A highly hydrophobic, wear-resistant, heavy-duty anti-corrosion coating material and its preparation method and application

Abstract

The present invention provides a highly hydrophobic, wear-resistant, heavy-duty anti-corrosion coating material, and its preparation method and application. The raw materials of the coating material include a first component and a second component, wherein the first component is an epoxy component, and the second component includes a VST modified resin; its preparation method includes mixing epoxy resin, graphene dispersion, additives, pigments and fillers, and solvents to obtain a first component, first mixing vinyl perfluorooctanoate with silanol epoxy silicone oil to carry out a silanol addition reaction, and then mixing with triethylenetetramine to carry out an addition reaction to generate a VST modified resin to obtain a second component; the first component and the second component are evenly mixed in proportion to obtain the coating material. The coating material provided by the present invention has high hydrophobicity, high wear resistance and high environmental resistance, and has an excellent protective effect on steel substrates; in addition, the preparation method provided by the present invention is simple, the conditions are mild, and it is easy to promote.

Description

Technical Field

[0001] The present application belongs to the technical field of anti-corrosion coating materials, and specifically relates to a highly hydrophobic, wear-resistant, heavy-duty anti-corrosion coating material, a preparation method thereof, and an application thereof. Background Art

[0002] In my country's infrastructure sector, the corrosion of steel substrates is mostly based on the principle of galvanic corrosion. The galvanic corrosion process usually requires three basic conditions: electrolyte water, oxygen, and potential difference. Among them, the shielding of electrolyte water has always been a focus of heavy-duty anti-corrosion coating materials and is one of the factors that most easily reflect the anti-corrosion performance of heavy-duty anti-corrosion coating materials. In the past, the way heavy-duty anti-corrosion coating materials shielded water vapor was simply to use flaky fillers to form a "maze effect" to extend the permeation path of water vapor. The hydrophobic properties of the film-forming material itself were not paid attention to. Therefore, the water vapor shielding effect was generally poor. After long-term immersion in electrolyte water or chemical media, the paint film is prone to blistering or falling off and becoming ineffective. In addition, the wear resistance of the paint film is generally poor. In natural environments, the coating film is easily worn, causing the surface to gradually become rough, forming a hydrophilic interface, and further reducing the water vapor shielding effect of the coating film. For the above reasons, there is an urgent need to develop a high-performance hydrophobic and wear-resistant heavy-duty anti-corrosion coating material to solve this problem. Summary of the Invention

[0003] The main purpose of the present invention is to provide a highly hydrophobic, wear-resistant, heavy-duty anti-corrosion coating material and its preparation method and application to overcome the shortcomings of the prior art.

[0004] In order to achieve the above technical objectives, the present invention adopts the following technical solutions:

[0005] First, the present invention provides a highly hydrophobic, wear-resistant, and heavy-duty anti-corrosion coating material, the raw materials of which include a first component and a second component.

[0006] Furthermore, the first component is an epoxy component, and the second component includes a VST modified resin.

[0007] Furthermore, the VST modified resin is a VST modified amine resin prepared by a silylation reaction between vinyl perfluorooctanoate and silyl epoxy silicone oil, and then an addition reaction with triethylenetetramine.

[0008] Secondly, the present invention also provides a preparation method of the highly hydrophobic, wear-resistant and heavy-duty anti-corrosion coating material, which includes: uniformly mixing epoxy resin, graphene dispersion, pigment filler, additive, and solvent to form a mixture, and adjusting the viscosity of the mixture to 100-120KU with a solvent to obtain a first component.

[0009] Vinyl perfluorooctanoate and silanol epoxy silicone oil are mixed to obtain a fluorine prepolymer containing epoxy groups, and the fluorine prepolymer is mixed with triethylenetetramine to react to obtain a second component;

[0010] The first component and the second component are uniformly mixed to prepare the highly hydrophobic, wear-resistant and heavy-duty anti-corrosion coating material.

[0011] Another aspect of the present invention also provides the use of the highly hydrophobic, wear-resistant, heavy-duty anti-corrosion coating material in the corrosion protection of steel substrates.

[0012] Compared with the prior art, the present invention has the following beneficial effects:

[0013] 1. The highly hydrophobic, wear-resistant and heavy-duty anti-corrosion coating material provided by the present invention has excellent hydrophobicity, wear resistance and environmental resistance, can effectively alleviate the corrosion of the steel substrate, and play a good protective role on the steel substrate.

[0014] 2. The preparation method provided by the present invention is simple, the reaction conditions are mild, and it is easy to promote. DETAILED DESCRIPTION

[0015] Detailed embodiments of the present invention are disclosed herein; however, it should be understood that the disclosed embodiments are merely exemplary of the present invention, which can be embodied in various forms. Therefore, the specific functional details disclosed herein should not be construed as limiting, but rather as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed embodiment.

[0016] In view of the defects of the prior art, the inventors of this case have proposed the technical solution of the present invention after long-term research and extensive practice. The technical solution of the present invention will be clearly and completely described below. It is mainly a highly hydrophobic, wear-resistant and heavy-duty anti-corrosion coating material and its preparation method and application.

[0017] The first aspect of the present invention provides a highly hydrophobic, wear-resistant, heavy-duty corrosion-resistant coating material, the raw materials of which include a first component and a second component, the first component being an epoxy component, and the second component comprising a VST-modified resin; the VST-modified resin is a VST-modified amine resin prepared by a silylation reaction of vinyl perfluorooctanoate with a silyl-epoxy silicone oil, followed by an addition reaction with triethylenetetramine.

[0018] Furthermore, the second component is a VST-modified resin produced by reacting vinyl perfluorooctanoate with a hydrosilyl epoxy silicone oil at a molar ratio of 1:1.05-1.10 to form a fluorinated prepolymer with epoxy groups, which is then reacted with triethylenetetramine at a molar ratio of 2:1.1-1.2. In some specific embodiments, the mass ratio of the first component to the second component is 1-1.2:1.

[0019] In some specific embodiments, the weight average molecular weight of the VST modified resin is 1390-1420, and the VST modified resin has 4 secondary amine groups.

[0020] Furthermore, the active hydrogen equivalent of the VST modified resin is 347.5-355.

[0021] Furthermore, the second component includes the following components calculated in parts by weight: 100 parts of VST modified resin solution.

[0022] In some specific embodiments, the active hydrogen equivalent of the VST modified resin solution at a concentration of 50% is 695-710, and the soluble fluorine content is 40-41 wt %.

[0023] Furthermore, the second component is a VST-modified amine resin solution, which is prepared by a silylation reaction of vinyl perfluorooctanoate (VDFEA) with a weight-average molecular weight of 430-450 and a silyl-epoxy silicone oil (SHPEG) with a weight-average molecular weight of 190-210 at a molar ratio of 1:1.05-1.10 to generate a fluorine-containing prepolymer (VDFEA-SHPEG) with an epoxy group, which is then reacted with triethylenetetramine (TETA) at a molar ratio of 2:1.10-1.20 to generate a VST-modified amine resin with four secondary amino groups and a molecular weight range of 1390-1420.

[0024] In one embodiment, the weight-average molecular weight of the vinyl perfluorooctanoate (VDFEA) is 430-450. This resin has a high fluorine content and contains vinyl groups, making it suitable for addition reaction grafting of other functional groups. The high fluorine content can give the product higher hydrophobicity and wear resistance. In one embodiment, the weight-average molecular weight of the silanol-epoxy silicone oil (SHPEG) is 190-210, and the molecule contains one epoxy group and one silanol group. The silanol group can undergo a silanol hydroaddition reaction with the vinyl group, thereby grafting vinyl perfluorooctanoate onto the molecule to form a high-fluorine-containing prepolymer (VDFEA-SHPEG) containing epoxy groups.

[0025] In one embodiment, triethylenetetramine (TETA) has a weight-average molecular weight of 140-150 and an active hydrogen equivalent of 24-25. Its molecule contains four primary and two secondary amines, allowing it to further react with VDFEA-SHPEG, consuming the primary amines and generating a VST-modified amine resin with four secondary amine groups and a molecular weight ranging from 1390 to 1420. This resin, when reacting with the first component, provides four crosslinking points, resulting in a denser coating with improved media resistance. Furthermore, the resin's fluorine content, which can reach 40-41% by weight, imparts excellent hydrophobicity and wear resistance to the coating.

[0026] In some specific embodiments, the first component includes the following components: epoxy resin, graphene dispersion, additives, pigments and fillers, and solvents.

[0027] In some more preferred embodiments, the first component includes the following components calculated in parts by mass: 20-30 parts of epoxy resin, 1-1.5 parts of graphene dispersion, 2-3 parts of additives, 45-55 parts of pigments and fillers, and 10-20 parts of solvents.

[0028] In some preferred embodiments, the epoxy resin has an epoxy equivalent weight of 184-190 and contains 1-2 epoxy functional groups.

[0029] Furthermore, the weight average molecular weight of the epoxy resin is 368-380.

[0030] In some preferred embodiments, the specific surface area of the graphene dispersion is ≥500m 2 / g, the graphene carbon content in the dispersion is ≥98%, the number of layers is ≤10, and the oxygen content is ≤0.5%.

[0031] Furthermore, the graphene dispersion may include graphene and xylene.

[0032] In some preferred embodiments, the auxiliary agent includes any one or more combinations of defoaming agents, leveling agents, and rheological additives, but is not limited thereto.

[0033] In some preferred embodiments, the pigments and fillers include any one or more combinations of titanium dioxide, black iron oxide, red iron oxide, talc, and silica powder, but are not limited thereto.

[0034] In some preferred embodiments, the solvent includes any one or more combinations of xylene, No. 100 solvent oil, No. 150 solvent oil, etc., but is not limited thereto.

[0035] The second aspect of the present invention provides a method for preparing the aforementioned highly hydrophobic, wear-resistant and heavy-duty anti-corrosion coating material, comprising: uniformly mixing the first component and the second component to obtain the highly hydrophobic, wear-resistant and heavy-duty anti-corrosion coating material.

[0036] Furthermore, the above-mentioned preparation method includes: evenly mixing epoxy resin, graphene dispersion, pigment filler, additive, and solvent to form a mixture, and adjusting the viscosity of the mixture to 100-120KU with the solvent to obtain a first component; mixing vinyl perfluorooctanoate with silicon hydrogen epoxy silicone oil to obtain a fluorine-containing prepolymer with an epoxy group, and mixing the fluorine-containing prepolymer with an epoxy group with triethylenetetramine to react to obtain a second component; evenly mixing the first component and the second component to obtain the highly hydrophobic, wear-resistant, and heavy-duty anti-corrosion coating material.

[0037] In some specific embodiments, the preparation of the second component includes: heating a 49-51 wt% vinyl perfluorooctanoate solution to 55-65°C, adding a catalyst, and then mixing it with a 49-51 wt% silane-epoxy silicone oil solution, and then performing a silane-hydrogen addition reaction at 55-65°C for 2h-2.5h to obtain a fluorine-containing prepolymer with an epoxy group, mixing the fluorine-containing prepolymer with a 49-51 wt% triethylenetetramine solution, and then performing an addition reaction at 55-65°C for 2h-2.5h.

[0038] More specifically, the preparation steps of the second component are as follows:

[0039] A VDFEA solution diluted with xylene to a content of 49-51 wt% was added to a container equipped with a thermometer, a reflux condenser, a stirring device, a dropping device and a nitrogen protection device, and the temperature was raised to 55-65 ° C under low-speed stirring conditions. Then, SHPEG diluted with xylene to a content of 49-51 wt% was slowly added dropwise in the presence of a KARSTEDT catalyst. After reacting for 2h-2.5h, the mixture was cooled to room temperature to obtain a VDFEA-SHPEG resin solution.

[0040] A TETA solution diluted with xylene to a content of 49-51 wt% was added to the reactor, and the temperature was raised to 55-65° C. under low-speed stirring. Then, the VDFEA-SHPEG resin solution was slowly added. After reacting for 2 h to 2.5 h, the mixture was cooled to room temperature to obtain a VST resin solution, i.e., the second component.

[0041] In the present invention, the second component uses VDFEA and SHPEG to graft fluorinated segments onto the TETA structure, forming a poly-secondary amine structure with a high fluorine content (VST-modified resin). During this process, VDFEA and SHPEG are both monofunctional, small-molecule compounds, which prevents chain growth of the product structure during the hydrosilylation process. This reduces side reactions while effectively controlling the molecular weight and purity of the intermediate VDFEA-SHPEG, providing more favorable reaction conditions for further hydrosilylation reactions.

[0042] When VDFEA-SHPEG is added dropwise to TETA, the primary amines in TETA are more reactive. Therefore, in the presence of an excess of primary amines, the monoepoxy groups in the VDFEA-SHPEG structure preferentially react and graft with the primary amines at the ends of the structure, converting the primary amines into secondary amines. By controlling the reaction weight, the resulting VST-modified resin can contain only four secondary amines, with a long fluorinated chain segment grafted to each end. Since VDFEA-SHPEG contains only one epoxy group, chain polymerization is prevented during the addition reaction, thereby controlling the product's molecular weight within a suitable range. Due to the minimal side reactions and the low molecular weight of the raw materials, the final reaction product maintains a molecular weight of 1390-1420, while exhibiting good fluidity.

[0043] When the first and second components are mixed, the epoxy resin and VST resin react to form a three-dimensional network coating material. This coating material has excellent hydrophobic properties due to the extremely low surface free energy and surface polarity of the fluorinated segments. Water molecules have relatively high surface tension and polarity, making them difficult to spread on low-free-energy surfaces. Furthermore, due to the significant difference in polarity, they are also difficult to adsorb on low-polarity coating surfaces.

[0044] The coating is also effective against environmental erosion for three reasons. First, the fluorine atoms in the fluorinated segments are larger, and the bond energy of the FC bond (485 kJ / mol) is greater than the CC bond energy (345.6 kJ / mol). Therefore, the fluorinated segments create a shielding effect within the coating, protecting the polymer structure and providing excellent wear resistance. Second, the coating incorporates graphene nanopowder for synergistic benefits, significantly enhancing its shielding properties. This prevents corrosive media from reaching the substrate due to a "maze effect," thereby extending the coating's protective life. Furthermore, graphene's excellent wear resistance, synergistic with the fluorinated segments, further enhances its wear-resistant properties. Third, the VST resin provides four crosslinking points, and the three-dimensional network formed by its addition to the epoxy component creates a denser structure, making it less susceptible to erosion. These three factors contribute to the highly hydrophobic, wear-resistant, and heavy-duty anti-corrosion coating's enhanced environmental resistance, ensuring long-term hydrophobicity in harsh environments.

[0045] In some preferred embodiments, the catalyst comprises KARSTEDT.

[0046] In some preferred embodiments, the vinyl perfluorooctanoate solution is added to the hydridosilicone epoxy silicone oil solution at a rate of 80-100 g / min to carry out a hydrosilylation reaction.

[0047] In some preferred embodiments, the fluorine-containing prepolymer is added to the triethylenetetramine solution at a rate of 80-100 g / min to carry out an addition reaction.

[0048] The third aspect of the present invention provides a coating formed from the aforementioned highly hydrophobic, wear-resistant, heavy-duty corrosion-resistant coating material.

[0049] In some preferred embodiments, the contact angle between the coating surface and water is 122.3-125.0°, and under a load of 1000 g, the friction loss of 1000 r (C-17 grinding wheel) is ≤30 mg.

[0050] In some preferred embodiments, the coating material has good environmental resistance. After 3000 hours of acid and alkali resistance and salt spray resistance tests, the coating can still maintain an adhesion of not less than 10 MPa, and the coating does not blister or fall off.

[0051] The fourth aspect of the present invention provides the application of the aforementioned highly hydrophobic, wear-resistant and heavy-duty anti-corrosion coating material in the field of corrosion protection of steel substrates.

[0052] The present invention is further illustrated below by way of examples, but the invention is not limited to the scope of the examples described. The reagents and raw materials used in the following examples are all commercially available. The test methods where specific conditions are not specified are generally carried out under conventional conditions or according to the conditions recommended by the respective manufacturers. For example, the weight-average molecular weight of the silhydro-epoxy silicone oil used in the examples is 190-210 (SHPEG-200); vinyl perfluorooctanoate and triethylenetetramine are both high-grade pure industrial products, with a weight-average molecular weight of 430-450 for vinyl perfluorooctanoate and a molecular weight of 146 for triethylenetetramine; the epoxy resin has an epoxy equivalent of 184-190, a weight-average molecular weight of 368-380, and contains 1-2 epoxy functional groups (Nan Ya NPEL-128). Furthermore, the defoamer used in the examples includes BYK-052N, the dispersant includes EFKA-4010, and the rheological additive includes Arkema Crayvallac ULTRA. The manufacturer of silanol-epoxy silicone oil SHPEG-200 is Dow Chemical; the manufacturer of vinyl perfluorooctanoate is Shanghai Aladdin Biochemical Technology Co., Ltd.; triethylenetetramine is purchased from Shandong Jinqianrun New Materials Co., Ltd.; and epoxy resin is purchased from Nan Ya Chemical. In the examples, low-speed stirring refers to a speed of 500 rpm or less, high-speed stirring or dispersing refers to a speed of 2000 rpm or more, and 1500-2000 rpm is considered medium-speed stirring.

[0053] Example 1

[0054] This embodiment provides a highly hydrophobic, wear-resistant, and heavy-duty anti-corrosion coating material, the preparation method of which includes:

[0055] (1) Add 280g epoxy resin and 100g mixed solvent (mixed solvent with a mass ratio of xylene and 100# solvent oil of 9:1) into a stirring kettle, add 16g rheological additive under low-speed stirring, stir for 5min until uniform, disperse at high speed for 20min and then switch to low-speed stirring, then add 5g dispersant and 5g defoamer, stir at medium speed for 10min, then add 200g titanium dioxide, 100g talc, 222g silicon powder and 10g graphene dispersion (purchased from Xinhe Graphene Research Institute, with a specific surface area of 500-510m 2 / g, carbon content ≥98%, oxygen content ≤0.5%), high-speed dispersion for 25 min, and finally adjusting the viscosity to 110 KU with 62 g of xylene to obtain the first component.

[0056] (2) In a container equipped with a thermometer, a reflux condenser, a stirring device, a dripping device and a nitrogen protection device, 1000 g of a VDFEA solution diluted with xylene to 50 wt% was added, and the temperature was raised to 60°C under low-speed stirring. Then, 5 g of a KARSTEDT catalyst was added, and 500 g of a SHPEG solution diluted with xylene to 50 wt% was added dropwise at a rate of 80 g / min. The mixture was stirred continuously and the temperature was controlled at 55°C for 2 h. After the reaction was completed, the mixture was cooled to room temperature to obtain a fluorine-containing prepolymer, a VDFEA-SHPEG resin solution.

[0057] (3) 140 g of TETA solution diluted to 50 wt% by xylene was added to a container, and the temperature was raised to 60° C. under low-speed stirring. Then, 1000 g of VDFEA-SHPEG resin solution was added at a rate of 80 g / min. The mixture was stirred continuously and the temperature was controlled at 55° C. for 2 h. The mixture was then cooled to room temperature to obtain a VST resin solution, i.e., the second component was obtained.

[0058] (4) The first component and the second component are evenly mixed in a mass ratio of 1.2:1 to obtain a highly hydrophobic, wear-resistant and heavy-duty anti-corrosion coating material.

[0059] Example 2

[0060] This embodiment provides a highly hydrophobic, wear-resistant, and heavy-duty anti-corrosion coating material, the preparation method of which includes:

[0061] (1) Add 200g of epoxy resin and 80g of mixed solvent to a stirring kettle, add 10g of rheological additive under low-speed stirring, stir for 5min until uniform, disperse at high speed for 20min and then switch to low-speed stirring, then add 5g of dispersant and 5g of defoamer, stir at medium speed for 10min, then add 150g of titanium dioxide, 100g of talc, 200g of silicon micropowder and 10g of graphene dispersion in sequence, disperse at high speed for 30min, and finally adjust the viscosity to 120KU with 20g of xylene to obtain the first component.

[0062] (2) In a container equipped with a thermometer, a reflux condenser, a stirring device, a dripping device and a nitrogen protection device, 1000 g of a VDFEA solution diluted with xylene to 50 wt% was added, and the temperature was raised to 60°C under low-speed stirring. Then, a KARSTEDT catalyst was added, and 480 g of a SHPEG solution diluted with xylene to 50 wt% was added dropwise at a rate of 100 g / min. The mixture was stirred continuously and the temperature was controlled at 55°C for 2 h, and then cooled to room temperature to obtain a VDFEA-SHPEG resin solution.

[0063] (3) 130 g of TETA solution diluted to 50 wt% by xylene was added to a container, and the temperature was raised to 60° C. under low-speed stirring. Then, 1000 g of VDFEA-SHPEG resin solution was added at a rate of 100 g / min. The mixture was stirred continuously and the temperature was controlled at 55° C. for 2 h. The mixture was then cooled to room temperature to obtain a VST resin solution, i.e., the second component was obtained.

[0064] (4) The first component and the second component are mixed evenly in a mass ratio of 1:1 to obtain a highly hydrophobic, wear-resistant and heavy-duty anti-corrosion coating material.

[0065] Example 3

[0066] In this embodiment, the solvent is No. 100 solvent oil, and the viscosity is adjusted to 100 KU with xylene to obtain the first component. The other conditions remain the same as in Example 1.

[0067] Example 4

[0068] In this embodiment, the solvent is No. 150 solvent oil, and the other conditions are consistent with those in Example 1.

[0069] Example 5

[0070] In this embodiment, the fluorine-containing prepolymer VDFEA-SHPEG resin and triethylenetetramine were mixed in a molar ratio of 2:1.10 for reaction, and the other conditions remained the same as in Example 1.

[0071] Example 6

[0072] In this embodiment, vinyl perfluorooctanoate and silyl epoxy silicone oil were subjected to a hydrosilylation reaction at a molar ratio of 1:1.05 to generate a fluorine-containing prepolymer VDFEA-SHPEG resin. Other conditions remained the same as in Example 1.

[0073] Example 7

[0074] In this embodiment, VDFEA-SHPEG resin and triethylenetetramine were mixed in a molar ratio of 2:1.20 for reaction, that is, a mass ratio of the two was 1:0.14, and the other conditions remained the same as in Example 1.

[0075] Example 8

[0076] In this embodiment, vinyl perfluorooctanoate and silyl epoxy silicone oil were reacted at a molar ratio of 1:1.1, that is, a mass ratio of 1:0.5. The other conditions remained the same as in Example 1.

[0077] Example 9

[0078] Compared with Example 2, this embodiment differs in that step (2) is:

[0079] (2) In a container equipped with a thermometer, a reflux condenser, a stirring device, a dripping device and a nitrogen protection device, 1000 g of a VDFEA solution diluted with xylene to 51 wt% was added, and the temperature was raised to 65°C under low-speed stirring. Then, a KARSTEDT catalyst was added, and 480 g of a SHPEG solution diluted with xylene to 51 wt% was added dropwise at a rate of 90 g / min. The mixture was stirred continuously and the temperature was controlled at 65°C for 2.5 h, and then cooled to room temperature to obtain a VDFEA-SHPEG resin solution.

[0080] (3) 130 g of a TETA solution diluted to 51 wt% by weight in xylene was added to a container, and the temperature was raised to 65° C. under low-speed stirring. Then, 1000 g of a VDFEA-SHPEG resin solution was added at a rate of 90 g / min. The mixture was stirred continuously and the temperature was controlled at 65° C. for 2.5 h, and then cooled to room temperature to obtain a VST resin solution, i.e., the second component was obtained.

[0081] (4) The first component and the second component are mixed evenly in a mass ratio of 1.2:1 to obtain a highly hydrophobic, wear-resistant and heavy-duty anti-corrosion coating material.

[0082] Example 10

[0083] Compared with Example 2, this embodiment differs in that step (2) is:

[0084] (2) In a container equipped with a thermometer, a reflux condenser, a stirring device, a dripping device and a nitrogen protection device, 1000 g of a VDFEA solution diluted with xylene to 49 wt% was added, and the temperature was raised to 55°C under low-speed stirring. Then, a KARSTEDT catalyst was added, and 480 g of a SHPEG solution diluted with xylene to 49 wt% was added dropwise at a rate of 80 g / min. The mixture was stirred continuously and the temperature was controlled at 60°C for 2.2 h, and then cooled to room temperature to obtain a VDFEA-SHPEG resin solution.

[0085] (3) 130 g of a TETA solution diluted to 49 wt% by weight in xylene was added to a container, and the temperature was raised to 55° C. under low-speed stirring. Then, 1000 g of a VDFEA-SHPEG resin solution was added at a rate of 80 g / min. The mixture was stirred continuously and the temperature was controlled at 60° C. for 2.2 h. The mixture was then cooled to room temperature to obtain a VST resin solution, i.e., the second component was obtained.

[0086] (4) The first component and the second component are mixed evenly in a mass ratio of 1:1 to obtain a highly hydrophobic, wear-resistant and heavy-duty anti-corrosion coating material.

[0087] Comparative Example 1

[0088] The difference between Comparative Example 1 and Example 1 is that in Comparative Example 1, after the first component is prepared, it is directly mixed with unmodified triethylenetetramine, and the other conditions remain the same as in Example 1.

[0089] Comparative Example 2

[0090] The difference between Comparative Example 2 and Example 1 is that in Comparative Example 2, the mixing ratio of the first component to the second component is 1.3:1. The other conditions remain the same as in Example 1.

[0091] Comparative Example 3

[0092] The difference between Comparative Example 3 and Example 1 is that in Comparative Example 3, no hydrosilylation reaction is performed, and vinyl perfluorooctanoate and triethylenetetramine are directly mixed. The other conditions remain the same as in Example 1.

[0093] Comparative Example 4

[0094] The difference between Comparative Example 4 and Example 1 is that in Comparative Example 4, no graphene dispersion is added to the first component. The other conditions remain the same as in Example 1.

[0095] Comparative Example 5

[0096] The difference between Comparative Example 5 and Example 1 is that in Comparative Example 5, when preparing the second component, triethylenetetramine is replaced by commercially available 140 polyamide.

[0097] Comparative Example 6

[0098] In Comparative Example 6, the fluorine-containing prepolymer and triethylenetetramine were mixed all at once, and the other conditions remained the same as in Example 1.

[0099] The hydrophobicity, wear resistance and environmental resistance of the anti-corrosion coating materials prepared in Examples 1-10 and Comparative Examples 1-6 were tested respectively. The test results are shown in Table 1.

[0100] Table 1 Comparative table of performance test of anticorrosive coating materials prepared in Examples 1-10 and Comparative Examples 1-6

[0101]

[0102] It can be seen from the data in the table that the water contact angle of the coating material provided by the present invention can reach 122.3°-125°, and under a load of 1000g, the friction loss of 1000r (C-17 grinding wheel) is ≤30mg. After 3000 hours of acid and alkali resistance and salt spray resistance tests, the coating can still maintain an adhesion of not less than 10MPa, and the coating has no blistering, falling off, etc., indicating that the coating materials provided in Examples 1-10 of the present invention have high hydrophobicity, high wear resistance and excellent environmental resistance.

[0103] The various aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and are not intended to limit the present invention, the scope of which is defined solely by the claims. Other embodiments, modifications and uses will be apparent to those skilled in the art without departing from the spirit and scope of the invention as claimed.

Claims

1. A highly hydrophobic, wear-resistant, heavy-duty anti-corrosion coating material, characterized by: The raw materials of the highly hydrophobic, wear-resistant and heavy-duty anti-corrosion coating material include a first component and a second component, wherein the first component is an epoxy component, and the second component is a VST modified resin prepared by a silylation reaction between vinyl perfluorooctanoate and silyl epoxy silicone oil in a molar ratio of 1:1.05-1.10 to generate a fluorine-containing prepolymer having an epoxy group, and then an addition reaction with triethylenetetramine in a molar ratio of 2:1.1-1.2; the weight-average molecular weight of the VST modified resin is 1390-1420, and the VST modified resin has 4 secondary amino groups.

2. The highly hydrophobic, wear-resistant, heavy-duty anti-corrosion coating material according to claim 1, characterized in that: The mass ratio of the first component to the second component is 1-1.2:

1.

3. The highly hydrophobic, wear-resistant, heavy-duty anti-corrosion coating material according to claim 1, characterized in that: The weight average molecular weight of the vinyl perfluorooctanoate is 430-450.

4. The highly hydrophobic, wear-resistant, heavy-duty anti-corrosion coating material according to claim 1, characterized in that: The weight average molecular weight of the silicon hydrogen epoxy silicone oil is 190-210.

5. The highly hydrophobic, wear-resistant, heavy-duty anti-corrosion coating material according to claim 1, characterized in that: The first component includes epoxy resin, graphene dispersion, additives, pigments and fillers, and solvents.

6. The highly hydrophobic, wear-resistant, heavy-duty anti-corrosion coating material according to claim 5, characterized in that: The first component includes the following components calculated in parts by mass: 20-30 parts of epoxy resin, 1-1.5 parts of graphene dispersion, 2-3 parts of additives, 45-55 parts of pigments and fillers, and 10-20 parts of solvents.

7. The highly hydrophobic, wear-resistant, heavy-duty anti-corrosion coating material according to claim 5, characterized in that: The epoxy resin has an epoxy equivalent of 184-190 and contains 1-2 epoxy functional groups.

8. The highly hydrophobic, wear-resistant, heavy-duty anti-corrosion coating material according to claim 5, characterized in that: The weight average molecular weight of the epoxy resin is 368-380.

9. The highly hydrophobic, wear-resistant, heavy-duty anti-corrosion coating material according to claim 5, characterized in that: The specific surface area of the graphene dispersion is ≥500m 2 / g, the graphene carbon element content in the dispersion is ≥98%, the number of layers is ≤10, and the oxygen content is ≤0.5%, and the graphene dispersion comprises graphene and xylene.

10. The highly hydrophobic, wear-resistant, heavy-duty anti-corrosion coating material according to claim 5, characterized in that: The auxiliary agent includes any one or more combinations of defoaming agents, leveling agents and rheological additives.

11. The highly hydrophobic, wear-resistant, heavy-duty anti-corrosion coating material according to claim 5, characterized in that: The pigments and fillers include any one or more combinations of titanium dioxide, black iron oxide, red iron oxide, talcum powder and silica powder.

12. The highly hydrophobic, wear-resistant, heavy-duty anti-corrosion coating material according to claim 5, characterized in that: The solvent includes any one or more combinations of xylene, No. 100 solvent oil, and No. 150 solvent oil.

13. The method for preparing a highly hydrophobic, wear-resistant, heavy-duty anti-corrosion coating material according to any one of claims 1 to 12, characterized in that: include: The epoxy resin, graphene dispersion, pigment, filler, additive, and solvent are uniformly mixed to form a mixture, and the viscosity of the mixture is adjusted to 100-120 KU with the solvent to obtain a first component; A 49-51 wt% vinyl perfluorooctanoate solution is heated to 55-65° C., a catalyst is added, and the mixture is mixed with a 49-51 wt% silanol-epoxy silicone oil solution, followed by a hydrosilylation reaction at 55-65° C. for 2 h to 2.5 h to obtain a fluorine-containing prepolymer having epoxy groups. The fluorine-containing prepolymer is added to a 49-51 wt% triethylenetetramine solution at a rate of 80-100 g / min, followed by an addition reaction at 55-65° C. for 2 h to 2.5 h to obtain a second component; The first component and the second component are uniformly mixed to prepare the highly hydrophobic, wear-resistant and heavy-duty anti-corrosion coating material.

14. The method for preparing a highly hydrophobic, wear-resistant, heavy-duty anti-corrosion coating material according to claim 13, characterized in that: The catalyst includes KARSTEDT.

15. The method for preparing a highly hydrophobic, wear-resistant, heavy-duty anti-corrosion coating material according to claim 13, characterized in that: include: The vinyl perfluorooctanoate solution is added to the hydridosilicone epoxy silicone oil solution at a rate of 80-100 g / min to carry out a hydrosilylation reaction.

16. A coating, characterized in that The coating is formed by the highly hydrophobic, wear-resistant, heavy-duty anti-corrosion coating material according to any one of claims 1 to 12.

17. The coating according to claim 16, characterized in that: The contact angle between the coating surface and water is 122.3-125.0°, and under a load condition of 1000g, the friction loss of 1000r is ≤30mg.

18. The coating according to claim 17, characterized in that: After 3000 hours of acid and alkali resistance and salt spray resistance tests, the coating can still maintain an adhesion of no less than 10 MPa.

19. Use of the highly hydrophobic, wear-resistant, heavy-duty anti-corrosion coating material according to any one of claims 1 to 12 in the field of corrosion protection of steel substrates.

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