult to be widely used due to its high cost and poor feasibility. Compared with electrochemical anti-corrosion, surface coating technology has outstanding advantages in cost economy, feasibility, etc., and is currently one of the most effective technical methods for surface protection of metal materials. Although polymer coatings have made some progress, the coatings currently available on the market generally have problems such as limited protective performance and low hardness, and are not very practical in harsh environments such as strong ultraviolet rays, strong winds and sand, and high salt fog. Summary of the invention

[0003] In order to overcome the problems existing in the above-mentioned prior art, one of the objects of the present invention is to provide an organosilicon coating, which has excellent anti-corrosion performance, anti-fouling performance, hydrophobicity, strong adhesion performance and high hardness.

[0004] A second object of the present invention is to provide a method for preparing the above-mentioned organosilicon coating.

[0005] A third object of the present invention is to provide an organosilicon coating prepared from the above-mentioned organosilicon coating.

[0006] A fourth object of the present invention is to provide a method for preparing the above-mentioned organosilicon coating.

[0007] A fifth object of the present invention is to provide an application of the above-mentioned organosilicon paint or the above-mentioned organosilicon coating in the field of protection.

[0008] In order to achieve the above object, the technical solution adopted by the present invention is:

[0009] The first aspect of the present invention provides an organosilicon coating, comprising the following preparation raw materials: polyether polyol diglycidyl ether, epoxy-containing silane coupling agent, amino silicone oil, and catecholamine.

[0010] The present invention uses polyether polyol diglycidyl ether, epoxy-containing silane coupling agent, amino silicone oil and catecholamine together. The epoxy groups in polyether polyol diglycidyl ether and epoxy-containing silane coupling agent can react with the amine groups in amino silicone oil and catecholamine. Meanwhile, the epoxy-containing silane coupling agent contains alkoxy groups and epoxy groups, and condensation reactions can occur between molecules. After the above reactions, an organic silicon coating containing ether bonds, hydroxyl groups, catechol groups and polysiloxane segments can be obtained. The ether bonds, hydroxyl groups and catechol groups in the above groups can not only form hydrogen bonds with each other to improve the coating strength to a certain extent, but also can further have physical effects and chemical reactions with hydroxyl groups and ions on the surface of metal materials, so that the organic silicon coating can firmly adhere to the metal material and achieve stable adhesion to the metal material. In particular, the catechol groups in the organic silicon coating can greatly improve the adhesion of the coating to the metal. In addition, the polysiloxane chain segment can give the coating good anti-corrosion, anti-fouling and hydrophobic properties due to its low surface energy and corrosion resistance.

[0011] Preferably, in the silicone coating, the mass fraction of polyether polyol diglycidyl ether is 0.2 to 12 parts; more preferably 0.4 to 10 parts; further preferably 0.6 to 7 parts; more preferably 0.8 to 5 parts.

[0012] Preferably, in the organosilicon coating, the mass fraction of the epoxy-containing silane coupling agent is 0.2 to 25 parts; more preferably 0.4 to 20 parts; further preferably 0.6 to 15 parts; more preferably 0.8 to 10 parts.

[0013] Preferably, in the organosilicon coating, the mass fraction of amino silicone oil is 0.2 to 25 parts; more preferably 0.4 to 20 parts; further preferably 0.6 to 15 parts; more preferably 0.8 to 10 parts.

[0014] Preferably, in the organosilicon coating, the mass fraction of catecholamine is 0.05 to 12 parts; more preferably 0.07 to 10 parts; further preferably 0.1 to 5 parts; more preferably 0.5 to 2 parts.

[0015] Preferably, the organosilicon coating comprises the following raw materials in parts by weight: 0.2 to 12 parts of polyether polyol diglycidyl ether, 0.2 to 25 parts of epoxy-containing silane coupling agent, 0.2 to 25 parts of amino silicone oil, and 0.05 to 12 parts of catecholamine.

[0016] Further preferably, the organosilicon coating comprises the following raw materials in parts by weight: 0.4 to 10 parts of polyether polyol diglycidyl ether, 0.4 to 20 parts of epoxy-containing silane coupling agent, 0.4 to 20 parts of amino silicone oil, and 0.07 to 10 parts of catecholamine.

[0017] More preferably, the organosilicon coating comprises the following raw materials in parts by weight: 0.6 to 7 parts of polyether polyol diglycidyl ether, 0.6 to 15 parts of epoxy-containing silane coupling agent, 0.6 to 15 parts of amino silicone oil, and 0.1 to 5 parts of catecholamine.

[0018] More preferably, the organosilicon coating comprises the following raw materials in parts by weight: 0.8 to 5 parts of polyether polyol diglycidyl ether, 0.8 to 10 parts of epoxy-containing silane coupling agent, 0.8 to 10 parts of amino silicone oil, and 0.5 to 2 parts of catecholamine.

[0019] Preferably, in the silicone coating, the polyether polyol diglycidyl ether includes at least one of polyethylene glycol-polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether; further preferably, the polyether polyol diglycidyl ether includes polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether or a combination thereof; further preferably, the polyether polyol diglycidyl ether is selected from polyethylene glycol diglycidyl ether.

[0020] Preferably, the average molecular weight of the polyether polyol diglycidyl ether is 100 to 10,000; more preferably, it is 150 to 5,000; and even more preferably, it is 200 to 2,000.

[0021] Preferably, the epoxy value of the polyether polyol diglycidyl ether is 0.01 to 1 mol / 100 g; more preferably, it is 0.2 to 0.9 mol / 100 g; and even more preferably, it is 0.5 to 0.85 mol / 100 g.

[0022] Preferably, in the silicone coating, the epoxy-containing silane coupling agent includes at least one of 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane or triethoxyoctylsilane; further preferably, the epoxy-containing silane coupling agent includes at least one of 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane or γ-mercaptopropyltriethoxysilane; further preferably, the epoxy-containing silane coupling agent is selected from 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane.

[0023] Wherein, the 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane is a silane coupling agent A-186 or WD-63, CAS number: 3388-04-3; the γ-glycidoxypropyltrimethoxysilane is a silane coupling agent KH-560, CAS number: 2530-83-8; the γ-mercaptopropyltriethoxysilane is a silane coupling agent KH-580, CAS number: 14814-09-6; the triethoxyoctylsilane is a silane coupling agent KH-832, CAS number: 2943-75-1.

[0024] Preferably, in the organosilicon coating, the aminosilicone oil is selected from an organosiloxane or a polymer thereof containing at least two primary or secondary amines; further preferably, the aminosilicone oil has a structural formula of M[SiR2O] n -SiR2M'; wherein M and M' are independently selected from -NH2 and -NHR groups, each of the above Rs are independently selected from C1~C8 straight chain or branched alkyl, C1~C8 straight chain or branched substituted alkyl, aryl alkenyl and derivatives thereof, and n is 1 to 3000.

[0025] Preferably, the average molecular weight of the amino silicone oil is 200 to 200,000; more preferably, it is 250 to 50,000; and even more preferably, it is 300 to 5,000.

[0026] In the organic silicon coating, catecholamine is an amine compound containing a catechol structure; and the amine compound is an organic compound containing at least one primary amine group (-NH2) or secondary amine group (-NH-).

[0027] Preferably, the catecholamine includes at least one of dopamine, dopamine hydrochloride, norepinephrine or epinephrine; more preferably, dopamine and dopamine hydrochloride; and even more preferably, dopamine hydrochloride.

[0028] Preferably, the raw materials for preparing the organosilicon coating further include a solvent and / or a catalyst; further preferably, the raw materials for preparing the organosilicon coating further include a solvent and a catalyst.

[0029] Preferably, the solvent is selected from organic solvents; further preferably, the solvent includes at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isopropanol, isobutanol, octanol, ethylene glycol, methyl ether, ethyl ether, acetone, chloroform, propylene glycol methyl ether acetate, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol methyl ether acetate, ethyl acetate or tetrahydrofuran; further preferably, it includes at least one of N,N-dimethylformamide, N,N-dimethylacetamide or propylene glycol methyl ether acetate.

[0030] Preferably, the catalyst comprises at least one of an inorganic acid, an organic acid, an inorganic base or an organic base; more preferably, it comprises an inorganic acid, an organic acid or a combination thereof; and even more preferably, it is an inorganic acid.

[0031] Preferably, the inorganic acid includes at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, carbonic acid, iodic acid, hypochlorous acid, perchloric acid, nitrous acid, hypobromous acid or hypophosphorous acid; further preferably includes at least one of hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid; further preferably, it is hydrochloric acid, sulfuric acid or a combination thereof.

[0032] Preferably, the organic acid comprises at least one of formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, oxalic acid, succinic acid, phthalic acid, isophthalic acid or terephthalic acid; further preferably comprises at least one of formic acid, acetic acid, propionic acid, n-butyric acid or isobutyric acid; further preferably comprises at least one of formic acid, acetic acid or propionic acid.

[0033] Under the action of the catalyst, the epoxy groups of polyether polyol diglycidyl ether and epoxy-containing silane coupling agent in the silicone coating can efficiently undergo ring-opening addition reaction with the amine groups in amino silicone oil and catecholamine. In addition, epoxy-containing silane coupling agent can also efficiently undergo condensation reaction under the action of the catalyst.

[0034] Amine and epoxy groups can undergo a ring-opening addition reaction under the catalysis of acid or base. Under acid catalysis, the addition reaction is greatly affected by the stability of the carbon cation; under base catalysis, the addition reaction is greatly affected by steric hindrance. In addition, epoxy-containing silane coupling agents can also undergo condensation reactions under the catalysis of acid or base. Considering that catecholamines are easily oxidized under alkaline conditions, catecholamines and amino silicone oils both have a certain alkalinity. In some embodiments of the present invention, inorganic acids, organic acids or combinations thereof are preferably used as catalysts, and inorganic acids are more preferably used as catalysts.

[0035] Preferably, the mass of the solvent is 10-600% of the total mass of the polyether polyol diglycidyl ether, the epoxy-containing silane coupling agent, the amino silicone oil and the catecholamine; more preferably 20-400%; and even more preferably 50-250%.

[0036] Preferably, the mass of the catalyst is 0.001-1% of the total mass of polyether polyol diglycidyl ether, epoxy-containing silane coupling agent, amino silicone oil and catecholamine; more preferably 0.003-0.8%; and even more preferably 0.005-0.5%.

[0037] Preferably, in the organosilicon coating, the mass fraction of the solvent is 1 to 80 parts; more preferably 2 to 70 parts; further preferably 3 to 50 parts; more preferably 5 to 40 parts.

[0038] Preferably, in the organosilicon coating, the mass fraction of the catalyst is 0.001 to 7 parts; more preferably 0.005 to 5 parts; further preferably 0.01 to 3 parts; more preferably 0.02 to 1 part.

[0039] Preferably, the organic silicone coating comprises the following raw materials in parts by weight: 0.2 to 12 parts of polyether polyol diglycidyl ether, 0.2 to 25 parts of epoxy-containing silane coupling agent, 0.2 to 25 parts of amino silicone oil, 0.05 to 12 parts of catecholamine, 1 to 80 parts of solvent, and 0.001 to 7 parts of catalyst.

[0040] Further preferably, the organosilicon coating comprises the following raw materials in parts by mass: 0.4 to 10 parts of polyether polyol diglycidyl ether, 0.4 to 20 parts of epoxy-containing silane coupling agent, 0.4 to 20 parts of amino silicone oil, 0.07 to 10 parts of catecholamine, 2 to 70 parts of solvent, and 0.005 to 5 parts of catalyst.

[0041] More preferably, the organosilicon coating comprises the following raw materials in parts by weight: 0.6 to 7 parts of polyether polyol diglycidyl ether, 0.6 to 15 parts of epoxy-containing silane coupling agent, 0.6 to 15 parts of amino silicone oil, 0.1 to 5 parts of catecholamine, 3 to 50 parts of solvent, and 0.01 to 3 parts of catalyst.

[0042] More preferably, the organic silicone coating comprises the following raw materials in parts by weight: 0.8 to 5 parts of polyether polyol diglycidyl ether, 0.8 to 10 parts of epoxy-containing silane coupling agent, 0.8 to 10 parts of amino silicone oil, 0.5 to 2 parts of catecholamine, 5 to 40 parts of solvent, and 0.02 to 1 part of catalyst.

[0043] The second aspect of the present invention provides a method for preparing the organosilicon coating according to the first aspect of the present invention, comprising the following steps: mixing various preparation raw materials for reaction to obtain the organosilicon coating.

[0044] Preferably, the preparation method of the silicone coating comprises the following steps: firstly dissolving polyether polyol diglycidyl ether and catecholamine in a solvent, adding a catalyst, carrying out a first step reaction, then adding an epoxy-containing silane coupling agent and amino silicone oil, carrying out a second step reaction, and obtaining the silicone coating.

[0045] Preferably, in the preparation method of the organosilicon coating, after the first step of the reaction, the epoxy-containing silane coupling agent and the amino silicone oil are added after the temperature drops below 80°C; more preferably, the temperature drops below 60°C.

[0046] Preferably, in the method for preparing the organosilicon coating, the temperature of the first step reaction is 0 to 200°C; more preferably 20 to 150°C; and even more preferably 40 to 100°C.

[0047] Preferably, in the method for preparing the organosilicon coating, the first step reaction time is 0.1 to 12 h; more preferably 0.2 to 6 h; and even more preferably 0.5 to 3 h.

[0048] Preferably, in the method for preparing the organosilicon coating, the temperature of the second step reaction is 0 to 200°C; more preferably 20 to 150°C; and even more preferably 40 to 100°C.

[0049] Preferably, in the method for preparing the organosilicon coating, the reaction time of the second step is 0.1 to 24 hours; more preferably 1 to 12 hours; and even more preferably 2 to 6 hours.

[0050] The third aspect of the present invention provides an organosilicon coating prepared from the organosilicon coating described in the first aspect of the present invention.

[0051] In a specific embodiment of the present invention, the thickness of the organic silicon coating is 60 to 180 microns; in a specific example of the present invention, the thickness of the organic silicon coating is 70 to 170 microns; in an example of the present invention, the thickness of the organic silicon coating is 80 to 160 microns.

[0052] The fourth aspect of the present invention provides a method for preparing the organosilicon coating described in the third aspect of the present invention, comprising the following steps: coating the organosilicon coating on the surface of a substrate, and obtaining the organosilicon coating after curing.

[0053] Preferably, the substrate includes an organic substrate or an inorganic substrate; more preferably an inorganic substrate.

[0054] Preferably, the inorganic substrate includes at least one of a metal substrate, a wood board or a ceramic; more preferably, the inorganic substrate is a metal substrate.

[0055] Preferably, the substrate includes at least one of a solid wood board, a density board, an iron sheet, a copper sheet, an aluminum sheet, a silicate wall or a ceramic; more preferably, it includes at least one of an iron sheet, a copper sheet or an aluminum sheet.

[0056] The solid wood board is not limited to any tree species.

[0057] Preferably, in the method for preparing the organosilicon coating, the curing temperature is 0 to 300°C; more preferably 30 to 200°C; and even more preferably 60 to 150°C.

[0058] Preferably, in the method for preparing the organosilicon coating, the curing time is 0.1 to 24 hours; more preferably 0.5 to 12 hours; and even more preferably 1 to 6 hours.

[0059] Preferably, the curing is: first curing at 30-100°C for 0.1-2h; then curing at 100-300°C for 2-24h; further preferably, the curing is: first curing at 60-100°C for 0.1-1h; then curing at 100-150°C for 4-8h.

[0060] Preferably, the coating step can be repeated, that is, the coating can be repeated after the organic silicon coating is cured, and the number of repetitions is 1 to 100 times; more preferably 1 to 20 times; and even more preferably 1 to 5 times.

[0061] Preferably, the coating amount for each coating is 0.01 to 0.5 mL / cm 2 ; More preferably, 0.02 to 0.3 mL / cm 2 ; More preferably, 0.03 to 0.2 mL / cm 2 .

[0062] The present invention does not impose strict restrictions on the coating method of the organosilicon coating, and the coating method can be any one or more of spin coating, drip coating, dip coating, scraper coating, brush coating, spray coating, etc.

[0063] The fifth aspect of the present invention provides an application of the organosilicon coating described in the first aspect of the present invention, or the organosilicon coating described in the third aspect of the present invention in the field of material protection.

[0064] The beneficial effects of the present invention are:

[0065] The present invention successfully applies an organic silicon component with low surface energy to coatings based on the ring-opening addition reaction characteristics between amino groups and epoxy groups and the condensation reaction characteristics between silane molecules containing hydrolyzable groups. The present invention combines the advantages of various raw materials such as polyether polyol diglycidyl ether, epoxy-containing silane coupling agent, amino silicone oil, catecholamine, etc. to obtain a system containing groups such as ether bonds, hydroxyl groups, catechol groups and polysiloxane segments. Through the interaction of various groups, an organic silicon coating with high hardness, good adhesion and significant anti-corrosion and anti-fouling effects is obtained.

[0066] Specifically, compared with the prior art, the present invention has the following advantages:

[0067] 1. The functional groups such as ether bonds and hydroxyl groups contained in the organosilicon coating of the present invention can physically act or chemically react with the groups or ions on the surface of the inorganic or organic substrate, not only having good film-forming properties, but also achieving a firm bond with the surface of the substrate, especially the catechol groups in catecholamines, which can greatly improve the adhesion of the coating. In addition, the polysiloxane segments of amino silicone oil make the organosilicon protective coating have excellent anti-liquid adhesion properties. The coating is not only difficult to be attached by stains with high surface energy, but also can block the corrosion of corrosive substances to the substrate under the coating.

[0068] 2. Organic siloxanes have the excellent properties of both inorganic and organic materials, and have the characteristics of good weather resistance, good corrosion resistance, low surface energy, and good chemical stability. Introducing a certain amount of organic siloxane components on the surface of substrates such as metal materials can make their surfaces have certain hydrophobic properties and corrosion resistance.

[0069] 3. The preparation method of the organosilicon coating of the present invention is simple, does not require high temperature and high pressure, has low equipment requirements, and is conducive to large-scale industrial production. The coating formed by the organosilicon coating of the present invention after coating and curing has good hardness, adhesion, hydrophobicity, antifouling and anti-corrosion properties, and can be used for surface protection of various materials, especially inorganic materials. The organosilicon coating and the organosilicon coating prepared therefrom have a wide range of applications in the field of protection. BRIEF DESCRIPTION OF THE DRAWINGS

[0070] Figure 1 The contact angle test results of Examples 1 to 6 and Comparative Examples 1 to 2 are shown.

[0071] Figure 2 The actual pictures of the hundred-grid scratches of Examples 1-2 and Comparative Examples 1-2 are shown.

[0072] Figure 3 This is the test result of the liquid-proof performance of Example 4.

[0073] Figure 4 It is the transmittance curve diagram of Example 1 and Comparative Example 1.

[0074] Figure 5 This is the test result of the ultraviolet light irradiation experiment of Example 4.

[0075] Figure 6 The antifouling performance test results of Example 2 and Example 4 are shown. DETAILED DESCRIPTION

[0076] The content of the present invention is further described in detail below through specific examples. It should also be understood that the following examples are only used to further illustrate the present invention and cannot be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the principles set forth in the present invention all belong to the scope of protection of the present invention. The specific process parameters and the like in the following examples are also only examples within a suitable range, that is, those skilled in the art can make a selection within a suitable range through the description herein, and are not limited to the specific data exemplified below. The raw materials, reagents or devices used in the following examples and comparative examples, unless otherwise specified, can all be obtained from conventional commercial sources, or can be obtained by existing known methods.

[0077] Example 1

[0078] This example provides an organic silicon coating, and the preparation method comprises the following steps:

[0079] The first step is to dissolve 3 parts of polyethylene glycol diglycidyl ether (epoxy value: 0.7 mol / 100 g) and 0.5 parts of dopamine hydrochloride in 30 parts of N, N-dimethylformamide according to the mass ratio, add 0.05 parts of concentrated hydrochloric acid, and react at 80°C for 120 minutes to obtain an intermediate product; the second step is to add 6 parts of 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane and 10 parts of aminosilicone oil (Mn=500) according to the mass ratio when the temperature of the reaction system drops below 60°C, and heat to 80°C and react for 240 minutes to obtain the silicone coating.

[0080] This example also provides an organic silicon coating, and the preparation method includes the following steps:

[0081] The organic silicon coating obtained in this example was dripped on the surface of the iron sheet (coating amount: 0.15 mL / cm 2 ), first cure at 70°C for 30 minutes, then heat to 125°C for 240 minutes, and then obtain a silicone coating with a thickness of 80 to 160 microns.

[0082] Example 2

[0083] This example provides an organic silicon coating, and the preparation method comprises the following steps:

[0084] The first step is to dissolve 3 parts of polyethylene glycol diglycidyl ether (epoxy value: 0.7 mol / 100 g) and 0.7 parts of dopamine hydrochloride in 35 parts of N, N-dimethylformamide according to the mass ratio, add 0.06 parts of concentrated hydrochloric acid, and react at 80°C for 120 minutes to obtain an intermediate product; the second step is to add 6 parts of 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane and 12 parts of aminosilicone oil (Mn=500) according to the mass ratio when the temperature of the reaction system drops below 60°C, and heat to 80°C and react for 240 minutes to obtain the silicone coating.

[0085] This example also provides an organic silicon coating, and the preparation method includes the following steps:

[0086] In this example, the obtained organic silicon coating was dripped onto the surface of the iron sheet (coating amount: 0.15 mL / cm 2 ), first cure at 70°C for 30 minutes, then heat to 125°C for 240 minutes, and then obtain a silicone coating with a thickness of 80 to 160 microns.

[0087] Example 3

[0088] This example provides an organic silicon coating, and the preparation method comprises the following steps:

[0089] The first step is to dissolve 3 parts of polyethylene glycol diglycidyl ether (epoxy value: 0.7 mol / 100g) and 1 part of dopamine hydrochloride in 25 parts of propylene glycol methyl ether acetate according to the mass ratio, add 0.04 parts of concentrated hydrochloric acid, and react at 70°C for 60 minutes to obtain an intermediate product; the second step is to add 5 parts of 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane and 6 parts of aminosilicone oil (Mn=500) according to the mass ratio when the temperature of the reaction system drops below 60°C, and heat to 70°C and react for 180 minutes to obtain the silicone coating.

[0090] This example also provides an organic silicon coating, and the preparation method includes the following steps:

[0091] In this example, the obtained organic silicon coating was dripped onto the surface of the iron sheet (coating amount: 0.15 mL / cm 2 ), first cure at 60°C for 30 minutes, then heat to 120°C for 180 minutes, and then obtain a silicone coating with a thickness of 80 to 160 microns.

[0092] Example 4

[0093] This example provides an organic silicon coating, and the preparation method comprises the following steps:

[0094] The first step is to dissolve 3 parts of polyethylene glycol diglycidyl ether (epoxy value: 0.7 mol / 100g) and 1 part of dopamine hydrochloride in 25 parts of N, N-dimethylacetamide according to the mass ratio, add 0.06 parts of concentrated hydrochloric acid, and react at 100°C for 60 minutes to obtain an intermediate product; the second step is to add 5 parts of 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane and 15 parts of aminosilicone oil (Mn=500) according to the mass ratio when the temperature of the reaction system drops below 60°C, and heat to 100°C and react for 180 minutes to obtain the silicone coating.

[0095] This example also provides an organic silicon coating, and the preparation method includes the following steps:

[0096] In this example, the obtained organic silicon coating was dripped onto the surface of the iron sheet (coating amount: 0.15 mL / cm 2 ), first cure at 80°C for 30 minutes, then heat to 130°C for 240 minutes, and then obtain a silicone coating with a thickness of 80 to 160 microns.

[0097] Example 5

[0098] This example provides an organic silicon coating, and the preparation method comprises the following steps:

[0099] The first step is to dissolve 3 parts of polyethylene glycol diglycidyl ether (epoxy value: 0.7 mol / 100g) and 1 part of dopamine hydrochloride in 24 parts of propylene glycol methyl ether acetate according to the mass ratio, add 0.04 parts of concentrated hydrochloric acid, and react at 80°C for 120 minutes to obtain an intermediate product; the second step is to add 4 parts of 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane and 8 parts of aminosilicone oil (Mn=500) according to the mass ratio when the temperature of the reaction system drops below 60°C, and heat to 80°C and react for 240 minutes to obtain the silicone coating.

[0100] This example also provides an organic silicon coating, and the preparation method includes the following steps:

[0101] In this example, the obtained organic silicon coating was dripped onto the surface of the iron sheet (coating amount: 0.15 mL / cm 2 ), first cured at 60°C for 30 min, then heated to 125°C for 180 min, and after curing, the obtained silicone coating was repeatedly coated on the substrate surface (coating amount: 0.05 mL / cm 2 ), the coating-curing-coating process is repeated once to obtain a silicone coating with a thickness of 80 to 160 microns.

[0102] Example 6

[0103] This example provides an organic silicon coating, and the preparation method comprises the following steps:

[0104] The first step is to dissolve 3 parts of polyethylene glycol diglycidyl ether (epoxy value: 0.7 mol / 100 g) and 0.5 parts of dopamine hydrochloride in 25 parts of N, N-dimethylformamide according to the mass ratio, add 0.05 parts of concentrated hydrochloric acid, and react at 80°C for 120 minutes to obtain an intermediate product; the second step is to add 5 parts of 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane and 10 parts of aminosilicone oil (Mn=500) according to the mass ratio when the temperature of the reaction system drops below 60°C, and heat to 80°C and react for 240 minutes to obtain the silicone coating.

[0105] This example also provides an organic silicon coating, and the preparation method includes the following steps:

[0106] In this example, the obtained organic silicon coating was dripped onto the surface of the iron sheet (coating amount: 0.15 mL / cm 2 ), first cured at 70°C for 30 min, then heated to 125°C for 180 min, and after curing, the obtained silicone coating was repeatedly coated on the substrate surface (coating amount: 0.05 mL / cm 2 ), the coating-curing-coating process is repeated once to obtain a silicone coating with a thickness of 80 to 160 microns.

[0107] Comparative Example 1

[0108] This example provides an organic silicon coating, and the preparation method comprises the following steps:

[0109] According to the mass ratio, 3 parts of polyethylene glycol diglycidyl ether (epoxy value: 0.7 mol / 100 g), 6 parts of 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, 10 parts of aminosilicone oil (Mn=500) and 0.05 parts of concentrated hydrochloric acid were dissolved in 30 parts of N,N-dimethylformamide, and reacted at 80°C for 240 minutes to obtain the silicone coating.

[0110] This example also provides an organic silicon coating, and the preparation method includes the following steps:

[0111] In this example, the obtained organic silicon coating was dripped onto the surface of the iron sheet (coating amount 0.15 mL / cm 2 ), first cure at 70°C for 30 minutes, then heat to 125°C for 240 minutes, and then obtain a silicone coating with a thickness of 80 to 160 microns.

[0112] Comparative Example 2

[0113] This example provides an organic silicon coating, and the preparation method comprises the following steps:

[0114] According to the mass ratio, 3 parts of polyethylene glycol diglycidyl ether (epoxy value: 0.7 mol / 100 g), 6 parts of 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, 12 parts of aminosilicone oil (Mn=500) and 0.06 parts of concentrated hydrochloric acid were dissolved in 35 parts of N,N-dimethylformamide, and reacted at 80°C for 240 minutes to obtain the silicone coating.

[0115] This example also provides an organic silicon coating, and the preparation method includes the following steps:

[0116] In this example, the obtained organic silicon coating was dripped onto the surface of the iron sheet (coating amount 0.15 mL / cm 2 ), first cure at 70°C for 30 minutes, then heat to 125°C for 240 minutes, and then obtain a silicone coating with a thickness of 80 to 160 microns.

[0117] The compositions and proportions of the raw materials of Examples 1 to 6 and Comparative Examples 1 to 2 are shown in Table 1.

[0118] Table 1 Composition and ratio of raw materials in Examples 1 to 6 and Comparative Examples 1 to 2 (unit: mass parts)

[0119]

[0120] Performance testing and results

[0121] (1) The water drop contact angle test was performed on the organic silicon coating on the surface of the iron sheet of Examples 1 to 6 and Comparative Examples 1 to 2 using a contact angle tester (JY-PHb, Chengde Jinhe Instrument Manufacturing Co., Ltd.). The results are as follows: Figure 1 shown.

[0122] (2) The adhesion (hundred-grid scratch test) and hardness (pencil hardness) tests were performed on the silicone coating on the surface of the iron sheet of Examples 1 to 6 and Comparative Examples 1 to 2. The adhesion test was performed with reference to GB / T 9286-2021 using an adhesion tester (QFH type, Taizhou Aice Instrument Co., Ltd.); the hardness test was performed with reference to GB / T 6739-2006 using a pencil hardness tester (QHQ-A type, Dongguan Huaguo Precision Instrument Co., Ltd.). At the same time, the color characteristics and surface characteristics were observed, and the results are shown in Table 2. It can be seen that after adding dopamine hydrochloride, the adhesion of Examples 1 to 2 is greatly improved compared with Comparative Examples 1 to 2, and the actual picture of the hundred-grid scratch test is shown in Table 2. Figure 2 shown.

[0123] (3) The organic silicon coating on the surface of the iron sheet of Example 4 was tilted 30°, and a small water droplet (test liquid volume 50 μL) was dropped on the surface of the organic silicon protective coating to test its surface anti-liquid adhesion performance. The results are as follows: Figure 3As shown in the figure, it can be seen that when the inclination angle is 30°, the small water droplets quickly slide down from the high point on the surface of the iron sheet within a few seconds, showing excellent anti-liquid adhesion performance.

[0124] (4) The glass slide was coated with the organic silicon coating of Example 1 and Comparative Example 1, and an organic silicon coating was formed after curing. The coating thickness was about 10 μm. Then, a UV-visible light spectrophotometer (U-2910, Hitachi High-Technologies Corporation) was used to scan the transmittance and perform a transmittance test. The transmittance curve is shown in FIG. Figure 4 It can be seen that the light transmittance of the glass sheet coated with comparative example 1 is only slightly reduced compared with the blank glass sheet; while the glass sheet coated with example 1 has poor transmittance for light with a wavelength below 600nm, but still maintains a relatively high transmittance for light with a wavelength above 600nm, indicating good transmittance.

[0125] (5) The organic silicon coating on the surface of the iron sheet of Example 4 was placed under ultraviolet light for irradiation, and the water drop contact angle test was performed regularly. The contact angle change curve was as follows: Figure 5 As shown in the figure, it can be seen that as the irradiation time goes by, the advancing contact angle remains almost unchanged, while the receding contact angle gradually decreases, and the anti-liquid adhesion performance of the coating surface decreases to a certain extent.

[0126] (6) The organosilicon coatings of Example 2 and Example 4 were used to coat the tinplate sheet, and the organosilicon coating was formed after curing. A blank iron sheet of the same type was selected as a comparison. Then, two different commercially available markers (any model) were used to graffiti on Example 2, Example 4 and the blank iron sheet. After the graffiti dried, it was wiped back and forth with a dry paper towel. The test results are as follows: Figure 6 As shown in the figure, it can be seen that the iron sheet coated with the silicone coating has a good repelling effect on the ink of the marker pen, and the ink can be easily wiped off with a dry paper towel after it dries.

[0127] Table 2 Performance test results of silicone coatings of Examples 1 to 6 and Comparative Examples 1 to 2

[0128]

[0129]

[0130] The present invention successfully applies a silicone component with low surface energy to a coating based on the ring-opening addition reaction characteristics between amino and epoxy groups and the condensation reaction characteristics between silane molecules containing hydrolyzable groups. The present invention combines the advantages of various raw materials such as polyether polyol diglycidyl ether, epoxy-containing silane coupling agent, amino silicone oil, and catecholamine to obtain a system containing groups such as ether bonds, hydroxyl groups, catechol groups, and polysiloxane segments. Through the interaction of various groups, a silicone coating with high hardness, good adhesion, and significant anticorrosion and antifouling effects is obtained. The polyether polyol diglycidyl ether, epoxy-containing silane coupling agent, and amino silicone oil of the present invention are used as basic components of the coating. If one or more of them are missing, the coating is difficult to form.

[0131] The functional groups such as ether bonds and hydroxyl groups contained in the organosilicon coating of the present invention can physically act or chemically react with groups or ions on the surface of inorganic or organic substrates, not only having good film-forming properties, but also achieving a firm bond with the surface of the substrate, especially the catechol groups in catecholamines, which can greatly improve the adhesion of the coating. In addition, the polysiloxane segments of amino silicone oil make the organosilicon protective coating have excellent anti-liquid adhesion properties. The coating is not only difficult to be attached by stains with high surface energy, but also can block the corrosion of corrosive substances to the substrate under the coating.

[0132] Organosiloxanes have the excellent properties of both inorganic and organic materials, and have the characteristics of good weather resistance, good corrosion resistance, low surface energy, and good chemical stability. Introducing a certain amount of organosiloxane components on the surface of a substrate such as a metal material can make its surface have certain hydrophobic properties and corrosion resistance.

[0133] The preparation method of the organosilicon coating of the present invention is simple, does not require high temperature and high pressure, has low equipment requirements, and is conducive to large-scale industrial production. The coating formed by the organosilicon coating of the present invention after coating and curing has good hardness, adhesion, hydrophobicity, antifouling and anti-corrosion properties, and can be used for surface protection of various materials, especially inorganic materials. The organosilicon coating and the organosilicon coating prepared therefrom have wide applications in the field of protection.

Claims

1. An organosilicon coating, characterized in that: The preparation method comprises the following raw materials in parts by weight: 0.2 to 12 parts of polyether polyol diglycidyl ether, 0.2 to 25 parts of epoxy-containing silane coupling agent, 0.2 to 25 parts of amino silicone oil and 0.05 to 12 parts of catecholamine.

2. The organosilicon coating according to claim 1, characterized in that: The polyether polyol diglycidyl ether comprises at least one of polyethylene glycol-polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether; and / or, the average molecular weight of the polyether polyol diglycidyl ether is 100 to 10000; And / or, the epoxy value of the polyether polyol diglycidyl ether is 0.01 to 1 mol / 100g.

3. The organosilicon coating according to claim 1, characterized in that: The epoxy-containing silane coupling agent includes at least one of 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane; and / or, the amino silicone oil is selected from an organosiloxane or a polymer thereof containing at least two primary or secondary amine groups; And / or, the average molecular weight of the amino silicone oil is 200 to 200,000.

4. The organosilicon coating according to claim 1, characterized in that: The catecholamine includes at least one of dopamine, dopamine hydrochloride, norepinephrine or epinephrine.

5. The organosilicon coating according to claim 1, characterized in that: Also includes solvents and / or catalysts; And / or, the mass parts of the solvent are 1 to 80 parts; And / or, the mass part of the catalyst is 0.001 to 7 parts; and / or, the solvent comprises at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, octanol, propylene glycol methyl ether acetate, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide or acetone; And / or, the catalyst includes at least one of an inorganic acid, an organic acid, an inorganic base or an organic base.

6. The method for preparing the organosilicon coating according to any one of claims 1 to 5, characterized in that: The following steps are involved: The prepared raw materials are mixed and reacted to obtain the organosilicon coating.

7. An organosilicon coating, characterized in that: The organic silicon coating is prepared from the organic silicon coating according to any one of claims 1 to 5.

8. A method for preparing an organosilicon coating, characterized in that: The following steps are involved: The organic silicon coating according to any one of claims 1 to 5 is applied on the surface of a substrate and cured to obtain the organic silicon coating.

9. Use of the organosilicon coating according to any one of claims 1 to 5 or the organosilicon coating according to claim 7 in the field of material protection.

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