Waterproof anticorrosive paint as well as preparation method and application thereof

Abstract

The invention discloses a waterproof anticorrosive coating and a preparation method and application thereof, and relates to the technical field of coatings, and the waterproof anticorrosive coating is prepared from the following raw materials in parts by weight: 30-40 parts of carboxyl-terminated hyperbranched polyester resin, 20-30 parts of carboxyl-terminated functional polyamide, 10-15 parts of hyperbranched polyurethane containing epoxy groups, 15-20 parts of filler, 1-3 parts of (3, 6-diamino acridine-9-yl) boric acid, 1-3 parts of 1, 3, 5-trimethyl-1, 3, 5-trimethyl-1, 3, 5-trimethyl-1, 3, 5-trimethyl-1, 3, 5-trimethyl-1, 3, 5-trimethyl-1, 3, 5-trimethyl-1, 3, 5-trimethyl-1, 3, 5- the component A is prepared from the following components in parts by weight: 3-5 parts of 2, 3, 5-triglycidyl-S-triazinetrione, 1-2 parts of a coupling agent, 0.8-1.2 parts of a flatting agent and 0.6-1.3 parts of a defoaming agent; the carboxyl-terminated functional polyamide comprises a structural unit introduced by the following monomers: N-(4H-1, 2, 4-triazole-4-yl) diphenylamine-4, 4 '-dicarboxylic acid, and 3, 3'-diamino-4, 4 '-difluorodiphenyl sulfone. The coating is good in waterproof and anti-corrosion performance, high in adhesive force with a base material, sufficient in solvent resistance and aging resistance and long in service life.

Description

Technical Field

[0001] The present invention relates to the technical field of coatings, and in particular to a waterproof and anti-corrosion coating and a preparation method and application thereof. Background Art

[0002] Paint is an important chemical material, widely used in construction, automobiles, machinery, household appliances, light industrial instruments, durable consumer goods, aerospace, ships and other fields, and is an indispensable material in the national economy. At present, the vast majority of domestic bicycle industry still uses oil-based paint, which contains a large amount of volatile, toxic and harmful organic solvents, and its safety and environmental protection need to be further improved.

[0003] Compared with traditional oily paints, water-based paints such as water-based acrylic resins have the advantages of being pollution-free, green and environmentally friendly, and having excellent film-forming properties. They are widely used in the fields of metal anti-corrosion and wood protection. However, water-based acrylic resin paints have poor water resistance, poor bonding strength with metal substrates, and the paint film is easy to fall off under long-term conditions, and cannot protect and prevent the metal substrate from corrosion. It is in this situation that powder coatings came into being. Powder coatings have more prominent green and environmentally friendly performance and are more applicable. However, waterproof and anti-corrosion powder coatings suitable for the bicycle industry are relatively rare. Existing powder coatings used in the bicycle industry also have more or less technical defects such as limited waterproof and anti-corrosion performance, poor adhesion to the substrate, insufficient solvent resistance and aging resistance, and short service life.

[0004] In order to solve the above problems, the Chinese invention patent with the authorization announcement number CN111073470B discloses a friction-resistant and anti-fading powder coating and application for bicycles. Its components and their weight proportions are as follows: 63-69 parts of polyester resin; 4.2-5.1 parts of TGIC; 14-23 parts of filler; 1-10 parts of rutile titanium dioxide; 2-15 parts of homemade colorant; 3.1-3.9 parts of additives. The powder coating of the invention has high leveling and high gloss, and is also friction-resistant and anti-fading. The coating formed by the powder coating on the bicycle has good leveling and high gloss. At the same time, the wear resistance is greatly improved compared with the ordinary powder coating coating, and it does not fade when wiped. It has excellent decorative and protective properties, providing decorative and protective properties for bicycles. However, its waterproof and anti-corrosion properties and solvent resistance still need to be further improved.

[0005] It can be seen that it is particularly important to develop a waterproof and anti-corrosion coating with good waterproof and anti-corrosion properties, strong adhesion to the substrate, sufficient solvent resistance and aging resistance, and long service life, as well as its preparation method and application. Summary of the invention

[0006] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a waterproof and anti-corrosion coating with good waterproof and anti-corrosion properties, strong adhesion to the substrate, sufficient solvent resistance and aging resistance, and long service life, as well as a preparation method and application thereof.

[0007] To achieve the above-mentioned purpose, the technical scheme adopted by the present invention is: a waterproof and anticorrosive coating, which is made of the following raw materials in parts by weight: 30-40 parts of terminal carboxyl hyperbranched polyester resin, 20-30 parts of terminal carboxyl functional polyamide, 10-15 parts of epoxy-containing hyperbranched polyurethane, 15-20 parts of filler, 1-3 parts of (3,6-diaminoacridine-9-yl)boric acid, 3-5 parts of 1,3,5-triglycidyl-S-triazinetrione, 1-2 parts of coupling agent, 0.8-1.2 parts of leveling agent, and 0.6-1.3 parts of defoaming agent; the terminal carboxyl functional polyamide includes structural units introduced by the following monomers: N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid and 3,3'-diamino-4,4'-difluorodiphenyl sulfone.

[0008] Preferably, the carboxyl-terminated hyperbranched polyester resin is carboxyl-terminated hyperbranched polyester resin Hyper C203, which is provided by Wuhan Hyperbranched Resin Technology Co., Ltd.

[0009] Preferably, the preparation method of the terminal carboxyl functional polyamide comprises the following steps: adding N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid, 3,3'-diamino-4,4'-difluorodiphenyl sulfone and a catalyst to a high boiling point solvent and mixing them evenly to obtain a mixture, then adding the mixture to a reactor, replacing the air in the reactor with an inert gas, reacting at 120-130°C under normal pressure for 3-5 hours, then heating to 235-255°C, and performing a condensation reaction at 100-300 Pa for 18-22 hours, then adding a chain terminator, continuing to stir the reaction for 1-2 hours, then cooling to room temperature, adjusting to normal pressure, precipitating in water, washing the crude product with ethanol for 3-6 times, and then drying it in a vacuum drying oven at 85-95°C to constant weight to obtain the terminal carboxyl functional polyamide.

[0010] Preferably, the molar ratio of N-(4H-1,2,4-triazol-4-yl)diphenylamine-4,4'-dicarboxylic acid, 3,3'-diamino-4,4'-difluorodiphenyl sulfone, catalyst, high boiling point solvent and chain terminator is 1:1:(0.8-1):(8-15):0.1.

[0011] Preferably, the catalyst is at least one of thiophosphonate, phosphorous acid, and thiophosphoramide; the high boiling point solvent is dimethyl sulfoxide; and the inert gas is any one of nitrogen, helium, neon, and argon.

[0012] Preferably, the chain terminator is N-(4H-1,2,4-triazol-4-yl)diphenylamine-4,4'-dicarboxylic acid.

[0013] Preferably, there is no special requirement for the source of the hyperbranched polyurethane containing epoxy groups. In one embodiment of the present invention, the hyperbranched polyurethane containing epoxy groups is prepared according to the method of Example 3 of the Chinese invention patent with application announcement number CN105085866A.

[0014] Preferably, the filler is a mixture of high-gloss barium and precipitated barium in a mass ratio of 1:(0.8-1.2).

[0015] Preferably, the particle size of the filler is 1200-2000 mesh.

[0016] Preferably, the coupling agent is at least one of silane coupling agent KH550, silane coupling agent KH560, and silane coupling agent KH570.

[0017] Preferably, the defoaming agent is one or more of tributyl phosphate, defoaming agent Deqian 3100, and defoaming agent BYK088; the leveling agent is at least one of German BYK leveling agent BYK-333 and silicone leveling agent HY-5030.

[0018] Another object of the present invention is to provide a method for preparing a waterproof and anti-corrosion coating, comprising the following steps: mixing the raw materials uniformly by weight, feeding them into a twin-screw extruder for extrusion, crushing them, and then feeding them into a grinder for crushing and grading, separating out fine powder and impurities through a cyclone separator, and separating out the product with a powder sieve having a mesh size of 100-200, and ripening them for 1-3 days to obtain a finished waterproof and anti-corrosion coating.

[0019] Another object of the present invention is to provide an application of the waterproof and anti-corrosion coating in bicycle painting.

[0020] Due to the application of the above technical solution, the present invention has the following beneficial effects:

[0021] (1) The preparation method of the waterproof and anti-corrosion coating disclosed in the present invention has simple process, convenient operation and control, high preparation efficiency and finished product qualification rate, low dependence on equipment, suitable for continuous large-scale production, and has high promotion and application value.

[0022] (2) The waterproof and anticorrosive coating disclosed in the present invention is prepared from the following raw materials in parts by weight: 30-40 parts of a carboxyl-terminated hyperbranched polyester resin, 20-30 parts of a carboxyl-terminated functional polyamide, 10-15 parts of a hyperbranched polyurethane containing an epoxy group, 15-20 parts of a filler, 1-3 parts of (3,6-diaminoacridine-9-yl)boric acid, 3-5 parts of 1,3,5-triglycidyl-S-triazinetrione, 1-2 parts of a coupling agent, 0.8-1.2 parts of a leveling agent, and 0.6-1.3 parts of a defoaming agent; the carboxyl-terminated functional polyamide includes a structural unit introduced by the following monomers: N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid and 3,3'-diamino-4,4'-difluorodiphenyl sulfone. Through the mutual coordination and joint action of various raw materials, the finished coating has excellent waterproof and anti-corrosion properties, strong adhesion to the substrate, sufficient solvent resistance and aging resistance, and a long service life.

[0023] (3) The waterproof and anticorrosive coating disclosed in the present invention comprises raw materials containing carboxyl and boric acid groups which can react chemically with raw materials containing epoxy groups to be cured. Meanwhile, raw materials containing amino groups can react chemically with raw materials containing epoxy groups, so that after the powder coating is cured, the molecular structure of the coating film formed contains multiple interpenetrating network structures at the same time. These interpenetrating network structures cooperate with each other to improve the waterproof and anticorrosive properties of the coating film. By rationally selecting the types and dosage ratios of various raw materials, triazole diphenylamine, difluorodiphenyl sulfone, acridine, triazine trione, boric acid group, hydroxyl group, hyperbranched polyester, amide and hyperbranched polyurethane structures are simultaneously introduced into the molecular structure of the coating film. Under the multiple effects of electronic effect, steric effect and conjugation effect, these groups or structures make the prepared coating have better waterproof and anticorrosive properties, stronger adhesion to the substrate, better solvent resistance and aging resistance, and longer service life.

[0024] (4) The waterproof and anticorrosive coating disclosed in the present invention, the terminal carboxyl functional polyamide includes structural units introduced by the following monomers: N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid, 3,3'-diamino-4,4'-difluorodiphenyl sulfone; by simultaneously introducing triazole, difluorodiphenyl sulfone and amide groups into the molecular structure of the raw material, it is endowed with excellent film-forming property and aging resistance. After being added to the coating, it cooperates with other raw material components in the coating to effectively improve the waterproof and anticorrosive performance and solvent resistance. DETAILED DESCRIPTION

[0025] The following description is used to disclose the present invention so that those skilled in the art can implement the present invention. The preferred embodiments described below are only examples, and those skilled in the art may think of other obvious variations.

[0026] Example 1

[0027] A waterproof and anticorrosive coating is prepared from the following raw materials in parts by weight: 30 parts of carboxyl-terminated hyperbranched polyester resin, 20 parts of carboxyl-terminated functional polyamide, 10 parts of hyperbranched polyurethane containing epoxy groups, 15 parts of fillers, 1 part of (3,6-diaminoacridine-9-yl)boric acid, 3 parts of 1,3,5-triglycidyl-S-triazinetrione, 1 part of coupling agent, 0.8 parts of leveling agent, and 0.6 parts of defoaming agent; the carboxyl-terminated functional polyamide comprises structural units introduced by the following monomers: N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid and 3,3'-diamino-4,4'-difluorodiphenyl sulfone.

[0028] The carboxyl-terminated hyperbranched polyester resin is carboxyl-terminated hyperbranched polyester resin Hyper C203, which is provided by Wuhan Hyperbranched Resin Technology Co., Ltd.

[0029] The preparation method of the carboxyl-terminated functional polyamide comprises the following steps: adding N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid, 3,3'-diamino-4,4'-difluorodiphenyl sulfone and a catalyst into a high boiling point solvent and mixing them evenly to obtain a mixed material, then adding the mixed material into a reaction kettle, replacing the air in the kettle with an inert gas, reacting at 120°C for 3 hours at normal pressure, then heating to 235°C, performing a polycondensation reaction at 100 Pa for 18 hours, then adding a chain terminator, continuing to stir and react for 1 hour, then cooling to room temperature, adjusting to normal pressure, precipitating in water, washing the crude product with ethanol for 3 times, and then The catalyst is placed in a vacuum drying oven at 85° C. and dried to constant weight to obtain a carboxyl-terminated functional polyamide; the molar ratio of the N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid, 3,3'-diamino-4,4'-difluorodiphenyl sulfone, catalyst, high boiling point solvent, and chain terminator is 1:1:0.8:8:0.1; the catalyst is a phosphothioate; the high boiling point solvent is dimethyl sulfoxide; the inert gas is nitrogen; the chain terminator is N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid; the M of the obtained carboxyl-terminated functional polyamide is measured by GPC test. n =14170 g / mol, M W / M n =1.336; through elemental analysis and weight change calculation, the molar ratio of the structural units introduced by N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid and 3,3'-diamino-4,4'-difluorodiphenyl sulfone in the terminal carboxyl functional polyamide is the same as the theoretical value.

[0030] The epoxy-containing hyperbranched polyurethane is prepared according to the method of Example 3 of the Chinese invention patent with application announcement number CN105085866A; the filler is a mixture of high-gloss barium and precipitated barium in a mass ratio of 1:0.8; the particle size of the filler is 1200 mesh; the coupling agent is silane coupling agent KH550; the defoaming agent is tributyl phosphate; and the leveling agent is German BYK leveling agent BYK-333.

[0031] A preparation method of a waterproof and anti-corrosion coating comprises the following steps: mixing raw materials uniformly by weight, feeding them into a twin-screw extruder for extrusion, crushing them, and finally feeding them into a grinder for pulverization and classification, separating excessively fine powder and impurities through a cyclone separator, and separating the product through a powder sieve with a 100-mesh powder sieve, and aging them for 1 day to obtain a finished waterproof and anti-corrosion coating.

[0032] Example 2

[0033] A waterproof and anticorrosive coating is prepared from the following raw materials in parts by weight: 33 parts of carboxyl-terminated hyperbranched polyester resin, 23 parts of carboxyl-terminated functional polyamide, 12 parts of hyperbranched polyurethane containing epoxy groups, 17 parts of filler, 1.5 parts of (3,6-diaminoacridine-9-yl)boric acid, 3.5 parts of 1,3,5-triglycidyl-S-triazinetrione, 1.2 parts of coupling agent, 0.9 parts of leveling agent, and 0.8 parts of defoaming agent; the carboxyl-terminated functional polyamide comprises structural units introduced by the following monomers: N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid and 3,3'-diamino-4,4'-difluorodiphenyl sulfone.

[0034] The carboxyl-terminated hyperbranched polyester resin is carboxyl-terminated hyperbranched polyester resin Hyper C203, which is provided by Wuhan Hyperbranched Resin Technology Co., Ltd.

[0035] The preparation method of the carboxyl-terminated functional polyamide comprises the following steps: adding N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid, 3,3'-diamino-4,4'-difluorodiphenyl sulfone and a catalyst into a high boiling point solvent and mixing them evenly to obtain a mixed material; then adding the mixed material into a reaction kettle, replacing the air in the kettle with an inert gas, reacting at 123°C for 3.5 hours at normal pressure, then heating to 240°C, performing a polycondensation reaction at 150 Pa for 19 hours, then adding a chain terminator, continuing to stir and react for 1.2 hours, then cooling to room temperature, adjusting to normal pressure, and precipitating in water. The crude product is washed with ethanol for 4 times, and then placed in a vacuum drying oven at 87° C. to dry to constant weight to obtain a carboxyl-terminated functional polyamide; the molar ratio of N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid, 3,3'-diamino-4,4'-difluorodiphenyl sulfone, catalyst, high boiling point solvent, and chain terminator is 1:1:0.85:10:0.1; the catalyst is phosphorous acid; the high boiling point solvent is dimethyl sulfoxide; the inert gas is helium; and the chain terminator is N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid.

[0036] The hyperbranched polyurethane containing epoxy groups is made according to the method of Example 3 of the Chinese invention patent with application announcement number CN105085866A; the filler is a mixture of high-gloss barium and precipitated barium in a mass ratio of 1:0.9; the particle size of the filler is 1400 mesh; the coupling agent is silane coupling agent KH560; the defoamer is defoamer Deqian 3100; and the leveling agent is silicone leveling agent HY-5030.

[0037] A preparation method of a waterproof and anti-corrosion coating comprises the following steps: mixing raw materials uniformly by weight, feeding them into a twin-screw extruder for extrusion, crushing them, and finally feeding them into a grinder for pulverization and classification, separating out excessively fine powder and impurities through a cyclone separator, and separating out products through a powder sieve with a 130-mesh powder sieve, and aging them for 1.5 days to obtain a finished waterproof and anti-corrosion coating.

[0038] Example 3

[0039] A waterproof and anticorrosive coating is prepared from the following raw materials in parts by weight: 35 parts of carboxyl-terminated hyperbranched polyester resin, 25 parts of carboxyl-terminated functional polyamide, 13 parts of hyperbranched polyurethane containing epoxy groups, 18 parts of fillers, 2 parts of (3,6-diaminoacridine-9-yl)boric acid, 4 parts of 1,3,5-triglycidyl-S-triazinetrione, 1.5 parts of coupling agent, 1 part of leveling agent, and 0.9 part of defoaming agent; the carboxyl-terminated functional polyamide comprises structural units introduced by the following monomers: N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid and 3,3'-diamino-4,4'-difluorodiphenyl sulfone.

[0040] The carboxyl-terminated hyperbranched polyester resin is carboxyl-terminated hyperbranched polyester resin Hyper C203, which is provided by Wuhan Hyperbranched Resin Technology Co., Ltd.

[0041] The preparation method of the carboxyl-terminated functional polyamide comprises the following steps: adding N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid, 3,3'-diamino-4,4'-difluorodiphenyl sulfone and a catalyst into a high boiling point solvent and mixing them evenly to obtain a mixed material, then adding the mixed material into a reaction kettle, replacing the air in the kettle with an inert gas, reacting at 125°C for 4 hours at normal pressure, then heating to 245°C, performing a polycondensation reaction at 200 Pa for 20 hours, then adding a chain terminator, continuing to stir and react for 1.5 hours, then cooling to room temperature, adjusting to normal pressure, and precipitating in water. The crude product is washed with ethanol for 5 times, and then placed in a vacuum drying oven at 90°C to dry to constant weight to obtain a carboxyl-terminated functional polyamide; the molar ratio of the N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid, 3,3'-diamino-4,4'-difluorodiphenyl sulfone, catalyst, high boiling point solvent, and chain terminator is 1:1:0.9:12:0.1; the catalyst is thiophosphoramide; the high boiling point solvent is dimethyl sulfoxide; the inert gas is neon; and the chain terminator is N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid.

[0042] The hyperbranched polyurethane containing epoxy groups is made according to the method of Example 3 of the Chinese invention patent with application announcement number CN105085866A; the filler is a mixture of high-gloss barium and precipitated barium in a mass ratio of 1:1; the particle size of the filler is 1900 mesh; the coupling agent is silane coupling agent KH570; the defoamer is defoamer BYK088; and the leveling agent is German BYK leveling agent BYK-333.

[0043] A preparation method of a waterproof and anti-corrosion coating comprises the following steps: mixing raw materials uniformly by weight, feeding them into a twin-screw extruder for extrusion, crushing them, and finally feeding them into a grinder for pulverization and classification, separating excessively fine powder and impurities through a cyclone separator, and separating the product through a powder sieve with a 150-mesh powder sieve, and aging them for 2 days to obtain a finished waterproof and anti-corrosion coating.

[0044] Example 4

[0045] A waterproof and anticorrosive coating is prepared from the following raw materials in parts by weight: 38 parts of carboxyl-terminated hyperbranched polyester resin, 28 parts of carboxyl-terminated functional polyamide, 14 parts of hyperbranched polyurethane containing epoxy groups, 19 parts of filler, 2.5 parts of (3,6-diaminoacridine-9-yl)boric acid, 4.5 parts of 1,3,5-triglycidyl-S-triazinetrione, 1.8 parts of coupling agent, 1.1 parts of leveling agent, and 1.2 parts of defoaming agent; the carboxyl-terminated functional polyamide comprises structural units introduced by the following monomers: N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid and 3,3'-diamino-4,4'-difluorodiphenyl sulfone.

[0046] The carboxyl-terminated hyperbranched polyester resin is carboxyl-terminated hyperbranched polyester resin Hyper C203, which is provided by Wuhan Hyperbranched Resin Technology Co., Ltd.

[0047] The preparation method of the carboxyl-terminated functional polyamide comprises the following steps: adding N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid, 3,3'-diamino-4,4'-difluorodiphenyl sulfone and a catalyst into a high boiling point solvent and mixing them evenly to obtain a mixed material, then adding the mixed material into a reaction kettle, replacing the air in the kettle with an inert gas, reacting at 128°C for 4.5 hours at normal pressure, then heating to 250°C, performing a polycondensation reaction at 250 Pa for 21 hours, then adding a chain terminator, continuing to stir and react for 1.8 hours, then cooling to room temperature, adjusting to normal pressure, precipitating in water, washing the crude product with ethanol for 6 times, The mixture is then placed in a vacuum drying oven and dried at 93° C. to constant weight to obtain a carboxyl-terminated functional polyamide; the molar ratio of the N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid, 3,3'-diamino-4,4'-difluorodiphenyl sulfone, catalyst, high boiling point solvent, and chain terminator is 1:1:0.95:14:0.1; the catalyst is a mixture of thiophosphonate, phosphorous acid, and thiophosphoramide in a mass ratio of 1:1:1; the high boiling point solvent is dimethyl sulfoxide; the inert gas is argon; and the chain terminator is N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid.

[0048] The epoxy-containing hyperbranched polyurethane is prepared according to the method of Example 3 of the Chinese invention patent with application announcement number CN105085866A; the filler is a mixture of high-gloss barium and precipitated barium in a mass ratio of 1:1.1; the particle size of the filler is 1900 mesh; the coupling agent is a mixture of silane coupling agent KH550, silane coupling agent KH560, and silane coupling agent KH570 in a mass ratio of 1:2:3; the defoamer is a mixture of tributyl phosphate, defoamer Deqian 3100, and defoamer BYK088 in a mass ratio of 1:3:5; the leveling agent is a mixture of German BYK leveling agent BYK-333 and silicone leveling agent HY-5030 in a mass ratio of 1:2.

[0049] A preparation method of a waterproof and anti-corrosion coating comprises the following steps: mixing raw materials uniformly by weight, feeding them into a twin-screw extruder for extrusion, crushing them, and finally feeding them into a grinder for pulverization and classification, separating out excessively fine powder and impurities through a cyclone separator, and separating out products through a powder sieve with a 190-mesh powder sieve, and aging them for 2.5 days to obtain a finished waterproof and anti-corrosion coating.

[0050] Example 5

[0051] A waterproof and anticorrosive coating is prepared from the following raw materials in parts by weight: 40 parts of carboxyl-terminated hyperbranched polyester resin, 30 parts of carboxyl-terminated functional polyamide, 15 parts of hyperbranched polyurethane containing epoxy groups, 20 parts of filler, 3 parts of (3,6-diaminoacridine-9-yl)boric acid, 5 parts of 1,3,5-triglycidyl-S-triazinetrione, 2 parts of coupling agent, 1.2 parts of leveling agent, and 1.3 parts of defoaming agent; the carboxyl-terminated functional polyamide comprises structural units introduced by the following monomers: N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid and 3,3'-diamino-4,4'-difluorodiphenyl sulfone.

[0052] The carboxyl-terminated hyperbranched polyester resin is carboxyl-terminated hyperbranched polyester resin Hyper C203, which is provided by Wuhan Hyperbranched Resin Technology Co., Ltd.

[0053] The preparation method of the carboxyl-terminated functional polyamide comprises the following steps: adding N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid, 3,3'-diamino-4,4'-difluorodiphenyl sulfone and a catalyst into a high boiling point solvent and mixing them evenly to obtain a mixed material, then adding the mixed material into a reaction kettle, replacing the air in the kettle with an inert gas, reacting at 130° C. for 5 hours at normal pressure, then heating to 255° C., performing a polycondensation reaction at 300 Pa for 22 hours, then adding a chain terminator, continuing to stir and react for 2 hours, then cooling to room temperature, adjusting to normal pressure, and precipitating in water. The crude product is washed with ethanol for 6 times, and then dried in a vacuum drying oven at 95° C. to constant weight to obtain a carboxyl-terminated functional polyamide; the molar ratio of the N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid, 3,3'-diamino-4,4'-difluorodiphenyl sulfone, catalyst, high boiling point solvent, and chain terminator is 1:1:1:15:0.1; the catalyst is a thiophosphonate; the high boiling point solvent is dimethyl sulfoxide; the inert gas is nitrogen; and the chain terminator is N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid.

[0054] The hyperbranched polyurethane containing epoxy groups is made according to the method of Example 3 of the Chinese invention patent with application announcement number CN105085866A; the filler is a mixture of high-gloss barium and precipitated barium in a mass ratio of 1:1.2; the particle size of the filler is 2000 mesh; the coupling agent is silane coupling agent KH560; the defoaming agent is tributyl phosphate; and the leveling agent is German BYK leveling agent BYK-333.

[0055] A preparation method of a waterproof and anticorrosive coating comprises the following steps: mixing raw materials uniformly by weight, feeding them into a twin-screw extruder for extrusion, crushing them, and then feeding them into a grinder for pulverization and classification, separating excessively fine powder and impurities through a cyclone separator, and separating products through a powder sieve with a 200-mesh powder sieve, and aging them for a3 days to obtain a finished waterproof and anticorrosive coating.

[0056] Comparative Example 1

[0057] A waterproof and anticorrosive coating is substantially the same as Example 1, except that an equal amount of a carboxyl-terminated hyperbranched polyester resin is used to replace the carboxyl-terminated functional polyamide, and (3,6-diaminoacridine-9-yl)boric acid is not added.

[0058] Comparative Example 2

[0059] A waterproof and anticorrosive coating is substantially the same as Example 1, except that an equal amount of terephthalic acid is used to replace N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid, and 1,3,5-triglycidyl-S-triazinetrione is not added.

[0060] In order to further illustrate the beneficial technical effects of the waterproof and anticorrosive coatings involved in each embodiment of the present invention, the waterproof and anticorrosive coatings involved in Examples 1-5 and Comparative Examples 1-2 were subjected to relevant performance tests. The test methods and test results are shown in Table 1. The curing conditions of each coating during the test are: 200°C, 10min. The salt spray test is passed when the width of unilateral penetration corrosion under the membrane on both sides of the line does not exceed 2mm after 1320h of the salt spray test, otherwise it fails; the artificial aging test is passed when there is no abnormal phenomenon such as powdering, cracking, peeling, etc. after 1000h of artificial aging QUV, otherwise it fails. Water resistance is tested in accordance with GB / T1733-1993, and the time when rust spots begin to appear on the surface is recorded in days. The longer the time, the better the water resistance of the coating.

[0061] Table 1

[0062]

[0063]

[0064] As can be seen from Table 1, the waterproof and anticorrosive coatings involved in the embodiments of the present invention have better solvent resistance, moisture and heat resistance, artificial aging resistance, salt spray resistance and water resistance than the comparative example products, and have stronger adhesion to the substrate. The use of terminal carboxyl hyperbranched polyester resin, (3,6-diaminoacridine-9-yl)boric acid, N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid and 1,3,5-triglycidyl-S-triazinetrione is beneficial to improving the above properties.

[0065] The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the contents of the present invention and implement them accordingly. They cannot be used to limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A waterproof and anti-corrosion coating, characterized in that: The invention is prepared from the following raw materials in parts by weight: 30-40 parts of carboxyl-terminated hyperbranched polyester resin, 20-30 parts of carboxyl-terminated functional polyamide, 10-15 parts of hyperbranched polyurethane containing epoxy group, 15-20 parts of filler, 1-3 parts of (3,6-diaminoacridine-9-yl)boric acid, 3-5 parts of 1,3,5-triglycidyl-S-triazinetrione, 1-2 parts of coupling agent, 0.8-1.2 parts of leveling agent and 0.6-1.3 parts of defoaming agent; the carboxyl-terminated functional polyamide comprises structural units introduced by the following monomers: N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid and 3,3'-diamino-4,4'-difluorodiphenyl sulfone.

2. The waterproof and anticorrosive coating according to claim 1, characterized in that: The carboxyl-terminated hyperbranched polyester resin is carboxyl-terminated hyperbranched polyester resin Hyper C203.

3. The waterproof and anticorrosive coating according to claim 1, characterized in that: The preparation method of the terminal carboxyl functional polyamide comprises the following steps: adding N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid, 3,3'-diamino-4,4'-difluorodiphenyl sulfone and a catalyst into a high boiling point solvent and mixing them evenly to obtain a mixed material, then adding the mixed material into a reaction kettle, replacing the air in the kettle with an inert gas, reacting at 120-130° C. under normal pressure for 3-5 hours, then heating to 235-255° C., carrying out a polycondensation reaction at 100-300 Pa for 18-22 hours, then adding a chain terminator, continuing to stir and react for 1-2 hours, then cooling to room temperature, adjusting to normal pressure, precipitating in water, washing the crude product with ethanol for 3-6 times, and then drying it in a vacuum drying oven at 85-95° C. to constant weight to obtain the terminal carboxyl functional polyamide.

4. The waterproof and anticorrosive coating according to claim 3, characterized in that: The molar ratio of the N-(4H-1,2,4-triazole-4-yl)diphenylamine-4,4'-dicarboxylic acid, 3,3'-diamino-4,4'-difluorodiphenyl sulfone, catalyst, high boiling point solvent and chain terminator is 1:1:(0.8-1):(8-15):0.

1.

5. The waterproof and anticorrosive coating according to claim 3, characterized in that: The catalyst is at least one of thiophosphonate, phosphorous acid, and thiophosphoramide; the high boiling point solvent is dimethyl sulfoxide; and the inert gas is any one of nitrogen, helium, neon, and argon.

6. The waterproof and anticorrosive coating according to claim 3, characterized in that: The chain terminator is N-(4H-1,2,4-triazol-4-yl)diphenylamine-4,4'-dicarboxylic acid.

7. The waterproof and anticorrosive coating according to claim 1, characterized in that: The filler is formed by mixing high-gloss barium and precipitated barium in a mass ratio of 1:(0.8-1.2); the particle size of the filler is 1200-2000 meshes; and the coupling agent is at least one of silane coupling agent KH550, silane coupling agent KH560 and silane coupling agent KH570.

8. The waterproof and anticorrosive coating according to claim 1, characterized in that: The defoaming agent is one or more of tributyl phosphate, defoaming agent Deqian 3100, and defoaming agent BYK088; the leveling agent is at least one of German BYK leveling agent BYK-333 and silicone leveling agent HY-5030.

9. A method for preparing the waterproof and anticorrosive coating according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: mixing the raw materials uniformly according to weight, sending the raw materials into a twin-screw extruder for extrusion, crushing the raw materials, and finally sending the raw materials into a grinder for pulverization and classification, separating the excessively fine powder and impurities through a cyclone separator, and separating the product through a powder sieve with a mesh size of 100-200, and aging the mixture for 1-3 days to obtain a finished waterproof and anticorrosive coating.

10. Use of the waterproof and anti-corrosion coating according to any one of claims 1 to 8 in bicycle painting.

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