Interface permeation super-hydrophobic wear-resistant coating as well as preparation method and application thereof

Abstract

The invention discloses an interface permeation super-hydrophobic wear-resistant coating as well as a preparation method and application thereof. According to the interface permeation super-hydrophobic wear-resistant coating, low-viscosity epoxy cluster resin is added in the preparation process, epoxy silicon clusters or epoxy titanium clusters are added into low-viscosity organic resin on the basis of a traditional resin system, and the viscosity of the traditional resin system is reduced while the density of functional groups is not changed; the permeation of the coating on a substrate is facilitated. And a silica-silica highly-crosslinked network in the coating enables the coating to have good mechanical properties, fluorocarbon chains on the surface of the coating give hydrophobic properties to the coating, and titanium clusters give ultraviolet resistance to the coating. The preparation method of the interface permeation super-hydrophobic wear-resistant coating disclosed by the invention has universality. The preparation method is applicable to a combined system of various porous substrates (such as concrete, wood and rusty steel plates), and is wide in applicability.

Description

Technical Field

[0001] The present invention relates to the technical field of functional coating materials, and particularly relates to an interfacial penetration superhydrophobic and wear-resistant coating, a preparation method thereof, and an application thereof. Background Art

[0002] Superhydrophobic coatings have important application values in fields such as self-cleaning and anti-icing. Existing technologies mainly construct micro-nano structures through sol-gel methods, chemical vapor deposition, etc., and reduce the surface energy through fluorosilane modification. However, traditional technologies face three contradictions: First, the hydrophobicity degree is negatively correlated with mechanical durability, and superhydrophobicity often brings a significant decrease in wear resistance; Second, although traditional low-surface-energy materials such as polytetrafluoroethylene (PTFE), siloxane, etc. can reduce the surface energy, due to the high rigidity and poor fluidity of the molecular chains, it is difficult to effectively penetrate into the microscopic pores of the substrate, and the interface between the functional layer and the matrix is weakly bonded, resulting in insufficient coating adhesion and easy peeling during long-term use; Third, for porous or rough substrates, traditional coating processes are prone to form surface accumulation due to the mismatch between the solution viscosity and surface tension, rather than achieving deep interfacial penetration, and the multi-step processing technology leads to a cost increase. Therefore, developing a superhydrophobic and wear-resistant functional coating that can form a strong interfacial bond with the substrate under normal temperature conditions and achieve micro-nano level pore penetration has become a key challenge for the engineering applicability of superhydrophobic coatings. Summary of the Invention

[0003] In order to overcome the problem that the superhydrophobicity, durability, and high permeability of superhydrophobic coatings in the prior art cannot be achieved simultaneously, the primary object of the present invention is to provide a preparation method for an interfacial penetration superhydrophobic and wear-resistant coating. This preparation method is simple to operate, low in cost, and applicable to a variety of substrates. The low-viscosity organic resin used in the preparation of the interfacial penetration superhydrophobic and wear-resistant coating can help the coating achieve the effect of interfacial penetration, which is beneficial for the organic components to penetrate into the interior of the substrate and consolidate, so that the coating adhesion can be greatly improved; the epoxy oligosiloxane resin with highly cross-linked siloxane provides excellent mechanical properties for the coating; in addition, the titanium alkane clusters with a large number of fluorocarbon chains on the coating surface give the coating the ability to resist ultraviolet rays, and at the same time, the action of the fluorocarbon chains gives the coating superhydrophobic ability.

[0004] The second object of the present invention is to provide an interfacial penetration superhydrophobic and wear-resistant coating prepared by the above preparation method.

[0005] The third object of the present invention is to provide an application of the above interfacial penetration superhydrophobic and wear-resistant coating.

[0006] The primary object of the present invention is achieved through the following technical solutions:

[0007] A preparation method for an interfacial penetration superhydrophobic and wear-resistant coating includes the following steps

[0008] (1) Preparation of low-viscosity epoxy silane clusters: Mix silane mixed solution I, deionized water, hydrochloric acid with a mass fraction of 36-38%, and anhydrous ethanol in a mass ratio of 100:(10-40):(1-1.5):150, stir, and remove the solvent by rotary evaporation to obtain low-viscosity epoxy silane clusters; the preparation method of the silane mixed solution I is as follows: Mix the mixed solution I and 3-glycidyloxypropyltrimethoxysilane in a mass ratio of (0.1-1):1 to obtain a silane mixed solution I;

[0009] (2) Preparation of fluorinated epoxy silane clusters: Mix silane mixture II, deionized water, hydrochloric acid with a mass fraction of 36-38%, and anhydrous ethanol in a mass ratio of 100:(10-40):(1-1.5):150, stir, and remove the solvent by rotary evaporation to obtain fluorinated epoxy silane clusters; the preparation method of the silane mixture II is as follows: Silane monomer, fluorinated silane monomer and 3-glycidyloxypropyltrimethoxysilane are fully mixed in a mass ratio of (0.1-1):(0.1-0.5):1 to obtain silane mixture 2 Silane mixture II;

[0010] (3) Preparation of fluorinated epoxy titanane clusters: Mix a titanane mixture, deionized water, hydrochloric acid with a mass fraction of 36-38%, and anhydrous ethanol in a mass ratio of 100:(10-40):(1-1.5):150, stir, and evaporate the solvent to obtain a fluorinated epoxy titanane cluster; The preparation method of the titanane mixture is as follows: titanate, fluorinated silane monomer and 3-glycidyloxypropyltrimethoxysilane are fully mixed in a mass ratio of (0.1-2):(0.1-1):2 to obtain a titanane mixture;

[0011] (4) Preparation of component A of the composite coating: 30 to 40 parts of low-viscosity epoxy silane clusters, 30 to 40 parts of fluorine-containing epoxy silane clusters, and 20 to 30 parts of fluorine-containing epoxy titanane clusters are mixed to obtain component A of the composite coating;

[0012] (5) Preparation of component B of the composite coating: any two of 4,4'-diaminocyclohexylmethane, polyetheramine D230, polyetheramine D400, and polyetheramine D2000 are mixed in a mass ratio of (1-2): (0.5-1) to obtain component B of the composite coating;

[0013] (6) Preparation of an interfacial penetrating super-hydrophobic wear-resistant coating: The composite coating A and the composite coating B components in steps (4) and (5) are mixed and dispersed at a mass ratio of (2 to 10):1 to obtain a composite coating, and the composite coating is sprayed on a porous substrate to cure the composite coating to obtain an interfacial penetrating super-hydrophobic wear-resistant coating.

[0014] Preferably, the mixture I in step (1) is a silane monomer mixture, which is formed by mixing at least two of tetramethyl silicate, tetraethyl silicate, methyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, and diphenyldiethoxysilane in any proportion.

[0015] Preferably, the silane monomer in step (2) is one of tetramethyl silicate, tetraethyl silicate, methyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, and diphenyldiethoxysilane.

[0016] Preferably, the titanate in step (3) is one of tetrabutyl titanate or tetraisopropyl titanate.

[0017] Preferably, the fluorosilane monomer in steps (2) and (3) is one of perfluorooctyltrimethoxysilane, perfluorooctyltriethoxysilane, and tridecafluorooctyltrimethoxysilane.

[0018] Preferably, the stirring temperature in steps (1), (2), and (3) is 60 - 80 °C, and the stirring reaction time is 6 - 12 h for each.

[0019] Preferably, the high - speed dispersion rate in step (6) is 500 - 1500 r / min, and the high - speed dispersion time is 10 - 60 min.

[0020] Preferably, the viscosity of the composite coating in step (6) does not exceed 100 mPa·s, the surface - drying time is not less than 6 h; the curing temperature of the composite coating is 25 - 60 °C.

[0021] Preferably, the porous substrate in step (6) is at least one of concrete, rusty steel plate, and wood.

[0022] The working principle of the present invention:

[0023] In the preparation process of the interfacial penetration super - hydrophobic and wear - resistant coating of the present invention, a low - viscosity epoxy cluster resin is added. The low - viscosity organic resin adds epoxy - group silicon clusters or epoxy - group titanium clusters on the basis of the traditional resin system, reduces the viscosity of the traditional resin system without changing the functional group density, and is beneficial to the penetration of the coating on the substrate. Moreover, the highly cross - linked silicon - oxygen - silicon network inside the coating endows the coating with good mechanical properties. At the same time, the fluorocarbon chains on the coating surface give the coating hydrophobic properties, and the titanium clusters give the coating anti - ultraviolet properties.

[0024] The second object of the present invention can be achieved by the following technical solutions:

[0025] An interfacial penetration superhydrophobic and wear-resistant coating is prepared by the above preparation method.

[0026] Preferably, the thickness of the interfacial penetration superhydrophobic and wear-resistant coating is 100-300 μm.

[0027] The third object of the present invention can be achieved by the following technical solutions:

[0028] An application of an interfacial penetration superhydrophobic and wear-resistant coating in the field of coating protection such as construction engineering and ocean engineering.

[0029] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0030] (1) Although traditional low surface energy materials (such as polytetrafluoroethylene (PTFE), siloxane, etc.) can reduce the surface energy, due to the high rigidity and poor fluidity of the molecular chains, it is difficult to effectively penetrate into the microscopic pores of the substrate, resulting in insufficient coating adhesion and easy peeling during long-term use. The interfacial penetration superhydrophobic and wear-resistant coating of the present invention uses an organosilicon resin with low viscosity and low surface energy, so that while the coating has high permeability, the organic components penetrate into the interior of the substrate and solidify, and the coating adhesion is greatly improved;

[0031] (2) For porous or rough substrates, traditional coating processes are difficult to achieve uniform penetration, and it is easy to form surface accumulation rather than interfacial penetration. The method for preparing the interfacial penetration superhydrophobic and wear-resistant coating of the present invention has universality. This method is applicable to a combination system of various porous substrates (such as concrete, wood, rusty steel plates);

[0032] (3) The prepared interfacial penetration superhydrophobic and wear-resistant coating of the present invention has excellent mechanical properties. The highly cross-linked resin system makes the coating have the advantages of high hardness, high compressive strength, and high wear resistance;

[0033] (4) The organic titanium clusters on the surface of the prepared interfacial penetration superhydrophobic and wear-resistant coating of the present invention not only have a certain anti-ultraviolet effect, but also the fluorocarbon chains and the micro-nano structure formed by the large and small clusters on the surface have a superhydrophobic effect. Description of the Drawings

[0034] Figure 1 It is a schematic diagram of the principle of the interfacial penetration superhydrophobic and wear-resistant coating described in Example 1;

[0035] Figure 2 It is a contact angle photograph of the interfacial penetration superhydrophobic and wear-resistant coating described in Example 1;

[0036] Figure 3 It is the durability test (tape peeling cycle) of the interfacial penetration superhydrophobic and wear-resistant coating described in Example 1;

[0037] Figure 4This is a durability test (sandpaper wear cycle) of the interfacial penetration superhydrophobic wear-resistant coating described in Example 1. DETAILED DESCRIPTION

[0038] The present invention is further described in detail below in conjunction with specific examples, but the embodiments of the present invention are not limited thereto. The materials used in the examples of the present invention can all be purchased commercially.

[0039] Example 1

[0040] A method for preparing an interfacial permeable super-hydrophobic wear-resistant coating comprises the following steps:

[0041] 1) Preparation of low-viscosity epoxy silane clusters: 1 part of tetramethyl silicate, 1 part of methyltrimethoxysilane, 2 parts of 3-glycidyloxypropyltrimethoxysilane, 0.4 parts of deionized water, 0.06 parts of hydrochloric acid, and 5 parts of anhydrous ethanol were fully mixed, stirred and reacted at 60° C. for 6 hours, and the solvent was removed by rotary evaporation to obtain low-viscosity epoxy silane clusters;

[0042] 2) Preparation of fluorinated epoxy silane clusters: 1 part of tetramethyl silicate, 0.2 parts of perfluorooctyl trimethoxy silane, 2 parts of 3-glycidyloxypropyl trimethoxy silane, 0.5 parts of deionized water, 0.06 parts of hydrochloric acid, and 5 parts of anhydrous ethanol were fully mixed, stirred and reacted at 60° C. for 6 h, and the solvent was removed by rotary evaporation to obtain fluorinated epoxy silane clusters;

[0043] 3) Preparation of fluorinated epoxy titanate clusters: 1 part of tetrabutyl titanate, 0.5 parts of tridecafluorooctyl trimethoxysilane, 2 parts of 3-glycidyloxypropyl trimethoxysilane, 0.4 parts of deionized water, 0.06 parts of hydrochloric acid, and 5 parts of anhydrous ethanol were fully mixed, stirred and reacted at 60° C. for 6 h, and the solvent was removed by rotary evaporation to obtain fluorinated epoxy titanate clusters;

[0044] 4) Preparation of composite coating: 1 part of low-viscosity epoxy silane cluster, 1 part of fluorinated epoxy silane cluster, and 0.5 part of fluorinated epoxy titanane cluster were mixed to obtain component A of composite coating; 1 part of polyetheramine D230 and 0.5 part of 4,4'-diaminocyclohexylmethane were mixed to obtain component B; 80 parts of component A and 20 parts of component B were stirred at a rate of 1500 r / min for 60 min using a high-speed disperser until uniform, to obtain composite coating;

[0045] 5) Preparation of interfacial penetrating super-hydrophobic wear-resistant coating: The composite coating was sprayed on a rusty steel plate, and the coating was cured in an oven at 30°C for 12 h to obtain an interfacial penetrating super-hydrophobic wear-resistant coating on the rusty steel plate.

[0046] The schematic diagram of the penetration process of the composite coating on the substrate in this embodiment is as follows Figure 1 The contact angle photo of the interfacial penetration super hydrophobic wear-resistant coating in this embodiment is shown inFigure 2 The durability test results of the interfacial penetration super hydrophobic wear-resistant coating described in this embodiment are shown in Figure 3 and Figure 4 Shown, including a tape stripping cycle and a sandpaper abrasion cycle.

[0047] Example 2

[0048] A method for preparing an interfacial permeable super-hydrophobic wear-resistant coating comprises the following steps:

[0049] 1) Preparation of low-viscosity epoxy silane clusters: 1 part of tetraethyl silicate, 1 part of methyltrimethoxysilane, 2 parts of 3-glycidyloxypropyltrimethoxysilane, 0.4 parts of deionized water, 0.06 parts of hydrochloric acid, and 5 parts of anhydrous ethanol were fully mixed, stirred and reacted at 60° C. for 6 h, and the solvent was removed by rotary evaporation to obtain low-viscosity epoxy silane clusters;

[0050] 2) Preparation of fluorinated epoxy silane clusters: 1 part of tetramethyl silicate, 0.2 parts of perfluorooctyl trimethoxy silane, 2 parts of 3-glycidyloxypropyl trimethoxy silane, 0.4 parts of deionized water, 0.06 parts of hydrochloric acid, and 5 parts of anhydrous ethanol were fully mixed, stirred and reacted at 60° C. for 6 h, and the solvent was removed by rotary evaporation to obtain fluorinated epoxy silane clusters;

[0051] 3) Preparation of fluorinated epoxy titanate clusters: 1 part of tetrabutyl titanate, 0.5 parts of tridecafluorooctyl trimethoxysilane, 2 parts of 3-glycidyloxypropyl trimethoxysilane, 0.4 parts of deionized water, 0.06 parts of hydrochloric acid, and 5 parts of anhydrous ethanol were fully mixed, stirred and reacted at 60° C. for 6 h, and the solvent was removed by rotary evaporation to obtain fluorinated epoxy titanate clusters;

[0052] 4) Preparation of composite coating: 1 part of low-viscosity epoxy silane cluster, 1 part of fluorinated epoxy silane cluster, and 0.5 part of fluorinated epoxy titanane cluster were mixed to obtain component A of composite coating; 1 part of polyetheramine D230 and 0.5 part of 4,4'-diaminocyclohexylmethane were mixed to obtain component B; 83 parts of component A and 17 parts of component B were stirred at a rate of 1500 r / min for 60 min using a high-speed disperser until uniform, to obtain composite coating;

[0053] 5) Preparation of interfacial penetrating super-hydrophobic wear-resistant coating: The composite coating was sprayed on a rusty steel plate, and the coating was cured in an oven at 30°C for 12 h to obtain an interfacial penetrating super-hydrophobic wear-resistant coating on the rusty steel plate.

[0054] Example 3

[0055] A method for preparing an interfacial permeable super-hydrophobic wear-resistant coating comprises the following steps:

[0056] 1) Preparation of low-viscosity epoxy silane clusters: Mix 1 part of tetramethyl orthosilicate, 1 part of ethyltrimethoxysilane, 2 parts of 3-glycidoxypropyltrimethoxysilane, 0.4 part of deionized water, 0.06 part of hydrochloric acid, and 5 parts of absolute ethanol thoroughly. Stir and react at 60 °C for 6 h, and then remove the solvent by rotary evaporation to obtain low-viscosity epoxy silane clusters;

[0057] 2) Preparation of fluorinated epoxy silane clusters: Mix 1 part of tetramethyl orthosilicate, 0.2 part of perfluorooctyltriethoxysilane, 2 parts of 3-glycidoxypropyltrimethoxysilane, 0.5 part of deionized water, 0.06 part of hydrochloric acid, and 5 parts of absolute ethanol thoroughly. Stir and react at 60 °C for 6 h, and then remove the solvent by rotary evaporation to obtain fluorinated epoxy silane clusters;

[0058] 3) Preparation of fluorinated epoxy titanate clusters: Mix 1 part of titanium tetraisopropoxide, 0.5 part of tridecafluorooctyltrimethoxysilane, 2 parts of 3-glycidoxypropyltrimethoxysilane, 0.4 part of deionized water, 0.06 part of hydrochloric acid, and 5 parts of absolute ethanol thoroughly. Stir and react at 60 °C for 6 h, and then remove the solvent by rotary evaporation to obtain fluorinated epoxy titanate clusters;

[0059] 4) Preparation of the composite coating: Mix 1 part of low-viscosity epoxy silane clusters, 1 part of fluorinated epoxy silane clusters, and 0.5 part of fluorinated epoxy titanate clusters to obtain Component A of the composite coating; Mix 1 part of polyetheramine D400 and 0.5 part of 4,4'-diaminocyclohexylmethane to obtain Component B; Stir 90 parts of Component A and 10 parts of Component B at a rate of 1500 r / min for 60 min using a high-speed disperser until uniform to obtain the composite coating;

[0060] 5) Preparation of the interfacially penetrating superhydrophobic and wear-resistant coating: Spray the composite coating on the concrete, and cure the coating in an oven at 30 °C for 12 h to obtain the interfacially penetrating superhydrophobic and wear-resistant coating on the concrete.

[0061] Example 4

[0062] A method for preparing an interfacially penetrating superhydrophobic and wear-resistant coating, comprising the following steps,

[0063] 1) Preparation of low-viscosity epoxy silane clusters: Mix 1 part of tetramethyl orthosilicate, 1 part of ethyltrimethoxysilane, 2 parts of 3-glycidoxypropyltrimethoxysilane, 0.4 part of deionized water, 0.06 part of hydrochloric acid, and 5 parts of absolute ethanol thoroughly. Stir and react at 60 °C for 6 h, and then remove the solvent by rotary evaporation to obtain low-viscosity epoxy silane clusters;

[0064] 2) Preparation of fluorinated epoxy silane clusters: Mix 1 part of tetraethyl orthosilicate, 0.2 part of perfluorooctyltriethoxysilane, 2 parts of 3-glycidoxypropyltrimethoxysilane, 0.5 part of deionized water, 0.06 part of hydrochloric acid, and 5 parts of absolute ethanol thoroughly. Stir and react at 60 °C for 6 h, and then remove the solvent by rotary evaporation to obtain fluorinated epoxy silane clusters;

[0065] 3) Preparation of fluorinated epoxy titanate clusters: Mix 1 part of titanium tetraisopropoxide, 0.4 part of perfluorooctyltriethoxysilane, 2 parts of 3-glycidoxypropyltrimethoxysilane, 0.4 part of deionized water, 0.06 part of hydrochloric acid, and 5 parts of absolute ethanol thoroughly. Stir and react at 60 °C for 6 h, and then remove the solvent by rotary evaporation to obtain fluorinated epoxy titanate clusters;

[0066] 4) Preparation of composite coating: Mix 1 part of low-viscosity epoxy silane clusters, 1 part of fluorinated epoxy silane clusters, and 0.5 part of fluorinated epoxy titanate clusters to obtain Component A of the composite coating; Mix 1 part of polyetheramine D400 and 0.5 part of 4,4'-diaminocyclohexylmethane to obtain Component B; Stir 75 parts of Component A and 25 parts of Component B at a rate of 1500 r / min for 60 min using a high-speed disperser until homogeneous to obtain the composite coating;

[0067] 5) Preparation of interfacial penetration superhydrophobic and wear-resistant coating: Spray the composite coating on the rusty steel plate, and cure the coating in an oven at 30 °C for 12 h to obtain an interfacial penetration superhydrophobic and wear-resistant coating on the rusty steel plate.

[0068] Example 5

[0069] A preparation method of an interfacial penetration superhydrophobic and wear-resistant coating includes the following steps:

[0070] 1) Preparation of low-viscosity epoxy silane clusters: Mix 1 part of tetramethyl orthosilicate, 1 part of dimethyldiethoxysilane, 2 parts of 3-glycidoxypropyltrimethoxysilane, 0.4 part of deionized water, 0.06 part of hydrochloric acid, and 5 parts of absolute ethanol thoroughly. Stir and react at 60 °C for 6 h, and then remove the solvent by rotary evaporation to obtain low-viscosity epoxy silane clusters;

[0071] 2) Preparation of fluorinated epoxy silane clusters: Mix 1 part of phenyltriethoxysilane, 0.2 part of tridecafluorooctyltrimethoxysilane, 2 parts of 3-glycidoxypropyltrimethoxysilane, 0.5 part of deionized water, 0.06 part of hydrochloric acid, and 5 parts of absolute ethanol thoroughly. Stir and react at 60 °C for 6 h, and then remove the solvent by rotary evaporation to obtain fluorinated epoxy silane clusters;

[0072] 3) Preparation of fluorinated epoxy titanate clusters: 1 part of tetra-isopropyl titanate, 0.5 part of tridecafluorooctyltrimethoxysilane, 2 parts of 3-glycidoxypropyltrimethoxysilane, 0.4 part of deionized water, 0.06 part of hydrochloric acid, and 5 parts of absolute ethanol were thoroughly mixed and stirred at 60 °C for 6 h. The solvent was removed by rotary evaporation to obtain fluorinated epoxy titanate clusters;

[0073] 4) Preparation of the composite coating: 1 part of low-viscosity epoxy silane clusters, 1 part of fluorinated epoxy silane clusters, and 0.5 part of fluorinated epoxy titanate clusters were mixed to obtain component A of the composite coating; 1 part of polyetheramine D230 and 0.5 part of 4,4'-diaminocyclohexylmethane were mixed to obtain component B; 88 parts of component A and 12 parts of component B were stirred at a rate of 1500 r / min for 60 min using a high-speed disperser until homogeneous to obtain the composite coating;

[0074] 5) Preparation of the interfacial penetration superhydrophobic and wear-resistant coating: The composite coating was sprayed on the concrete, and the coating was cured in an oven at 30 °C for 12 h to obtain an interfacial penetration superhydrophobic and wear-resistant coating on the concrete.

[0075] Example 6

[0076] A preparation method of an interfacial penetration superhydrophobic and wear-resistant coating, comprising the following steps

[0077] 1) Preparation of low-viscosity epoxy silane clusters: 1 part of tetraethyl orthosilicate, 1 part of ethyltriethoxysilane, 2 parts of 3-glycidoxypropyltrimethoxysilane, 0.4 part of deionized water, 0.06 part of hydrochloric acid, and 5 parts of absolute ethanol were thoroughly mixed and stirred at 60 °C for 6 h. The solvent was removed by rotary evaporation to obtain low-viscosity epoxy silane clusters;

[0078] 2) Preparation of fluorinated epoxy silane clusters: 1 part of ethyltriethoxysilane, 0.2 part of perfluorooctyltriethoxysilane, 2 parts of 3-glycidoxypropyltrimethoxysilane, 0.5 part of deionized water, 0.06 part of hydrochloric acid, and 5 parts of absolute ethanol were thoroughly mixed and stirred at 60 °C for 6 h. The solvent was removed by rotary evaporation to obtain fluorinated epoxy silane clusters;

[0079] 3) Preparation of fluorinated epoxy titanate clusters: 1 part of tetra-isopropyl titanate, 0.5 part of tridecafluorooctyltrimethoxysilane, 2 parts of 3-glycidoxypropyltrimethoxysilane, 0.4 part of deionized water, 0.05 part of hydrochloric acid, and 5 parts of absolute ethanol were thoroughly mixed and stirred at 60 °C for 6 h. The solvent was removed by rotary evaporation to obtain fluorinated epoxy titanate clusters;

[0080] 4) Preparation of composite coating: 1 part of low-viscosity epoxy silane cluster, 1 part of fluorinated epoxy silane cluster, and 0.5 part of fluorinated epoxy titanane cluster were mixed to obtain component A of composite coating; 1 part of polyetheramine D2000 and 0.5 part of 4,4'-diaminocyclohexylmethane were mixed to obtain component B; 80 parts of component A and 20 parts of component B were stirred at a rate of 1500 r / min for 60 min using a high-speed disperser until uniform, to obtain composite coating;

[0081] 5) Preparation of interfacial penetrating super-hydrophobic wear-resistant coating: The composite coating is sprayed on the wood, and the coating is cured in an oven at 30°C for 12 hours to obtain an interfacial penetrating super-hydrophobic wear-resistant coating on the wood.

[0082] Example 7

[0083] A method for preparing an interfacial permeable super-hydrophobic wear-resistant coating comprises the following steps:

[0084] 1) Preparation of low-viscosity epoxy silane clusters: 1 part of tetramethyl silicate, 1 part of ethyltriethoxysilane, 2 parts of 3-glycidyloxypropyltrimethoxysilane, 0.4 parts of deionized water, 0.06 parts of hydrochloric acid, and 5 parts of anhydrous ethanol were fully mixed, stirred and reacted at 60° C. for 6 hours, and the solvent was removed by rotary evaporation to obtain low-viscosity epoxy silane clusters;

[0085] 2) Preparation of fluorinated epoxy silane clusters: 1 part of tetramethyl silicate, 0.2 parts of perfluorooctyl triethoxysilane, 2 parts of 3-glycidyloxypropyl trimethoxysilane, 0.5 parts of deionized water, 0.06 parts of hydrochloric acid, and 5 parts of anhydrous ethanol were fully mixed, stirred and reacted at 60° C. for 6 h, and the solvent was removed by rotary evaporation to obtain fluorinated epoxy silane clusters;

[0086] 3) Preparation of fluorinated epoxy titanate clusters: 1 part of tetraisopropyl titanate, 0.5 part of tridecafluorooctyl trimethoxysilane, 2 parts of 3-glycidyloxypropyl trimethoxysilane, 0.4 part of deionized water, 0.06 part of hydrochloric acid, and 5 parts of anhydrous ethanol were fully mixed, stirred and reacted at 60° C. for 6 h, and the solvent was removed by rotary evaporation to obtain fluorinated epoxy titanate clusters;

[0087] 4) Preparation of composite coating: 1 part of low-viscosity epoxy silane cluster, 1 part of fluorinated epoxy silane cluster, and 0.5 part of fluorinated epoxy titanane cluster were mixed to obtain component A of composite coating; 1 part of polyetheramine D2000 and 0.5 part of polyetheramine D230 were mixed to obtain component B; 90 parts of component A and 10 parts of component B were stirred at a rate of 1500 r / min for 60 min using a high-speed disperser until uniform, to obtain composite coating;

[0088] 5) Preparation of interfacial penetrating super-hydrophobic wear-resistant coating: The composite coating is sprayed on the wood, and the coating is cured in an oven at 30°C for 12 hours to obtain an interfacial penetrating super-hydrophobic wear-resistant coating on the wood.

[0089] Example 8

[0090] A method for preparing an interfacial permeable super-hydrophobic wear-resistant coating comprises the following steps:

[0091] 1) Preparation of low-viscosity epoxy silane clusters: 1 part of tetramethyl silicate, 1 part of diphenyldiethoxysilane, 2 parts of 3-glycidyloxypropyltrimethoxysilane, 0.4 parts of deionized water, 0.06 parts of hydrochloric acid, and 5 parts of anhydrous ethanol were fully mixed, stirred and reacted at 60° C. for 6 hours, and the solvent was removed by rotary evaporation to obtain low-viscosity epoxy silane clusters;

[0092] 2) Preparation of fluorinated epoxy silane clusters: 1 part of tetramethyl silicate, 0.2 parts of perfluorooctyl triethoxysilane, 2 parts of 3-glycidyloxypropyl trimethoxysilane, 0.5 parts of deionized water, 0.06 parts of hydrochloric acid, and 5 parts of anhydrous ethanol were fully mixed, stirred and reacted at 60° C. for 6 h, and the solvent was removed by rotary evaporation to obtain fluorinated epoxy silane clusters;

[0093] 3) Preparation of fluorinated epoxy titanate clusters: 1 part of tetrabutyl titanate, 0.5 parts of tridecafluorooctyl trimethoxysilane, 2 parts of 3-glycidyloxypropyl trimethoxysilane, 0.4 parts of deionized water, 0.06 parts of hydrochloric acid, and 5 parts of anhydrous ethanol were fully mixed, stirred and reacted at 60° C. for 6 h, and the solvent was removed by rotary evaporation to obtain fluorinated epoxy titanate clusters;

[0094] 4) Preparation of composite coating: 1 part of low-viscosity epoxy silane cluster, 1 part of fluorinated epoxy silane cluster, and 0.5 part of fluorinated epoxy titanane cluster were mixed to obtain component A of composite coating; 1 part of polyetheramine D2000 and 0.5 part of polyetheramine D400 were mixed to obtain component B; 75 parts of component A and 25 parts of component B were stirred at a rate of 1500 r / min for 60 min using a high-speed disperser until uniform, to obtain composite coating;

[0095] 5) Preparation of interfacial penetrating super-hydrophobic wear-resistant coating: The composite coating is sprayed on the wood, and the coating is cured in an oven at 30°C for 12 hours to obtain an interfacial penetrating super-hydrophobic wear-resistant coating on the wood.

[0096] Comparative Example 1

[0097] A method for preparing a super hydrophobic wear-resistant coating comprises the following steps:

[0098] 1) Preparation of fluorinated epoxy titanate clusters: 1 part of tetrabutyl titanate, 0.5 part of tridecafluorooctyl trimethoxysilane, 2 parts of 3-glycidyloxypropyl trimethoxysilane, 0.4 part of deionized water, 0.06 part of hydrochloric acid, and 5 parts of anhydrous ethanol were fully mixed, stirred and reacted at 60° C. for 6 h, and the solvent was removed by rotary evaporation to obtain fluorinated epoxy titanate clusters;

[0099] 2) Preparation of interfacial penetration super-hydrophobic wear-resistant coating: 2 parts of bisphenol A epoxy resin E44 resin and 0.5 parts of fluorinated epoxy titanane clusters are mixed to obtain component A of the composite coating; 1 part of polyetheramine D2000 and 0.5 parts of polyetheramine D400 are mixed to obtain component B; 75 parts of component A and 25 parts of component B are stirred at a rate of 1500 r / min for 60 minutes using a high-speed disperser until uniform to obtain a composite coating, the composite coating is sprayed on concrete, the coating is cured in an oven at 30°C for 12 hours, and a super-hydrophobic wear-resistant coating is obtained on the concrete.

[0100] Due to the high viscosity of epoxy resin, the initial system viscosity is large, the penetration effect into concrete is poor, the adhesion of the coating is weak, and the linear structure of bisphenol A epoxy resin makes the mechanical properties of the coating weak.

[0101] Comparative Example 2

[0102] A method for preparing a super hydrophobic wear-resistant coating comprises the following steps:

[0103] 1) Preparation of low-viscosity epoxy silane clusters: 1 part of tetramethyl silicate, 1 part of diphenyldiethoxysilane, 2 parts of 3-glycidyloxypropyltrimethoxysilane, 0.4 parts of deionized water, 0.06 parts of hydrochloric acid, and 5 parts of anhydrous ethanol were fully mixed, stirred and reacted at 60° C. for 6 hours, and the solvent was removed by rotary evaporation to obtain low-viscosity epoxy silane clusters;

[0104] 2) Preparation of fluorinated nano-silica: 3 parts of nano-silica were dispersed in 50 parts of anhydrous ethanol, 1.5 parts of PFTS, 0.5 parts of deionized water and 0.2 parts of HCl were added, and the mixture was stirred at 60°C for 24 hours. The product was then filtered, washed and dried to obtain fluorinated nano-silica.

[0105] 3) Preparation of interfacial penetration super-hydrophobic wear-resistant coating: 2 parts are used as component A of the composite coating; 1 part of polyetheramine D2000 and 0.5 parts of polyetheramine D400 are mixed to obtain component B; 75 parts of component A and 25 parts of component B are stirred at a rate of 1500 r / min for 60 min using a high-speed disperser until uniform to obtain a composite coating, the composite coating is sprayed on the concrete, and then fluorinated nano-silica is dispersed in acetone and sprayed on the coating to form a composite coating, and the composite coating is cured in an oven at 30°C for 12 h to obtain a super-hydrophobic wear-resistant coating on the concrete.

[0106] Due to the lack of chemical bonding between fluorinated nano-silica and the coating, it does not adhere firmly to the coating and falls off severely during repeated wear, causing the coating to quickly lose its super-hydrophobicity and be difficult to use for a long time.

[0107] The performance of the super hydrophobic wear-resistant coatings prepared in Examples 1 to 8 and Comparative Examples 1 to 2 was tested under the following test conditions:

[0108] (1) Test at 25 °C using an NDJ-5S rotational viscometer.

[0109] (2) At 25 °C, cut the substrate coated with the coating and measure the penetration depth from the cross-section.

[0110] (3) Refer to GB / T 5210-2006.

[0111] (4) At 25 °C, use a Theta Auto 113 contact angle tester to drop 4 μL of deionized water on the surface of the coated glass slide, and observe and record the contact angle.

[0112] (5) At 25 °C, place the substrate with the coated side facing down on 1000-mesh sandpaper, place a 100 g weight on the back, and push the substrate back and forth on the sandpaper. Each 100 cm movement is recorded as one wear cycle and 100 wear cycles are carried out. Use a Theta Auto 113 contact angle tester to drop 4 μL of deionized water on the surface of the coated glass slide, and observe and record the contact angle.

[0113] Table 1 below shows the performance test diagrams of the superhydrophobic and wear-resistant coatings prepared in Examples 1 to 8 and Comparative Examples 1 to 2.

[0114] Table 1

[0115]

[0116] As can be seen from the above Examples 1 to 8 and Comparative Examples 1 to 2, the viscosity of the composite coatings prepared in Examples 1 to 8 of the present invention does not exceed 100 mPa·s. The low-viscosity epoxy-silica cluster resin can fully penetrate the porous substrate, and the penetration depth is 2 - 4 mm. The composite coating prepared in Comparative Example 1 has a high viscosity and poor penetration on the porous substrate. In Comparative Example 2, the superhydrophobic fluorinated nano-silica layer of the composite coating quickly falls off during wear, the contact angle of the coating decreases rapidly, and the superhydrophobic ability is quickly lost. The contact angles of the interfacial penetration superhydrophobic and wear-resistant coatings prepared in Examples 1 to 8 are all greater than 150° and still greater than 150° after 100 sandpaper wear cycles, and the adhesion is greater than 5 MPa, which are all superior to Comparative Example 1 and Comparative Example 2.

[0117] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and are all included in the protection scope of the present invention.

Claims

1. A method for preparing an interfacial penetration super-hydrophobic wear-resistant coating, characterized in that: The following steps are included: (1) Preparation of low-viscosity epoxy silane clusters: Mix silane mixed solution I, deionized water, hydrochloric acid with a mass fraction of 36-38%, and anhydrous ethanol in a mass ratio of 100:(10-40):(1-1.5):150, stir, and remove the solvent by rotary evaporation to obtain low-viscosity epoxy silane clusters; the preparation method of the silane mixed solution I is as follows: Mix the mixed solution I and 3-glycidyloxypropyltrimethoxysilane in a mass ratio of (0.1-1):1 to obtain a silane mixed solution I; (2) Preparation of fluorinated epoxy silane clusters: Mix silane mixture II, deionized water, hydrochloric acid with a mass fraction of 36-38%, and anhydrous ethanol in a mass ratio of 100:(10-40):(1-1.5):150, stir, and remove the solvent by rotary evaporation to obtain fluorinated epoxy silane clusters; the preparation method of the silane mixture II is as follows: Silane monomer, fluorinated silane monomer and 3-glycidyloxypropyltrimethoxysilane are fully mixed in a mass ratio of (0.1-1):(0.1-0.5):1 to obtain silane mixture 2 Silane mixture II; (3) Preparation of fluorinated epoxy titanane clusters: Mix a titanane mixture, deionized water, hydrochloric acid with a mass fraction of 36-38%, and anhydrous ethanol in a mass ratio of 100:(10-40):(1-1.5):150, stir, and evaporate the solvent to obtain a fluorinated epoxy titanane cluster; The preparation method of the titanane mixture is as follows: titanate, fluorinated silane monomer and 3-glycidyloxypropyltrimethoxysilane are fully mixed in a mass ratio of (0.1-2):(0.1-1):2 to obtain a titanane mixture; (4) Preparation of component A of the composite coating: 30 to 40 parts of low-viscosity epoxy silane clusters, 30 to 40 parts of fluorine-containing epoxy silane clusters, and 20 to 30 parts of fluorine-containing epoxy titanane clusters are mixed to obtain component A of the composite coating; (5) Preparation of component B of the composite coating: any two of 4,4'-diaminocyclohexylmethane, polyetheramine D230, polyetheramine D400, and polyetheramine D2000 are mixed in a mass ratio of (1-2): (0.5-1) to obtain component B of the composite coating; (6) Preparation of an interfacial penetrating super-hydrophobic wear-resistant coating: The composite coating A and the composite coating B components in steps (4) and (5) are mixed and dispersed at a mass ratio of (2 to 10):1 to obtain a composite coating, and the composite coating is sprayed on a porous substrate to cure the composite coating to obtain an interfacial penetrating super-hydrophobic wear-resistant coating.

2. The method for preparing the interfacial penetration super-hydrophobic wear-resistant coating according to claim 1, wherein: The mixed solution I in step (1) is a silane monomer mixed solution, which is formed by mixing at least two of tetramethyl silicate, tetraethyl silicate, methyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, and diphenyldiethoxysilane in any proportion.

3. The method for preparing the interfacial penetration super-hydrophobic wear-resistant coating according to claim 1, characterized in that: The silane monomer in step (2) is one of tetramethyl silicate, tetraethyl silicate, methyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane and diphenyldiethoxysilane.

4. The method for preparing the interfacial penetration super-hydrophobic wear-resistant coating according to claim 1, characterized in that: The titanate in step (3) is one of tetrabutyl titanate or tetraisopropyl titanate.

5. The method for preparing the interfacial penetration super-hydrophobic wear-resistant coating according to claim 1, characterized in that: The fluorine-containing silane monomer in step (2) and step (3) is one of perfluorooctyltrimethoxysilane, perfluorooctyltriethoxysilane and tridecafluorooctyltrimethoxysilane.

6. The method for preparing the interfacial penetration super-hydrophobic wear-resistant coating according to claim 1, characterized in that: The viscosity of the composite coating in step (6) is no more than 100 mPa·s, and the surface drying time is no less than 6 hours; the curing temperature of the composite coating is 25 to 60°C.

7. The method for preparing the interfacial penetration super-hydrophobic wear-resistant coating according to claim 1, characterized in that: The porous substrate in step (6) is at least one of concrete, rusted steel plate, and wood.

8. An interfacial penetration super hydrophobic wear-resistant coating, characterized in that: Prepared according to the preparation method according to any one of claims 1 to 7.

9. The interfacial penetration super hydrophobic wear-resistant coating according to claim 8, characterized in that: The thickness of the interfacial penetration super-hydrophobic wear-resistant coating is 100-300 μm.

10. Application of the interfacial penetration super-hydrophobic wear-resistant coating according to claim 8 or 9 in the field of coating protection of construction engineering and marine engineering.

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