Modified wear-resistant anticorrosive resin coating and preparation method thereof

Abstract

The invention belongs to the technical field of epoxy resin wear-resistant coatings, and discloses a modified wear-resistant anticorrosive resin coating and a preparation method thereof. And adding a modifier into the homogeneous mother liquor, and uniformly mixing for reaction to obtain the liquid modified wear-resistant anticorrosive coating. Then standing to eliminate bubbles generated in the reaction process; and finally, curing to obtain the solid modified wear-resistant anticorrosive resin coating. According to the invention, polyphenyl-terminated hydroxyl group siloxane is used as a filler, hydroxyl is used for reacting with an epoxy group in a matrix, and homogeneous toughening is carried out to crosslink the polyphenyl-terminated hydroxyl group siloxane into a curing network of epoxy resin, so that the risk of cracking of the coating is reduced; through the synergistic effect of a rigid ring benzene ring and a flexible bond Si-O, the hardness of a paint film can be improved, the brittleness of the paint film is reduced, and the possibility that the paint film is cracked due to impact is reduced.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of epoxy resin wear-resistant coatings, and in particular relates to a modified wear-resistant and corrosion-resistant resin coating and a preparation method thereof. BACKGROUND

[0002] Fretting corrosion is a damage to the contact interface under the combined action of mechanical load and chemical corrosion. Its essence lies in the interaction between friction mechanics behavior and oxidation corrosion process under fretting conditions, which leads to the degradation of material performance. The failure mechanism is embodied in two paths: wear-oxidation mechanism: mechanical wear produces metal debris, and friction heat promotes its oxidation. Oxidation-wear mechanism: the surface oxide film undergoes periodic rupture (exposure of fresh metal oxidation / cold welding) and regeneration cycle. This dynamic process forms pits and scratches on the contact surface, and the oxide debris produced aggravates three-body wear. The engineering hazards of fretting corrosion are obvious, including the induction of fatigue crack initiation by oxide accumulation; the increase of contact resistance due to surface topography change, which threatens the reliability of precision electronic devices (such as low-current relays); and the possibility of causing component jamming failure due to repeated adhesion-fracture.

[0003] Chinese Patent Application 202410535548.X discloses a high wear-resistant coating based on nano-graphene and a preparation method thereof, relating to the technical field of coatings. The high wear-resistant coating based on nano-graphene includes the following raw materials by weight: epoxy resin 10-15 parts, phenolic resin 1-10 parts, polyester resin 1-10 parts, nano-graphene 1-3 parts, micron-sized silicon carbide 3-5 parts, diamond sand 1-3 parts, dispersing agent 1-5 parts, aluminum oxide ceramic 1-5 parts, high manganese steel 1-5 parts, auxiliary agent 1-5 parts, and composite solvent 76-105 parts. The nano-graphene has a particle size of 20-100 microns, and the diamond sand has a particle size of 50-200 microns. The high strength and toughness of graphene make the coating have excellent wear resistance, which can protect the surface of the coated object from wear and corrosion. This coating can prolong the service life of the object under the coating, reduce maintenance costs and replacement frequency, and the high conductivity of graphene enables the coating to conduct current under the coating, which is suitable for application scenarios requiring conductivity. However, the toughening agent in this patent, graphene, and aluminum oxide are prone to deposition and agglomeration, which leads to cracking of the paint surface, reduced wear resistance, and adhesion.

[0004] Chinese patent application 202411702472.1 discloses a wear-resistant coating and its preparation method, workpiece and its processing method. The wear-resistant coating comprises polysilazane resin and auxiliary materials; the auxiliary materials include 1-10 parts of active filler, 5-50 parts of structural filler, 10-70 parts of solvent, and 0.1-2 parts of dispersion aid by weight; the polysilazane resin accounts for 20-40% of the weight of the wear-resistant coating. The preparation method is to crush and mix the active filler, structural filler, solvent and dispersion aid by ball milling, and then mix the polysilazane resin uniformly. The prepared wear-resistant coating has the characteristics of good wear resistance and strong adhesion, and the use of polysilazane resin and auxiliary materials can effectively solve the problem of easy cracking of silicon nitride ceramic coating. However, the silicon nitride filler of the silicon nitride ceramic coating prepared by the scheme cannot form a chemical bond with the resin matrix, which leads to separation of the filler and the matrix and reduces the wear resistance of the coating.

[0005] Chinese patent application 202411716234.6 discloses a water-based anticorrosive wear-resistant coating and its preparation method. The preparation method includes mixing modified MXene nanosheets with water-based epoxy resin emulsion uniformly to obtain a premixed emulsion; under stirring conditions, polytetrafluoroethylene powder, titanium dioxide, aluminum oxide, substrate wetting agent, dispersant, defoaming agent, surface adhesion promoter, deionized water and curing agent are added to the premixed emulsion in sequence, and mixed uniformly to obtain the water-based anticorrosive wear-resistant coating. The prepared water-based anticorrosive wear-resistant coating adds polytetrafluoroethylene and modified MXene nanosheets in the coating, which improves the anticorrosive performance of the water-based coating and the wear resistance of the water-based coating, overcoming the shortcomings of the existing water-based coating in terms of anticorrosive wear resistance. However, the anticorrosive coating in the scheme is water-based, and the application scenario is slightly narrower than that of organic coatings. It is easy to hydrolyze and greatly reduces the service life in a humid environment. SUMMARY

[0006] In view of the deficiencies of the prior art, the purpose of the present application is to provide a modified wear-resistant anticorrosive resin coating and its preparation method. The prepared wear-resistant coating can effectively prevent friction corrosion and reduce corrosion loss. In the present application, polyphenyl end hydroxyl cluster siloxane is used as a filler, the hydroxyl groups react with the epoxy groups in the matrix, and the polyphenyl end hydroxyl cluster siloxane is crosslinked into the curing network of the epoxy resin by homogeneous toughening, reducing the risk of coating cracking. The synergistic effect of rigid cyclophane rings and flexible Si-O bonds can improve the hardness of the paint film while reducing the brittleness of the paint film, reducing the possibility of cracking under impact.

[0007] In order to achieve the above-mentioned purpose of the application, the technical solutions are as follows:

[0008] According to one aspect of the present application, a modified wear-resistant anticorrosive resin coating is provided, which is obtained according to the following preparation method:

[0009] Mixing 50-60 parts by mass of epoxy resin with 30-40 parts by mass of curing agent to prepare a homogeneous mother liquor;

[0010] Adding 5-8 parts by mass of modifier to the homogeneous mother liquor, mixing uniformly to react, to obtain a liquid modified wear-resistant anticorrosive coating;

[0011] Standing to eliminate the bubbles generated in the reaction process;

[0012] Curing to obtain a solid modified wear-resistant anticorrosive resin coating.

[0013] According to another aspect of the present application, a preparation method of a modified wear-resistant anticorrosive resin coating is provided, comprising:

[0014] Mixing 50-60 parts by mass of epoxy resin with 30-40 parts by mass of curing agent to prepare a homogeneous mother liquor;

[0015] Adding 5-8 parts by mass of modifier to the homogeneous mother liquor, mixing uniformly to react, to obtain a liquid modified wear-resistant anticorrosive coating;

[0016] Standing to eliminate the bubbles generated in the reaction process;

[0017] Curing to obtain a solid modified wear-resistant anticorrosive resin coating.

[0018] In the above modified wear-resistant anticorrosive resin coating and the preparation method thereof:

[0019] Further, the epoxy resin is a bisphenol A type epoxy resin or an epoxidized olefin compound.

[0020] Further, the curing agent is one of methyl tetrahydrophthalic anhydride, phthalic anhydride, and methyl hexahydrophthalic anhydride.

[0021] Further, the modifier is a polyphenyl terminal hydroxyl cluster siloxane, and the preparation method of the polyphenyl terminal hydroxyl cluster siloxane is as follows: stirring 30-40 parts by mass of 1, 4-butanediol, 20-30 parts by mass of phenyl triethoxysilane, and 5-10 parts by mass of a catalyst at a temperature of 130-150°C for 3-5h, filtering through a semi-permeable membrane with a molecular weight pore size of 1000-3000, and then washing and drying to obtain the polyphenyl terminal hydroxyl cluster siloxane.

[0022] Still further, the polyphenyl terminal hydroxyl cluster siloxane is a mixture of polyphenyl terminal hydroxyl cluster siloxane A and polyphenyl terminal hydroxyl cluster siloxane B, or polyphenyl terminal hydroxyl cluster siloxane A alone, or polyphenyl terminal hydroxyl cluster siloxane B alone:

[0023] The structural formula of polyphenyl terminal hydroxyl cluster siloxane A is as follows:

[0024]

[0025] The structural formula of polybenzene-terminated hydroxyl cluster siloxane B is:

[0026]

[0027] Among them, the individual polyphenyl-terminated hydroxyl cluster siloxane A and the individual polyphenyl-terminated hydroxyl cluster siloxane B were separated by rotary evaporation, with the distillate being polyphenyl-terminated hydroxyl cluster siloxane A and the residue being polyphenyl-terminated hydroxyl cluster siloxane B.

[0028] The preferred temperature for rotary evaporation is 150-160 ℃.

[0029] Furthermore, the catalyst is one of barium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide.

[0030] Furthermore, the reaction process involves first adding 1,4-butanediol and phenyltriethoxysilane simultaneously into a reaction vessel according to their mass fractions, and mixing them for 5-10 minutes at a speed of 5-20 r / min under a nitrogen or argon atmosphere at 50-60°C; then adding a catalyst according to its mass fractions, and stirring the mixture at a speed of 50-60 r / min under a protective atmosphere.

[0031] Furthermore, the washing process involves washing with deionized water 2-5 times.

[0032] Furthermore, the drying process is carried out in a nitrogen-filled drying environment at 60-90°C for 8-10 hours.

[0033] Furthermore, the reaction temperature between the modifier and the homogeneous mother liquor is 20–80°C, and the mixing method is high-speed stirring or ultrasonic dispersion.

[0034] Preferably, the high-speed stirring rate is not less than 500 r / min, and the high-speed stirring time is 0.5-5 h;

[0035] Preferably, the ultrasonic dispersion time is 0.2h to 2h.

[0036] Furthermore, the settling period is 12-18 hours under a vacuum of 0.07MPa-0.08MPa.

[0037] Furthermore, the curing process involves pre-curing at 50-60℃ in an environment of 0.8KPa-0.6KPa for 3-4 hours, followed by curing at 140-160℃ in an atmospheric environment for 12-16 hours.

[0038] Furthermore, after curing, allow the material to stand to eliminate stress. The standing conditions are horizontal standing for 5-6 hours in an atmospheric environment at 50-60℃.

[0039] The beneficial effects of the present application are:

[0040] The modified wear-resistant anticorrosive resin coating prepared by the present application has the advantages of super wear resistance, excellent corrosion resistance, long-term stability

[0041] , and convenient application.

[0042] The modified wear-resistant anticorrosive resin coating prepared by the present application realizes the synergistic enhancement of "wear resistance" and "corrosion resistance", and forms a strong homogeneous physical protection network through cross-linking of phenyl in the epoxy resin. At the same time, since no second wear-resistant material is added, secondary friction corrosion caused by "three-body friction" is greatly avoided, and the high hardness can effectively resist particle erosion, mechanical friction and repeated scratching, greatly extending the service life of the equipment under heavy load and high frequency friction conditions.

[0043] The modified wear-resistant anticorrosive resin coating prepared by the present application is chemically modified by using a multi-phenyl end-hydroxyl cluster siloxane. The presence of end-hydroxyl groups can maximize the density of the coating itself, forming a dense and seamless interpenetrating network structure. This structure can effectively block the penetration of corrosion media such as water vapor, oxygen, and chloride ions, thereby providing a barrier protection effect far superior to ordinary coatings, with a salt spray resistance time of more than 1000 hours.

[0044] The modified wear-resistant anticorrosive resin coating prepared by the present application not only retains the excellent adhesion of epoxy resin to various substrates (steel, concrete, etc.), but also introduces the flexibility of organic silicon segments, overcoming the brittleness and cracking of traditional epoxy coatings, and significantly improving the impact resistance, flexibility and cold-heat resistance of the coating. Even when the substrate undergoes slight deformation, the coating remains intact, eliminating the risk of peeling.

[0045] The preparation method of the present application is more efficient and controllable: the step-by-step feeding and one-step polymerization method ensures the synthesis of the modifier to be simple, easy to disperse, and avoids the agglomeration phenomenon commonly seen in nano-toughening materials, fully utilizing the role of the reinforcing phase. The preparation process conditions are mild and controllable, the product quality is stable, and it is suitable for large-scale industrial production. BRIEF DESCRIPTION OF DRAWINGS

[0046] Figure 1 The synthesis equation of the multi-phenyl end-hydroxyl cluster siloxane A is as follows:

[0047] Figure 2 The synthesis equation of the multi-phenyl end-hydroxyl cluster siloxane B is as follows:

[0048] Figure 3Figure 1: SEM images of the solid modified wear-resistant anticorrosive resin coating prepared for Examples 1-5 before and after abrasion; (a) Example 1 before abrasion, (b) Example 1 after abrasion, (c) Example 2 before abrasion, (d) Example 2 after abrasion, (e) Example 3 before abrasion, (f) Example 3 after abrasion, (g) Example 16 before abrasion, (h) Example 16 after abrasion, (i) Example 19 before abrasion, (j) Example 19 after abrasion. DETAILED DESCRIPTION

[0049] The present application will be further described in detail by specific examples, which can make the professional technical personnel more comprehensive understanding of the present application, but not in any way limit the present application.

[0050] The present application provides a modified wear-resistant anticorrosive resin coating and a preparation method thereof, comprising:

[0051] Mixing 50-60 parts by mass of epoxy resin with 30-40 parts by mass of curing agent to prepare a homogeneous mother liquor;

[0052] Adding 5-8 parts by mass of modifier to the homogeneous mother liquor, mixing uniformly to react, to obtain a liquid modified wear-resistant anticorrosive coating;

[0053] Standing to eliminate the bubbles generated in the reaction process;

[0054] Curing to obtain a solid modified wear-resistant anticorrosive resin coating.

[0055] As some preferred embodiments of the present application, the epoxy resin is a bisphenol A type epoxy resin or an epoxidized olefin compound.

[0056] As some preferred embodiments of the present application, the curing agent is one of methyl tetrahydrophthalic anhydride, phthalic anhydride, and methyl hexahydrophthalic anhydride.

[0057] As some preferred embodiments of the present application, the modifier is a polyphenyl terminal hydroxyl cluster siloxane, and the preparation method of the polyphenyl terminal hydroxyl cluster siloxane is as follows: stirring 30-40 parts by mass of 1, 4-butanediol, 20-30 parts by mass of phenyl triethoxysilane, and 5-10 parts by mass of catalyst at a temperature of 130-150°C for 3-5h, filtering through a semi-permeable membrane with a molecular weight pore size of 1000-3000, washing and drying to obtain the polyphenyl terminal hydroxyl cluster siloxane. Figure 1 and Figure 2 as shown.

[0058] The polyphenyl terminal hydroxyl cluster siloxane is a mixture of polyphenyl terminal hydroxyl cluster siloxane A and structural polyphenyl terminal hydroxyl cluster siloxane B, or polyphenyl terminal hydroxyl cluster siloxane A alone, or polyphenyl terminal hydroxyl cluster siloxane B alone:

[0059] The structural formula of the polyphenyl end hydroxyl cluster siloxane A is:

[0060]

[0061] The structural formula of the polyphenyl end hydroxyl cluster siloxane B is:

[0062]

[0063] The polyphenyl end hydroxyl cluster siloxane A and the polyphenyl end hydroxyl cluster siloxane B are separated by the rotary evaporation method, the distillate is the polyphenyl end hydroxyl cluster siloxane A, and the residue is the polyphenyl end hydroxyl cluster siloxane B.

[0064] Further preferably, the temperature of the rotary evaporation method is 150-160 ℃.

[0065] As some preferred embodiments of the present application, in the preparation method of the polyphenyl end hydroxyl cluster siloxane: the catalyst is one of barium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide.

[0066] As some preferred embodiments of the present application, in the preparation method of the polyphenyl end hydroxyl cluster siloxane: the reaction process is that first, according to the mass fraction, 1, 4-butanediol and phenyltriethoxysilane are simultaneously put into a reaction container, and mixed at a speed of 5-20 r / min for 5-10 min under the protection of a nitrogen atmosphere or an argon atmosphere at 50-60 ℃; then, according to the mass fraction, the catalyst is put in, and the reaction is carried out by stirring at a speed of 50-60 r / min under the protection of the atmosphere.

[0067] As some preferred embodiments of the present application, in the preparation method of the polyphenyl end hydroxyl cluster siloxane: the washing is 2-5 times of washing with deionized water.

[0068] As some preferred embodiments of the present application, in the preparation method of the polyphenyl end hydroxyl cluster siloxane: the drying is carried out at 60-90 ℃ in a nitrogen blowing drying environment for 8-10 h.

[0069] As some preferred embodiments of the present application, the reaction temperature of the modifier and the homogeneous mother liquor is 20-80 ℃, and the mixing mode is high-speed stirring or ultrasonic dispersion.

[0070] More preferably, the speed of the high-speed stirring is not less than 500 r / min, and the time of the high-speed stirring is 0.5-5 h.

[0071] More preferably, the time of the ultrasonic dispersion is 0.2 h-2 h.

[0072] As some preferred embodiments of the present application, the standing is at 0.07-0.08 MPa vacuum for 12-18 h.

[0073] As some preferred embodiments of the present application, the curing process is pre-curing at 0.8-0.6 KPa at 50-60 °C for 3-4 h, and then curing at 140-160 °C in the atmosphere for 12-16 h.

[0074] As some preferred embodiments of the present application, after curing, the standing is to eliminate stress, and the standing condition is horizontal standing at 50-60 °C in the atmosphere for 5-6 h.

[0075] Specifically:

[0076] Example 1:

[0077] Step one: the preparation method of the polyphenyl end-hydroxyl cluster siloxane is as follows: 40 g of 1,4-butanediol, 30 g of phenyltriethoxysilane, and 10 g of a catalyst which is barium hydroxide are mixed according to the mass fraction; under the protection of nitrogen or argon atmosphere at 60 °C, the mixture is stirred at a speed of 20 r / min for 10 min; then, under the protection of the atmosphere, the mixture is stirred at a speed of 60 r / min at 150 °C for 5 h; after being filtered through a semi-permeable membrane with a molecular weight of 3000, the mixture is washed with deionized water for 5 times, and then dried in a nitrogen blowing drying environment at 90 °C for 10 h; a polyphenyl end-hydroxyl cluster siloxane A, B mixture is obtained.

[0078] Step two: 60 g of bisphenol A type epoxy resin and 40 g of methyltetrahydrophthalic anhydride curing agent are mixed to prepare a homogeneous mother liquor; 7 g of the modified polyphenyl end-hydroxyl cluster siloxane A, B mixture is added to the homogeneous mother liquor, and the mixture is uniformly reacted at a reaction temperature of 80 °C, with high-speed stirring or ultrasonic dispersion; the high-speed stirring rate is 500 r / min, and the high-speed stirring time is 5 h; the ultrasonic dispersion time is 2 h, and a liquid modified wear-resistant and corrosion-resistant coating is obtained; the liquid modified wear-resistant and corrosion-resistant coating is stood at 0.08 MPa vacuum for 18 h; then, the liquid modified wear-resistant and corrosion-resistant coating is pre-cured at 0.6 KPa at 60 °C for 4 h, and then cured at 160 °C in the atmosphere for 16 h; after curing, the liquid modified wear-resistant and corrosion-resistant coating is stood to eliminate stress, and the standing condition is horizontal standing at 60 °C in the atmosphere for 6 h to eliminate the bubbles generated in the reaction process; the liquid modified wear-resistant and corrosion-resistant coating is sprayed and cured to obtain a solid modified wear-resistant and corrosion-resistant resin coating.

[0079] Example 2:

[0080] The method of Example 1 is used for preparation, and the only difference is that the modified agent in step two is 6 g of the polyphenyl end-hydroxyl cluster siloxane A, B mixture.

[0081] Example 3:

[0082] Prepared by the method of Example 1, except that in Step 2 the modifier was 5 g of polyphenyl end-hydroxyl cluster siloxane A, B mixture.

[0083] Example 4:

[0084] Prepared by the method of Example 1, except that in Step 2 the modifier was 8 g of polyphenyl end-hydroxyl cluster siloxane A, B mixture.

[0085] Example 5:

[0086] Prepared by the method of Example 1, except that in Step 2 the bisphenol A epoxy resin added was 50 g.

[0087] Example 6:

[0088] Prepared by the method of Example 1, except that in Step 2 the bisphenol A epoxy resin added was 55 g.

[0089] Example 7:

[0090] Prepared by the method of Example 1, except that in Step 2 the methyltetrahydrophthalic anhydride curing agent added was 30 g.

[0091] Example 8:

[0092] Prepared by the method of Example 1, except that in Step 2 the methyltetrahydrophthalic anhydride curing agent added was 35 g.

[0093] Example 9:

[0094] Prepared by the method of Example 1, except that in Step 2 the methyltetrahydrophthalic anhydride curing agent added was 50 g.

[0095] Example 10:

[0096] Prepared by the method of Example 1, except that in Step 2 the curing agent added was 40 g of phthalic anhydride.

[0097] Example 11:

[0098] Prepared by the method of Example 1, except that in Step 2 the curing agent added was 40 g of methylhexahydrophthalic anhydride.

[0099] Example 12:

[0100] Prepared by the method of Example 1, except that in Step 1 the catalyst added was 10 g of potassium hydroxide.

[0101] Example 13:

[0102] Prepared by the method of Example 1, except that in Step 1, 10 g of sodium hydroxide was added as the catalyst.

[0103] Example 14:

[0104] Prepared by the method of Example 1, except that in Step 1, 10 g of calcium hydroxide was added as the catalyst.

[0105] Example 15:

[0106] Prepared by the method of Example 1, except that in Step 1, filtration was through a semi-permeable membrane with a 1000 molecular weight pore size.

[0107] Example 16:

[0108] Prepared by the method of Example 1, except that in Step 1, filtration was through a semi-permeable membrane with a 5000 molecular weight pore size.

[0109] Example 17:

[0110] Prepared by the method of Example 1, except that in Step 1, filtration was through a semi-permeable membrane with a 10000 molecular weight pore size.

[0111] Example 18:

[0112] Prepared by the method of Example 1, except that in Step 1, rotary evaporation was used at 150°C, and the distillate was tested to obtain polyphenyl terminated hydroxyl cluster siloxane A; and in Step 2, 6 g of polyphenyl terminated hydroxyl cluster siloxane A was added as the modifying agent.

[0113] Example 19:

[0114] Prepared by the method of Example 1, except that in Step 1, rotary evaporation was used at greater than 160°C, and the distillate was tested to obtain polyphenyl terminated hydroxyl cluster siloxane B; and in Step 2, 6 g of polyphenyl terminated hydroxyl cluster siloxane B was added as the modifying agent.

[0115] Example 20:

[0116] Prepared by the method of Example 1, except that in Step 1, rotary evaporation was used at 160°C, and the distillate was tested to obtain polyphenyl terminated hydroxyl cluster siloxane B; and in Step 2, 6 g of polyphenyl terminated hydroxyl cluster siloxane B was added as the modifying agent.

[0117] Example 21:

[0118] Prepared by the method of Example 1, except that in Step 1, rotary evaporation was used at 140°C, and the distillate was tested to obtain polyphenyl terminated hydroxyl cluster siloxane B polymorph; and in Step 2, 6 g of polyphenyl terminated hydroxyl cluster siloxane B polymorph was added as the modifying agent.

[0119] Example 22:

[0120] Prepared by the method of Example 1, except that the stirring temperature in Step 1 was 130°C.

[0121] Example 23:

[0122] Prepared by the method of Example 1, except that in Step 2, the standing was under atmospheric conditions for 18 h.

[0123] Example 24:

[0124] Prepared by the method of Example 1, except that in Step 2, the brush coating was cured, the speed of high-speed stirring was 1000 r / min, and the time of high-speed stirring was 0.5 h; wherein the time of ultrasonic dispersion was 0.2 h.

[0125] Example 25:

[0126] Prepared by the method of Example 1, except that in Step 2, no standing was performed and the coating was cured directly.

[0127] The modified wear-resistant anticorrosive resin coatings prepared in Examples 1-25 above were respectively coated on the surfaces of Q235 steel plates and tinplate for performance testing. The prepared anticorrosive coatings had a thickness of 40±2 μm. The Q235 steel plates were used as the substrate for salt spray testing, and the tinplate was used as the substrate for the remaining tests. The wear resistance was tested by the rotating rubber sand wheel method (GB / T 1768-2006 Test Method for Abrasion Resistance of Pigmented Coatings and Clear Coatings), the coating performance was evaluated by the salt spray test (GB / T 10125-2021 Artificial Atmosphere Corrosion Test Salt Spray Test), the impact test (GB / T 1732-2020 Test Method for Impact Resistance of Coatings), the hardness test (ISO 6508 Test Standard for Shore Hardness Tester), and the adhesion test (GB / T 1720-2020 Coating Film Scratch Test). In the salt spray test, no scratches were made, and the appearance of rust spots on the sample was the test endpoint. The test results are shown in Table 1, and the scanning images before and after wear for different amounts of added modifier are shown in Figure 3 .

[0128] It can be seen that the brush coating method has a smoother paint surface than the spray coating method, but there is no significant difference in the key performance data. Figure 3

[0129] Table 1: Performance data of coatings prepared with different amounts of added modifier

[0130] Item Control amount Wear amount (mg) Salt spray resistance (h) Coating impact resistance Paint film hardness (HR) Adhesion rating Example 1 7 g of modifier 17.1208 1248 50 cm 84 1 Example 2 6 g of modifier 17.1019 1218 50 cm 84 1 Example 3 5 g of modifier 18.1421 1024 50 cm 88 2 Example 4 8 g of modifier 19.2453 912 48 cm 79 1~2

[0131] ​From Table 1, with the increase of the amount of modifier, the paint surface produces a large number of bubbles due to the excessive amount of modifier, which affects the adhesion of the paint surface, and after friction, peeling begins to occur. When the amount of modifier is too small, the wear and tear is significantly increased, and without adding the modifier, the wear is the most serious. In summary, 5-8 mass parts of the modifier can improve the wear resistance of the paint film. The modified wear-resistant anticorrosive resin coating with 7 mass parts of the modifier has the most excellent performance, and the modified wear-resistant anticorrosive resin coating with 5 mass parts of the modifier has the highest hardness.

[0132] Table 2: Performance data of paint surfaces prepared with different amounts of bisphenol A type epoxy resin

[0133] Item Control amount Wear amount (mg) Salt spray resistance (h) Coating impact resistance Paint film hardness (HR) Adhesion rating Example 1 60g 17.1208 1218 50 cm 84 1 Example 5 50g 25.8764 826 47 cm 74.5 1~2 Example 6 55g 17.1214 1248 50 cm 84 1

[0134] From Table 2, the addition of 50-60 mass parts of epoxy resin can effectively improve the comprehensive performance of the coating.

[0135] Table 3: Performance data of paint surfaces prepared with different amounts of methyl tetrahydrophthalic anhydride curing agent

[0136] Item Control amount Wear amount (mg) Salt spray resistance (h) Coating impact resistance Paint film hardness (HR) Adhesion rating Example 1 40g 17.1208 1218 50 cm 84 1 Example 7 30g 17.1216 1247 50 cm 84 1 Example 8 35g 17.1224 1250 50 cm 84 1 Example 9 50g 24.1576 863 36 cm 84 1

[0137] From Table 3, different amounts of methyl tetrahydrophthalic anhydride curing agent have little effect on the performance of the coating, but excessive addition of the curing agent can cause the dense epoxy paint film to become loose, thereby reducing the comprehensive performance, and therefore 30-40 mass parts is preferred.

[0138] Table 4: Performance data of paint surfaces prepared with different curing agents

[0139] Item Control amount Wear amount (mg) Salt spray resistance (h) Coating impact resistance Paint film hardness (HR) Adhesion rating Example 1 50 cm 17.1208 1218 Example 10 84 1 Methyltetrahydrophthalic anhydride 50 cm 17.2675 1285 Example 11 82 1 Phthalic anhydride 50 cm 17.1185 1246 Example 12 84 1

[0140] From Table 4, different anhydride curing agents have little effect on the performance of the coating, and the most preferred is methyl hexahydrophthalic anhydride.

[0141] Table 5: Performance data of paint surfaces prepared with different catalysts

[0142] Methylhexahydrophthalic anhydride 50 cm Item Control amount Wear amount (mg) Salt spray resistance (h) Coating impact resistance Paint film hardness (HR) Adhesion rating 17.1208 1218 Example 1 84 1 Barium hydroxide 50 cm 16.9994 1225 Example 13 85 1 Potassium hydroxide 50 cm 17.1258 1256 Example 14 86 1 Sodium hydroxide 50 cm 17.6848 1278 Example 15 83 1

[0143] From Table 5, different catalysts have little effect on the performance of the coating, and the most preferred is potassium permanganate.

[0144] Table 6: Different molecular weight pore size semi-permeable membranes

[0145] Calcium hydroxide 50 cm Item Control amount Wear amount (mg) Salt spray resistance (h) Coating impact resistance Paint film hardness (HR) 3000 17.1208 1218 Adhesion rating 84 1 Example 1 1000 18.238 1105 50 cm 85 1 Example 16 5000 34.2860 828 50 cm 72 1~2 Example 17 10000 26 cm

[0146] From Table 6, the modified agent prepared by filtering the semi-permeable membrane with a molecular weight pore size of 1000-3000 has excellent performance, and the performance is best when the pore size is 3000, the performance decreases significantly when the pore size is 5000, and the coating cannot be cured when the pore size is 10000.

[0147] Table Seven: Performance data of paint surfaces prepared by different rotary evaporation temperatures

[0148] Example 18 Could not be cured Item Control amount Wear amount (mg) Salt spray resistance (h) Coating impact resistance Paint film hardness (HR) Adhesion rating 17.1208 1218 Example 1 84 1 Without rotavapor separation 150℃ 17.2356 1279 50 cm 83 1 Example 19 >160℃ 40.2356 642 50 cm 65 3 Example 20 160℃ 17.1482 1230 25 cm 86 1 Example 21 140℃ Could not be cured

[0149] As can be seen from Table Seven, when the rotary evaporation temperature is less than 150°C, small molecules cannot be separated from the modifier, resulting in the content of polybenzene end hydroxyl cluster siloxane being impure, which causes the paint surface to be unable to cure. Rotary evaporation at 150-160°C has good comprehensive performance, and at 140°C, the formation of polybenzene end hydroxyl cluster siloxane B polymorph cannot be cured, and at >160°C, the performance is severely decreased.

[0150] Table Eight: Performance data of paint surfaces prepared by different other control amounts

[0151] Item Control amount Wear amount (mg) Salt spray resistance (h) Coating impact resistance Paint film hardness (HR) Adhesion rating Example 1 17.1208 1218 50 cm 84 1 Example 22 Stirring temperature 130°C 17.9808 1223 50 cm 84 1 Example 23 Ambient standing for 18 h, atmospheric pre-curing at 60°C for 4 h, followed by curing at 160°C under atmosphere for 16 h 17.0045 1247 50 cm 84 1 Example 24 Spray curing, rate of high-speed stirring 1000 r / min, 0.5 h; ultrasonic dispersion time 0.2 h 17.1008 1247 50 cm 84 1 Example 25 Without standing, directly cured 19.2350 1123 46 cm 83 1

[0152] As can be seen from Table Eight, the paint film without vacuum standing causes internal micro-bubbles to be unable to be removed, thereby affecting the comprehensive performance of the paint film. The example without pre-curing shows that the wear of the paint film is increased and the salt spray resistance is decreased, which is because pre-curing can improve the density of the paint film, thereby improving the comprehensive performance.

[0153] Although the preferred embodiments of the present application are described above with reference to the accompanying drawings, the present application is not limited to the specific embodiments described above, and the specific embodiments described above are merely illustrative and are not limiting. Those of ordinary skill in the art can make many forms of specific changes under the inspiration of the present application without departing from the purpose of the present application and the scope protected by the claims, and these all belong to the scope of protection of the present application.

Claims

1. A process for the preparation of a modified abrasion resistant anticorrosive resinous coating characterized in that, The application relates to a modified wear-resistant and corrosion-resistant resin coating preparation method. The preparation method comprises the following steps: mixing 50-60 parts of epoxy resin with 30-40 parts of a curing agent to prepare a homogeneous mother liquor; 5-8 parts of a modifier are added into the homogeneous mother liquor, mixed uniformly, and reacted to obtain a liquid modified wear-resistant and corrosion-resistant coating; Standing to eliminate the bubbles generated in the reaction process; Curing to obtain a solid modified wear-resistant and corrosion-resistant resin coating.

2. A process for the preparation of a modified wear resistant anticorrosive resinous coating as claimed in claim 1, wherein, The epoxy resin is a bisphenol A type epoxy resin or an epoxidized olefin compound; The curing agent is one of methyl tetrahydrophthalic anhydride, phthalic anhydride and methyl hexahydrophthalic anhydride.

3. The method for preparing a modified wear-resistant and anti-corrosion resin coating according to claim 1, characterized in that, The modifier is a polyphenyl terminal hydroxyl cluster siloxane, and the preparation method of the polyphenyl terminal hydroxyl cluster siloxane is as follows: 30-40 parts of 1, 4-butanediol, 20-30 parts of phenyl triethoxysilane and 5-10 parts of a catalyst are stirred and reacted at 130-150 DEG C for 3-5 h, filtered through a semi-permeable membrane with a molecular weight pore size of 1000-3000, washed, and dried to obtain the polyphenyl terminal hydroxyl cluster siloxane.

4. The method of claim 3, wherein the modified wear-resistant anticorrosive resin coating is prepared by adding the anticorrosive agent to the resin coating, and then adding the wear-resistant agent to the resin coating. The polyphenyl terminal hydroxyl cluster siloxane is a mixture of polyphenyl terminal hydroxyl cluster siloxane A and structural polyphenyl terminal hydroxyl cluster siloxane B, or the polyphenyl terminal hydroxyl cluster siloxane A alone, or the polyphenyl terminal hydroxyl cluster siloxane B alone. The structural formula of the polyphenyl terminal hydroxyl cluster siloxane A is as follows: ; The structural formula of the polyphenyl terminal hydroxyl cluster siloxane B is as follows: ; The polyphenyl terminal hydroxyl cluster siloxane A alone and the polyphenyl terminal hydroxyl cluster siloxane B alone are separated by a rotary evaporation method, the distillate is the polyphenyl terminal hydroxyl cluster siloxane A, and the residue is the polyphenyl terminal hydroxyl cluster siloxane B. The temperature of the rotary evaporation method is 150-160 DEG C.

5. The method of preparing a modified wear resistant anticorrosive resinous coating as claimed in claim 3, wherein, The catalyst is one of barium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide.

6. The method of preparing a modified wear resistant anticorrosive resinous coating as claimed in claim 3, wherein, The reaction process is as follows: first, 1, 4-butanediol and phenyl triethoxysilane are simultaneously put into a reaction container according to the mass fraction, mixed at a rotating speed of 5-20 r / min under the protection of a nitrogen atmosphere or an argon atmosphere at 50-60 DEG C for 5-10 min; then, the catalyst is put into the reaction container according to the mass fraction, and the reaction is carried out under the protection of the atmosphere and the stirring at a rotating speed of 50-60 r / min; The washing is performed by using deionized water for 2-5 times; The drying is performed in a nitrogen blowing drying environment at 60-90 DEG C for 8-10 h.

7. The method for preparing a modified wear-resistant and corrosion-resistant resin coating according to claim 1, characterized in that, The reaction temperature of the modifier and the homogeneous mother liquor is 20-80 DEG C, and the mixing mode is high-speed stirring or ultrasonic dispersion. The rotating speed of the high-speed stirring is not less than 500 r / min, and the high-speed stirring time is 0.5-5 h. The ultrasonic dispersion time is 0.2 h-2 h.

8. The method for preparing a modified wear-resistant and corrosion-resistant resin coating according to claim 1, characterized in that, The standing is performed under a vacuum degree of 0.07 MPa-0.08 MPa for 12-18 h.

9. The method for preparing a modified wear-resistant and anti-corrosion resin coating according to claim 1, characterized in that, The curing process is as follows: first, pre-curing is performed at 50-60 DEG C under an environment of 0.8 KPa-0.6 KPa for 3-4 h, and then curing is performed under an atmospheric environment at 140-160 DEG C for 12-16 h; After the curing, standing is performed to eliminate the stress, and the standing condition is horizontal standing at 50-60 DEG C under an atmospheric environment for 5-6 h.

10. A modified abrasion resistant anticorrosive resinous coating characterized by, The preparation method is obtained by any one of claims 1-9.

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