A waterborne epoxy zinc-rich primer and a preparation method thereof

Abstract

The application discloses a water-based epoxy zinc-rich primer and a preparation method thereof, and belongs to the technical field of primers. The primer comprises component A and component B, wherein the weight ratio of the component A to the component B is 15-20:1; the component A comprises 10-15 parts of resin, 0.5-1 part of a coupling agent, 0.5-1 part of a defoaming agent, 0.1-1 part of a wetting agent, 0.1-1 part of a thickening agent, 1-2 parts of pigments, 65-85 parts of zinc powder and 8-10 parts of a first water-based solvent; the component B comprises 30-60 parts of a modified amine curing agent, 10-20 parts of a second water-based solvent, 20-30 parts of deionized water and 3-5 parts of a flash rust inhibitor; and the preparation method comprises the following steps: sequentially adding the first water-based solvent and the resin into a dispersion kettle, then adding the defoaming agent, the pigments, a compound of di-titanium telluride and nanometer materials and the zinc powder, and sequentially adding the defoaming agent, the wetting agent, the coupling agent, the thickening agent and the first water-based solvent to adjust the viscosity and obtain the component A; sequentially adding the modified amine curing agent, the second water-based solvent, the deionized water and the flash rust inhibitor into the dispersion kettle to obtain the component B; and finally, the component A is uniformly mixed with the component B to obtain the primer.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of epoxy primer, and particularly relates to a water-based epoxy zinc-rich primer and a preparation method thereof. BACKGROUND

[0002] The water-based epoxy zinc-rich primer is usually used as a base coating, cooperates with a top coating and a connecting coating, and provides comprehensive protection for a metal base. However, in the field of ships, the existing water-based epoxy zinc-rich primer still has some defects: the interface bonding force between the coating and the base is weak, and the coating is easy to peel off or delaminate in a high-humidity or high-salt environment; the zinc powder is easy to agglomerate and is not uniformly distributed, which affects the cathodic protection effect and reduces the overall protection performance of the coating; the top coating and the connecting coating are easy to be damaged due to mechanical damage, ultraviolet radiation, chemical corrosion and the like, and after the damage, the adhesion of microorganisms accelerates the damage of the primer by seawater and corrosive ions therein, and if no effective antifouling measures are taken, the metal structure will be quickly corroded and biologically fouled, which greatly shortens the service life of the facility and increases the maintenance cost and safety risk. Therefore, it is an urgent need in the industry to develop a water-based epoxy zinc-rich primer with strong coating adhesion, good zinc powder dispersion stability, excellent corrosion resistance and the ability to realize antifouling and long-term corrosion protection. SUMMARY

[0003] Based on the above problems, the application provides a water-based epoxy zinc-rich primer and a preparation method thereof. The water-based epoxy zinc-rich primer has a long pot life, good zinc powder dispersion stability, good coating flexibility, high impact resistance, excellent water resistance and corrosion resistance, and the coating has certain antifouling performance, strong adhesion in a high-humidity and high-heat environment, and is suitable for use in the field of ships.

[0004] To achieve the above-mentioned purpose, the application provides a water-based epoxy zinc-rich primer, which comprises component A and component B, and the weight ratio of the component A to the component B is 15-20:1. According to weight parts, the component A comprises 10-15 parts of resin, 0.5-1 part of coupling agent, 0.5-1 part of defoaming agent, 0.1-1 part of wetting agent, 0.1-1 part of thickening agent, 1-2 parts of pigment, 65-85 parts of zinc powder and 8-10 parts of first water-based solvent.

[0005] According to weight parts, the component B comprises 30-60 parts of modified amine curing agent, 10-20 parts of second water-based solvent and 20-30 parts of deionized water, and 3-5 parts of anti-flash rust agent.

[0006] The resin is a compound of bisphenol A liquid epoxy resin and styrene-maleic anhydride resin, and the epoxy equivalent weight of the bisphenol A liquid epoxy resin is 185-215 g / eq.

[0007] The modified amine curing agent is a compound of modified alicyclic amine curing agent and modified polyether amine curing agent.

[0008] As a preferred embodiment, the weight ratio of the bisphenol A liquid epoxy resin to the styrene-maleic anhydride resin is 8:1~2; the bisphenol A liquid epoxy resin is selected from at least one of EPIKOTE 3510-W-60A, Epikote WD-510A or Epikote WD-512A; the styrene-maleic anhydride resin is selected from at least one of SMA 2025, Polyscope XIRAN 6000 or Polyscope XIRAN 9000.

[0009] As a preferred embodiment, the coupling agent is a compound of a triamino silane coupling agent and succinic acid mono-2-(2-acryloyloxy)hydroxyethanol, the weight ratio of the triamino silane coupling agent to the succinic acid mono-2-(2-acryloyloxy)hydroxyethanol is 1:0.5~1.5, the triamino silane coupling agent is selected from at least one of Dynasylan® TRIAMO, QX-618.

[0010] As a preferred embodiment, the weight ratio of the modified alicyclic amine curing agent to the modified polyether amine curing agent is 3~4:1, the modified alicyclic amine curing agent is selected from at least one of MH-6618, ZY-S078, the modified polyether amine curing agent is selected from at least one of R-2257K, R-2257D, JEFFAMINE D-2010.

[0011] As a preferred embodiment, the defoaming agent is a silicone defoaming agent, the silicone defoaming agent is selected from at least one of Dow Corning® AFE-1510, TEGO® Foamex 810.

[0012] As a preferred embodiment, the wetting agent is a silicone gemini surfactant, the silicone gemini surfactant is selected from at least one of TEGO Twin 4100, TEGO Twin 4000, BSM-14100.

[0013] As a preferred embodiment, the thickening agent is selected from at least one of RHEOVIS® PE 1331, RHEOLATE® 350, TEGO® ViscoPlus 3030 or HOSTACERIN® WO 30; the anti-flashing agent is selected from at least one of ANTICOARCH 100S, NALZIN® FA 180, Coadd™ FR-6018; the pigment is selected from at least one of mica, iron oxide, zinc phosphate, zinc molybdate, calcium molybdate, iron oxide red, iron oxide yellow; the first aqueous solvent, the second aqueous solvent are respectively selected from at least one of isopropyl alcohol, ethylene glycol butyl ether, propylene glycol methyl ether.

[0014] As a preferred embodiment, the A component further comprises 1-3 parts of a compound of titanium ditelluride and nanomaterials, wherein the weight ratio of the nanomaterials to the titanium ditelluride is 7-9:1, and the nanomaterials are selected from at least one of nanographene, carbon nanotubes, nanosilica, and nanocalcium carbonate.

[0015] The application also provides a preparation method of the water-based epoxy zinc-rich primer.

[0016] S1: sequentially adding a first water-based solvent and a resin into a dispersion kettle and dispersing for 15-30 minutes;

[0017] S2: adding a defoaming agent into the dispersion kettle and dispersing for 5-10 minutes;

[0018] S3: adding pigments, a compound of titanium ditelluride and nanomaterials, and dispersing for 15-30 minutes under stirring;

[0019] S4: adding zinc powder under stirring and dispersing for 30-50 minutes;

[0020] S5: adding a defoaming agent, a wetting agent, and a coupling agent and dispersing for 20-30 minutes;

[0021] S6: adjusting the viscosity to 90-100 KU by using a thickening agent and the first water-based solvent, and filtering through a 150-mesh filter to obtain the A component;

[0022] S7: sequentially adding a modified amine curing agent, a second water-based solvent, deionized water, and a flash rust inhibitor into the dispersion kettle and dispersing for 15-30 minutes to obtain the B component;

[0023] S8: mixing the A component and the B component uniformly to obtain the water-based epoxy zinc-rich primer.

[0024] As a preferred embodiment, in step S1, the resin is a liquid bisphenol A epoxy resin and a styrene-maleic anhydride resin with a weight ratio of 8:1-2, which are sequentially added into the dispersion kettle for dispersion; in step S3, the nanomaterials and the titanium ditelluride are mixed in a ball mill at a weight ratio of 7-9:1 for 0.5-1 h to obtain a compound; in step S5, the coupling agent is a mixed solution of a triamino silane coupling agent and a succinic acid mono-2-(2-acryloyloxy)hydroxyethanol with a weight ratio of 1:0.5-1.5, which are dispersed uniformly; in step S7, the modified amine curing agent is a mixture of a modified alicyclic amine curing agent and a modified polyether amine curing agent with a weight ratio of 3-4:1, which are dispersed uniformly; and the ratio of the defoaming agent in step S2 to the defoaming agent in step S5 is 2-3:3.

[0025] Compared with the prior art, the application has the following beneficial effects:

[0026] 1.The waterborne zinc-rich epoxy primer of the present application is prepared by adding a styrene-maleic anhydride resin and a bisphenol A liquid epoxy resin, which can improve the hardness of the paint film, increase the crosslinking points, reduce the exposure of active groups, and enhance the water resistance of the paint film; the high reactivity of the styrene-maleic anhydride resin can react with the epoxy groups in the bisphenol A liquid epoxy resin to form chemical bonds or interact with the pigment surface, which can improve the interface compatibility and the adhesion of the coating.

[0027] 2.The coupling agent of the present application is prepared by compounding succinic acid mono-2-(2-acryloyloxy) glycol and aminosilane coupling agent, which can form stronger chemical bonds at the organic-inorganic interface, promote the uniform mixing of components, improve the gloss and color uniformity of the coating, enhance the corrosion resistance and water resistance of the coating, and prolong the pot life; in addition, the compounded coupling agent can react with inorganic materials and organic polymers to form chemical bonds and crosslinking structures, respectively, and form a network structure between the resin and the substrate due to the different molecular sizes of the compounds, which can effectively reduce the surface tension of the resin, significantly improve the wettability of the resin to the metal substrate and zinc powder, enhance the adhesion of the coating to the substrate, and significantly improve the adhesion of the coating to the substrate; the compounded coupling agent can also form a dense adsorption layer on the surface of the pigment and zinc powder through synergistic effect, which can effectively prevent pigment agglomeration and zinc powder deposition through steric hindrance effect and electrostatic repulsion, ensuring the uniformity and stability of the coating system; at the same time, the compounded coupling agent can balance the crosslinking density and the flexibility of the crosslinking network, effectively alleviate the rigidity problem of the coating caused by excessive crosslinking of the amino group, and impart good flexibility to the coating, significantly improving the impact resistance of the coating.

[0028] 3. The present application improves the micropore and defect in the coating, enhances the compactness of the coating, improves the hardness and corrosion resistance of the coating by adopting the compounding of titanium ditelluride and nanomaterial, utilizing the characteristic that the nanomaterial fills into the space gap with titanium ditelluride to form the staggered stacking structure; the uniform distribution of the corrosion product of zinc powder is realized by the synergistic effect of the conductivity of titanium ditelluride and the passivation of nanomaterial, forming a dense and stable protective film, enhancing the water resistance of the paint film; meanwhile, the compounding of titanium ditelluride and nanomaterial can synergistically act with mon-2-(2-acryloyloxy) hydroxyethanol succinate, significantly improving the dispersibility of zinc powder in the coating, improving the stability of the coating performance, and prolonging the anticorrosion life of the coating; in the case that the topcoat of the primer and the connecting paint are damaged due to external effects, the titanium ditelluride in the primer and mon-2-(2-acryloyloxy) hydroxyethanol succinate synergistically endow the paint film with certain antifouling performance, avoiding the rapid corrosion caused by the attachment and reproduction of microorganisms on the exposed primer at the damaged place. DETAILED DESCRIPTION

[0029] The present application provides a water-based epoxy zinc-rich primer, which comprises component A and component B, and the weight ratio of component A to component B is 15-20:1, and according to weight parts, component A comprises 10-15 parts of resin, 0.5-1 part of coupling agent, 0.5-1 part of defoaming agent, 0.1-1 part of wetting agent, 0.1-1 part of thickening agent, 1-2 parts of pigment, 65-85 parts of zinc powder and 8-10 parts of first water-based solvent; component B comprises, according to weight parts, 30-60 parts of modified amine curing agent, 10-20 parts of second water-based solvent, 20-30 parts of deionized water and 3-5 parts of anti-flash rust agent; the resin is a compounding of bisphenol A liquid epoxy resin and styrene-maleic anhydride resin, and the epoxy equivalent weight of the bisphenol A liquid epoxy resin is 185-215 g / eq; the modified amine curing agent is a compounding of modified alicyclic amine curing agent and modified polyether amine curing agent.

[0030] The epoxy groups of the bisphenol A liquid epoxy resin in the compounded resin of the bisphenol A liquid epoxy resin and the styrene-maleic anhydride resin are subjected to ring-opening polymerization reaction under the action of a curing agent to form a three-dimensional network polymer structure for wrapping zinc powder, the modified amine curing agent compounded system of the modified alicyclic amine curing agent and the modified polyether amine curing agent is used in the application to realize the emulsification of the compounded resin, promote phase inversion of the system, and then obtain the water-based epoxy zinc-rich primer; during the coating film forming process of the coating, the active hydrogen of the modified amine curing agent and the epoxy groups of the bisphenol A liquid epoxy resin are subjected to crosslinking reaction, the epoxy groups are subjected to ring-opening to generate hydroxyl groups, the hydroxyl groups are in a bare state and are easy to absorb water, thereby leading to the reduction of the water resistance of the paint film and the occurrence of phenomena such as blistering of the coating, the introduction of the styrene-maleic anhydride resin forms additional crosslinking points, research shows that the formation of the additional crosslinking points can not only enhance the overall chemical bonding strength of the coating, reduce the exposure of active groups, thereby enhancing the hardness and water resistance of the paint film, but also can improve the degree of mutual interweaving of molecular chains in the system, construct a more dense and three-dimensional network structure, provide more space accommodation sites for zinc powder, effectively inhibit the agglomeration between zinc powder particles, realize the uniform dispersion of zinc powder in the coating, and meanwhile, the highly interwoven three-dimensional network structure is helpful to enhancing the physical entanglement and chemical bonding between the resin and the curing agent, reducing the phase separation trend between them, thereby improving the compatibility of the resin and the curing agent and enhancing the corrosion resistance of the coating.

[0031] A lower epoxy equivalent weight will result in high crosslinking density of the coating film, good salt spray resistance, but the coating film is brittle, and the impact resistance and adhesion are poor; a higher epoxy equivalent weight will reduce the hardness of the paint film, although the adhesion is improved, but the water resistance will be poor, in order to ensure that the coating film has good hardness, impact resistance, water resistance and salt spray resistance after curing, preferably, the epoxy equivalent weight of the bisphenol A liquid epoxy resin is 185-215 g / eq.

[0032] Research shows that although the bisphenol A liquid epoxy resin and the styrene-maleic anhydride resin can both participate in the curing reaction, the amount of the two after compounding has an influence on the hardness, corrosion resistance, impact resistance and other properties of the coating, with the increase of the weight ratio of the bisphenol A liquid epoxy resin and the styrene-maleic anhydride resin, the hardness of the paint film shows an upward trend, but the corrosion resistance and impact resistance of the paint film will decrease, preferably, the weight ratio of the bisphenol A liquid epoxy resin and the styrene-maleic anhydride resin is 8:1-2, the bisphenol A liquid epoxy resin is selected from at least one of EPIKOTE 3510-W-60A, Epikote WD-510A or Epikote WD-512A, and the styrene-maleic anhydride resin is selected from at least one of SMA 2025, Polyscope XIRAN 6000 or Polyscope XIRAN 9000.

[0033] The modified amine curing agent of the present application adopts a modified alicyclic amine curing agent and a modified polyether amine curing agent compound system, wherein the modified alicyclic amine curing agent forms a high crosslinking density to give the paint film excellent hardness, and the modified polyether amine curing agent provides the paint film with good flexibility through the flexible chain segment in its molecular structure. The two compounds can effectively balance the hardness and flexibility of the paint film, and the paint film can resist external friction and collision, and also maintain good UV resistance, gloss, strength, impact resistance and other physical properties in different environments. The present application found that, in addition to the above advantages, the modified alicyclic amine curing agent has a relatively slow curing speed, and the modified polyether amine curing agent has a fast curing speed. By adjusting the proportion of the two, the speed of the curing reaction can be adjusted, so that the coating has a relatively long applicable period during the construction process, which is convenient for the operator to operate, and reduces the waste and inconvenience caused by the too fast curing of the coating. The weight ratio of the modified alicyclic amine curing agent to the modified polyether amine curing agent is 3-4:1, the modified alicyclic amine curing agent is selected from at least one of MH-6618 and ZY-S078, and the modified polyether amine curing agent is selected from at least one of R-2257K, R-2257D and JEFFAMINE D-2010.

[0034] The trisilane coupling agent in the prior art can directly react with the active groups in the bisphenol A liquid epoxy resin to promote the construction of the crosslinking network. However, due to the high reactivity of the trisilane coupling agent, the crosslinking speed of the resin and the curing agent is accelerated, thereby reducing the pot life of the coating, and even leading to the rigidification of the network structure, significantly increasing the rigidity of the paint film and reducing the toughness. The too fast crosslinking speed will inhibit the sufficient wetting of the resin to the zinc powder and the substrate surface, leaving micro cracks at the interface and exposing unreacted hydrophilic groups, thereby reducing the acid and alkali resistance and water resistance of the coating. The present application found that the introduction of butanedioic acid mono-2-(2-propenoyloxy) glycol and trisilane coupling agent as a coupling agent can prolong the induction period of the curing reaction, prolong the pot life of the coating, and form a stronger chemical bond between the organic-inorganic interface, promote the mixing between the pigment and the polymer, fully exert its dispersing effect, improve the gloss and color uniformity of the coating, and enhance the acid and alkali resistance, water resistance of the coating. In addition, the coupling agent can build a chemical bond network between the resin and the substrate, effectively reduce the surface tension of the resin, significantly improve the wettability of the resin to the substrate and zinc powder, enhance the physical adsorption and chemical bonding between the coating and the substrate, thereby greatly improving the adhesion of the coating, and maintaining high adhesion in a humid and hot environment. The acryloyl chloride group in the butanedioic acid mono-2-(2-propenoyloxy) glycol in the coupling agent reacts with the amino group in the trisilane coupling agent to form a crosslinking network, which can uniformly cover the surface of the pigment and zinc powder, thereby forming an adsorption layer, and effectively avoiding pigment agglomeration and zinc powder deposition by using steric hindrance effect and electrostatic repulsion effect, ensuring the uniform stability of the coating system. At the same time, the trisilane coupling agent has small molecule, high reactivity and fast curing speed, resulting in high hardness of the paint film, and the butanedioic acid mono-2-(2-propenoyloxy) glycol has large molecule and slow curing speed, and the balance of crosslinking density and network flexibility after compounding can effectively alleviate the rigidity problem of the coating caused by excessive crosslinking of the amino group in the silane coupling agent, and endow the coating with good flexibility and significantly improve the impact resistance of the coating.

[0035] The higher the weight ratio of the triaminosilane coupling agent to the succinic acid mono-2-(2-acryloyloxy)hydroxyethanol in the present application, the lower the flexibility of the coating and the shorter the pot life of the paint; on the contrary, the lower the weight ratio of the triaminosilane coupling agent to the succinic acid mono-2-(2-acryloyloxy)hydroxyethanol, the lower the hardness of the coating and the slower the curing speed of the coating, thereby reducing the construction efficiency. Preferably, the weight ratio of the triaminosilane coupling agent to the succinic acid mono-2-(2-acryloyloxy)hydroxyethanol is 1:0.5~1.5, and the triaminosilane coupling agent is selected from at least one of Dynasylan® TRIAMO, QX-618.

[0036] The present application has found that, after the nano material is compounded with titanium ditelluride, the nano material fills into the spatial gap of titanium ditelluride with two-dimensional layered structure and high specific surface area, forming staggered stacking structure, improving the micropores and defects in the coating, enhancing the compactness of the coating, helping to block the erosion of corrosive medium in the outside world to the inside of the coating and the protected substrate, thereby improving the hardness and corrosion resistance of the coating, and prolonging the service life of the protected object. The titanium ditelluride and the nano material are compounded to form a synergistic filling effect, which can accurately embed into the tiny gap between zinc powder particles, reduce the area of zinc powder exposed to the corrosive environment, and reduce the consumption rate of zinc powder. At the same time, the succinic acid mono-2-(2-acryloyloxy)hydroxyethanol reacts with the hydroxyl group on the surface of the nano material and the organic polymer molecules to form a cross-linked structure, embedding the zinc powder particles therein, significantly improving the dispersibility of zinc powder in the paint, improving the stability of the performance of the paint, and prolonging the anti-corrosion life of the coating. The conductivity of titanium ditelluride and the passivation effect of the nano material synergize to make the corrosion products of zinc powder uniformly distributed, forming a dense and stable protective film, and enhancing the water resistance of the paint film. When the anti-fouling topcoat and the connecting paint are damaged by external factors, the titanium ditelluride in the primer produces Te 4+ , Te 4+ under oxidation, and the carboxylate ions generated by the dissociation of the succinic acid mono-2-(2-acryloyloxy)hydroxyethanol form a charge environment that is not conducive to the adhesion of microorganisms, effectively inhibit the adhesion of microorganisms by improving the hydrophobicity of the paint film, and hinder the growth and reproduction of microorganisms by reacting with the enzymes in the body of microorganisms, thereby endowing the paint film with anti-fouling performance, avoiding the rapid corrosion caused by the adhesion and reproduction of microorganisms on the exposed primer at the damage site. The higher the weight ratio of the nano material to titanium ditelluride, the more difficult the filler dispersion, and thus the hardness and corrosion resistance of the paint film become unstable; the lower the weight ratio of the nano material to titanium ditelluride, the lower the hardness and corrosion resistance of the paint film. Preferably, the weight ratio of the nano material to titanium ditelluride is 7~9:1, and the nano material is selected from at least one of nano graphene, carbon nanotube, nano silicon dioxide, and nano calcium carbonate.

[0037] The defoaming agent used in the present application is a silicone defoaming agent. The silicone defoaming agent effectively plays a defoaming role in the water-based epoxy zinc-rich primer through mechanisms such as reducing surface tension, destroying foam structure, and inhibiting foam regeneration, while improving the application performance of the coating. The silicone defoaming agent is selected from at least one of Dow Corning® AFE-1510, TEGO® Foamex 810.

[0038] The wetting agent used in the present application is a silicone gemini surfactant. The silicone gemini surfactant has a low surface tension, making the coating more easily wet the substrate and more evenly coated on the substrate surface. At the same time, the silicone gemini surfactant synergistically acts with the defoaming agent to reduce shrinkage and bubble problems in the coating. The silicone gemini surfactant is selected from at least one of TEGO Twin 4100, TEGO Twin 4000, and BSM-14100.

[0039] The thickening agent used in the present application is selected from at least one of RHEOVIS® PE 1331, RHEOLATE® 350, TEGO® ViscoPlus 3030, or HOSTACERIN® WO 30; the pigment is selected from at least one of mica iron oxide, zinc phosphate, zinc molybdate, calcium molybdate, red iron oxide, and yellow iron oxide; the first and second aqueous solvents are selected from at least one of isopropyl alcohol, ethylene glycol butyl ether, and propylene glycol methyl ether; and the anti-flash rust agent is selected from at least one of ANTICO ARCH100S, NALZIN® FA180, and Coadd™ FR-6018.

[0040] The present application also provides a preparation method of a water-based epoxy zinc-rich primer, comprising the following steps:

[0041] S1: sequentially adding the first aqueous solvent and the resin into a dispersion kettle and dispersing for 15-30 minutes;

[0042] S2: adding the defoaming agent into the dispersion kettle and dispersing for 5-10 minutes;

[0043] S3: under stirring, adding a compound of the pigment, titanium ditelluride, and the nanomaterial and dispersing for 15-30 minutes;

[0044] S4: under stirring, adding the zinc powder and dispersing for 30-50 minutes;

[0045] S5: adding the defoaming agent, the wetting agent, and the coupling agent and dispersing for 20-30 minutes;

[0046] S6: using the thickening agent and the first aqueous solvent to adjust the viscosity to 90-100 KU, and filtering through a 150-mesh filter to obtain component A;

[0047] S7: The modified amine curing agent, the second aqueous solvent, deionized water, and the anti-flash rust agent are sequentially added into the dispersion kettle, and are dispersed for 15-30 minutes to obtain component B;

[0048] S8: Component A is mixed with component B uniformly to obtain the aqueous epoxy zinc-rich primer;

[0049] In step S1, the bisphenol A liquid epoxy resin and the styrene-maleic anhydride resin are sequentially added into the dispersion kettle in a weight ratio of 8:1-2 for dispersion; in step S3, the nanomaterial and the titanium ditelluride are mixed in a weight ratio of 7-9:1 in a drum-type ball mill for 0.5-1 hours to obtain a compound; in step S5, the triaminosilane coupling agent and the succinic acid mono-2-(2-acryloyloxy)hydroxyethanol are uniformly dispersed in a weight ratio of 1:0.5-1.5 to obtain a mixed solution; in step S7, the modified amine curing agent is a mixture of the modified alicyclic amine curing agent and the modified polyether amine curing agent in a weight ratio of 3-4:1; the defoaming agent in step S2 and the defoaming agent in step S5 are in a ratio of 2-3:3. Example 1

[0050] An aqueous epoxy zinc-rich primer, the weight ratio of component A to component B is 15:1, according to the weight parts, component A includes, resin 10 parts, coupling agent 0.6 parts, defoaming agent 0.5 parts, wetting agent 0.1 parts, thickening agent 0.1 parts, pigment 1 part, zinc powder 65 parts, first aqueous solvent 8 parts, compound 1.2 parts; component B includes, according to the weight parts, modified amine curing agent 30 parts, second aqueous solvent 10 parts, deionized water 20 parts, anti-flash rust agent 3 parts; nanomaterial 1 part, titanium ditelluride 0.2 part.

[0051] The embodiment provides a preparation method of an aqueous epoxy zinc-rich primer, including the following steps:

[0052] S1: 7 parts of isopropyl alcohol (first aqueous solvent), 8.9 parts of EPIKOTE 3510-W-60A (bisphenol A liquid epoxy resin), and 1.1 parts of SMA 2025 (styrene-maleic anhydride resin) are sequentially added into a dispersion kettle, and are dispersed for 15 minutes;

[0053] S2: 0.2 parts of Dow Corning® AFE-1510 (silicone defoaming agent) are added into the dispersion kettle, and are dispersed for 5 minutes;

[0054] S3: Under stirring, 1 part of mica iron oxide (pigment) and a compound obtained by uniformly mixing 1 part of nanographene (nanomaterial) and 0.2 parts of titanium ditelluride in a drum-type ball mill are added, and are dispersed for 15 minutes;

[0055] S4: Under stirring, 65 parts of zinc powder are added, and are dispersed for 30 minutes;

[0056] S5: adding 0.3 parts of Dow Corning® AFE-1510 (silicone defoamer), 0.1 parts of TEGO Twin 4100 (silicone twin structure surfactant), a coupling agent obtained by uniformly pre-dispersing 0.3 parts of Dynasylan® TRIAMO (triamino silane coupling agent) and 0.3 parts of succinic acid mono-2-(2-propenoyloxy) glycol, and dispersing for 20 minutes;

[0057] S6: using 0.1 parts of RHEOVIS® PE 1331 (thickening agent) and 1 parts of isopropyl alcohol (first aqueous solvent), adjusting to a viscosity of 90-100 KU, and filtering on a 150-mesh filter screen to obtain component A;

[0058] S7: adding a modified amine curing agent obtained by uniformly pre-dispersing 24 parts of MH-6618 (modified alicyclic amine curing agent) and 6 parts of R-2257K (modified polyether amine curing agent), 10 parts of isopropyl alcohol (second aqueous solvent), 20 parts of deionized water, and 3 parts of ANTICOARCH 100S (anti-flash rust agent) into a dispersing kettle in sequence, and dispersing for 15 minutes to obtain component B;

[0059] S8: mixing the component A and the component B in a mass ratio of 15:1 to obtain the waterborne epoxy zinc-rich primer. Example 2

[0060] A waterborne epoxy zinc-rich primer, the weight ratio of component A to component B is 18:1, and component A includes, by weight parts, 12 parts of resin, 0.5 parts of coupling agent, 0.6 parts of defoamer, 0.2 parts of wetting agent, 1 part of thickening agent, 1 part of pigment, 83 parts of zinc powder, 9 parts of first aqueous solvent, and 3 parts of complex; and component B includes, by weight parts, 40 parts of modified amine curing agent, 15 parts of second aqueous solvent, 25 parts of deionized water, and 4 parts of anti-flash rust agent.

[0061] The present embodiment provides a preparation method of a waterborne epoxy zinc-rich primer, including the following steps:

[0062] S1: adding 8 parts of ethylene glycol butyl ether (first aqueous solvent), 10 parts of Epikote WD-510A (bisphenol A liquid epoxy resin), and 2 parts of Polyscope XIRAN 6000 (styrene-maleic anhydride resin) into a dispersing kettle in sequence, and dispersing for 30 minutes;

[0063] S2: adding 0.3 parts of TEGO® Foamex 810 (silicone defoamer) into the dispersing kettle, and dispersing for 10 minutes;

[0064] S3: Add 1 part of iron oxide red (pigment), 2.7 parts of nano-silica (nanomaterial) and 0.3 parts of titanium ditelluride pre-mixed uniformly in a drum ball mill, and disperse for 30 minutes under stirring;

[0065] S4: Add 83 parts of zinc powder under stirring and disperse for 50 minutes;

[0066] S5: Add 0.3 parts of TEGO® Foamex 810 (silicone defoamer), 0.2 parts of BSM-14100 (silicone double structure surfactant), 0.2 parts of QX-618 (triamino silane coupling agent) and 0.3 parts of succinic acid mono-2-(2-acryloyloxy) glycol pre-dispersed uniformly, and disperse for 30 minutes;

[0067] S6: Use 1 part of RHEOLATE® 350 (thickening agent) and 1 part of ethylene glycol butyl ether (first aqueous solvent) to adjust the viscosity to 90-100 KU, and filter through a 150 mesh filter to obtain component A;

[0068] S7: Put 31 parts of ZY-S078 (modified alicyclic amine curing agent) and 9 parts of R-2257D (modified polyether amine curing agent) pre-dispersed uniformly, 15 parts of propylene glycol methyl ether (second aqueous solvent), 25 parts of deionized water, and 4 parts of NALZIN® FA180 (anti-flash rust agent) into a dispersion kettle in sequence, disperse for 30 minutes to obtain component B;

[0069] S8: Mix the component A and component B in a mass ratio of 18:1 to obtain the water-based epoxy zinc-rich primer. Example 3

[0070] A water-based epoxy zinc-rich primer, the weight ratio of component A to component B is 20:1, and component A includes, by weight parts, 15 parts of resin, 1 part of coupling agent, 1 part of defoamer, 1 part of wetting agent, 0.2 parts of thickening agent, 2 parts of pigment, 85 parts of zinc powder, 10 parts of first aqueous solvent, and 1 part of complex; component B includes, by weight parts, 60 parts of modified amine curing agent, 20 parts of second aqueous solvent, 30 parts of deionized water, and 3 parts of anti-flash rust agent.

[0071] The embodiment provides a preparation method of a water-based epoxy zinc-rich primer, including the following steps:

[0072] S1: Put 8 parts of ethylene glycol butyl ether (first aqueous solvent), 12 parts of Epikote WD-512A (bisphenol A liquid epoxy resin), and 3 parts of Polyscope XIRAN 9000 (styrene-maleic anhydride resin) into a dispersion kettle in sequence, and disperse for 20 minutes;

[0073] S2: Put 0.45 parts of Dow Corning® AFE-1510 (silicone defoamer) into the dispersion kettle, and disperse for 8 minutes;

[0074] S3: Under stirring, add 1 part of mica iron oxide (pigment), 1 part of zinc phosphate (pigment), a compound of 0.9 parts of nano calcium carbonate (nanomaterial) and 0.1 parts of titanium ditelluride uniformly pre-mixed in a roller-type ball mill, and disperse for 25 minutes;

[0075] S4: Under stirring, add 85 parts of zinc powder, and disperse for 40 minutes;

[0076] S5: Add 0.55 parts of TEGO® Foamex 810 (silicone defoamer), 0.5 parts of TEGO Twin 4000 (silicone twin structure surfactant), 0.5 parts of BSM-14100 (silicone twin structure surfactant), a coupling agent of 0.3 parts of Dynasylan® TRIAMO (triamino silane coupling agent) and 0.4 parts of QX-618 (triamino silane coupling agent) and 0.3 parts of succinic acid mono-2-(2-acryloyloxy) hydroxyethanol uniformly pre-dispersed, and disperse for 25 minutes;

[0077] S6: Adjust to a viscosity of 90-100 KU using 0.1 parts of TEGO® ViscoPlus 3030 (thickener), 0.1 parts of HOSTACERIN® WO 30 (thickener) and 2 parts of propylene glycol methyl ether (first aqueous solvent), and filter through a 150-mesh filter to obtain component A;

[0078] S7: Put curing agents of 20 parts of MH-6618 (modified aliphatic amine curing agent), 25 parts of ZY-S078 (modified aliphatic amine curing agent), 10 parts of R-2257K (modified polyether amine curing agent), 5 parts of JEFFAMINE D-2010 (modified polyether amine curing agent), 20 parts of ethylene glycol butyl ether (second aqueous solvent), 30 parts of deionized water, 2 parts of NALZIN® FA 180 (anti-flash rust agent), 3 parts of Coadd™ FR-6018 (anti-flash rust agent) into the dispersion kettle in sequence, disperse for 20 minutes to obtain component B;

[0079] S8: Mix the component A and the component B in a mass ratio of 20:1 to obtain the water-based epoxy zinc-rich primer;

[0080] Comparative Example 1

[0081] The preparation method of the comparative example is the same as that of Example 2, and the only difference from Example 2 is that the styrene-maleic anhydride resin Polyscope XIRAN 6000 is not used in the comparative example, and an equal amount of bisphenol A liquid epoxy resin Epikote WD-510A is used instead.

[0082] Comparative Example 2

[0083] The preparation method of the comparative example is the same as that of Example 2, and the only difference from Example 2 is that the styrene-maleic anhydride resin Polyscope XIRAN 6000 is not used in the comparative example, and an equal amount of bisphenol A liquid epoxy resin Epikote WD-510A is used instead.

[0084] Comparative Example 3

[0085] The preparation method of the comparative example is the same as that of Example 2, and the only difference from Example 2 is that the titanium ditelluride is not used in the comparative example, and an equal amount of nano-silicon dioxide is used instead.

[0086] Comparative Example 4

[0087] The preparation method of the comparative example is the same as that of Example 2, and the only difference from Example 2 is that the modified polyether amine curing agent R-2257D is not used in the comparative example, and an equal amount of modified alicyclic amine curing agent ZY-S078 is used instead.

[0088] Comparative Example 5

[0089] The preparation method of the comparative example is the same as that of Example 2, and the only difference from Example 2 is that the resin of the comparative example is 12 parts of bisphenol A liquid epoxy resin CYD-134 with an epoxy equivalent weight of 230-270 g / eq; the coupling agent is a triaminosilane coupling agent QX-618; an equal amount of nano-silicon dioxide is used instead of titanium ditelluride; and the modified amine curing agent is a modified alicyclic amine curing agent MH-6618.

[0090] The water-based epoxy zinc-rich primer prepared in the above Examples 1-3 and Comparative Examples 1-5 is subjected to performance testing (product execution standard: HG / T 3668-2020 zinc-rich primer), and the test results are shown in Table 1 below:

[0091] Table 1 Performance test results of water-based epoxy zinc-rich primer

[0092]

[0093] From the test results of Table 1, it can be obtained that, compared with Comparative Example 1, Example 2 shows that the bisphenol A liquid epoxy resin with an epoxy equivalent weight of 185-215 g / eq and the styrene-maleic anhydride resin can improve the hardness of the paint film, enhance the adhesion between the coating and the substrate, and significantly improve the water resistance, salt spray resistance, acid resistance and alkali resistance of the coating.

[0094] Compared with Comparative Example 2, Example 2 shows that, after the specific proportion of the triaminosilane coupling agent and the monosodium-2-(2-acryloyloxy) hydroxyethanol succinate are compounded, the adhesion between the coating and the substrate can be improved, the corrosion resistance and water resistance of the coating are enhanced, the pot life of the paint is prolonged, the coating has good flexibility, and the impact resistance of the coating is significantly improved.

[0095] Compared with Comparative Example 3, Example 2 shows that, when the specific proportion of titanium ditelluride and nanomaterials is used in the water-based epoxy zinc-rich primer provided by the application, the hardness, corrosion resistance and water resistance of the coating can be improved, the anti-corrosion life of the coating is prolonged, and the coating has good anti-fouling performance.

[0096] Compared with Comparative Examples 2 and 3, Example 2 shows that, under the action of oxidation, the titanium ditelluride and the monosodium-2-(2-acryloyloxy) hydroxyethanol succinate can cooperate to give the paint film anti-fouling performance.

[0097] Compared with Comparative Example 4, Example 2 shows that, after the specific proportion of the modified alicyclic amine curing agent and the modified polyether amine curing agent are compounded, the advantages are complementary, the hardness and flexibility of the paint film are effectively balanced, and the pot life of the paint is prolonged.

[0098] Compared with Comparative Example 5, Example 2 shows that, when the specific proportion of the bisphenol A liquid epoxy resin with an epoxy equivalent weight of 185-215 g / eq and the styrene-maleic anhydride resin, the triaminosilane coupling agent and the monosodium-2-(2-acryloyloxy) hydroxyethanol succinate, the titanium ditelluride and the nanomaterials, and the modified alicyclic amine curing agent and the modified polyether amine curing agent are compounded, the water-based epoxy zinc-rich primer has a long pot life, good zinc powder dispersion stability, good coating flexibility, high impact resistance, excellent water resistance and corrosion resistance, the coating hardness and flexibility meet the standard, the coating has certain anti-fouling performance, strong adhesion in high humidity and high temperature environment, and is suitable for the field of ships.

[0099] The above is only a specific embodiment of the present disclosure, enabling those skilled in the art to understand or implement the present disclosure. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present disclosure. Therefore, the present disclosure will not be limited to these embodiments described herein, but will conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A waterborne epoxy zinc-rich primer, characterized in that, The invention comprises component A and component B, wherein the weight ratio of component A to component B is 15-20:

1. Calculated by weight, component A comprises 10-15 parts of resin, 0.5-1 part of coupling agent, 0.5-1 part of defoaming agent, 0.1-1 part of wetting agent, 0.1-1 part of thickener, 1-2 parts of pigment, 65-85 parts of zinc powder, and 8-10 parts of a first aqueous solvent. Calculated by weight, the B component includes 30-60 parts of a modified amine curing agent, 10-20 parts of a second aqueous solvent, 20-30 parts of deionized water, and 3-5 parts of an anti-flash rust agent; The resin is a compound of bisphenol A liquid epoxy resin and styrene-maleic anhydride resin, and the epoxy equivalent of the bisphenol A liquid epoxy resin is 185-215 g / eq; The modified amine curing agent is a compound of a modified alicyclic amine curing agent and a modified polyetheramine curing agent; the coupling agent is a compound of a triaminosilane coupling agent and succinic acid mono-2-(2-acryloyloxy)hydroxyethanol; the component A further comprises 1 to 3 parts of a compound of titanium ditelluride and a nanomaterial, wherein the nanomaterial is selected from at least one of nanographene, carbon nanotubes, nanosilica, and nanocalcium carbonate.

2. A waterborne epoxy zinc-rich primer according to claim 1, characterized in that, The weight ratio of the bisphenol A liquid epoxy resin to the styrene-maleic anhydride resin is 8:1-2; the bisphenol A liquid epoxy resin is selected from at least one of EPIKOTE 3510-W-60A, Epikote WD-510A, and Epikote WD-512A; and the styrene-maleic anhydride resin is selected from at least one of SMA 2025, Polyscope XIRAN 6000, and Polyscope XIRAN 9000.

3. A waterborne epoxy zinc-rich primer according to claim 1, characterized in that, The weight ratio of the triaminosilane coupling agent to succinic acid mono-2-(2-acryloyloxy)hydroxyethanol is 1:0.5~1.5, and the triaminosilane coupling agent is selected from at least one of Dynasylan® TRIAMO and QX-618.

4. A waterborne epoxy zinc-rich primer according to claim 1, characterized in that, The weight ratio of the modified alicyclic amine curing agent to the modified polyetheramine curing agent is 3 to 4:1, the modified alicyclic amine curing agent is selected from at least one of MH-6618 and ZY-S078, and the modified polyetheramine curing agent is selected from at least one of R-2257K, R-2257D, and JEFFAMINE D-2010.

5. A waterborne epoxy zinc-rich primer according to claim 1, characterized in that, The defoaming agent is a silicone defoaming agent, and the silicone defoaming agent is TEGO® Foamex 810.

6. A waterborne epoxy zinc-rich primer according to claim 1, characterized in that, The wetting agent is an organosilicon twin structure surfactant, and the organosilicon twin structure surfactant is selected from at least one of TEGO Twin 4100, TEGO Twin 4000, and BSM-14100.

7. A waterborne epoxy zinc-rich primer according to claim 1, characterized in that, The thickener is selected from at least one of RHEOVIS® PE 1331, RHEOLATE® 350, and TEGO® ViscoPlus 3030; the flash rust inhibitor is selected from at least one of ANTICO ARCH100S, NALZIN® FA 180, and Coadd™ FR-6018; the pigment is selected from at least one of mica iron oxide, zinc phosphate, zinc molybdate, calcium molybdate, red iron oxide, and yellow iron oxide; and the first aqueous solvent and the second aqueous solvent are selected from at least one of isopropyl alcohol, ethylene glycol butyl ether, and propylene glycol methyl ether.

8. A waterborne epoxy zinc-rich primer according to claim 1, characterized in that, The weight ratio of the nanomaterial to titanium ditelluride in the composite is 7-9:

1.

9. A method for preparing a waterborne epoxy zinc-rich primer as claimed in any one of claims 1 to 8, characterized in that: The specific steps include: S1: First, add the first aqueous solvent and resin into the dispersion kettle in sequence and disperse for 15 to 30 minutes; S2: Add the defoamer into the dispersion kettle and disperse for 5 to 10 minutes; S3: Add pigment, titanium ditelluride and nanomaterial compound under stirring and disperse for 15 to 30 minutes; S4: Add zinc powder while stirring and disperse for 30-50 minutes; S5: Add defoamer, wetting agent, and coupling agent in sequence and disperse for 20-30 minutes; S6: Using the thickener and the first aqueous solvent, adjust the viscosity to 90-100 KU, and then filter through a 150-mesh filter to obtain component A; S7: Then, the modified amine curing agent, the second aqueous solvent, deionized water, and the flash rust preventer are sequentially added into a dispersion kettle and dispersed for 15 to 30 minutes to obtain component B; S8: Finally, component A and component B are mixed evenly to obtain a water-based epoxy zinc-rich primer.

10. The method for preparing a waterborne epoxy zinc-rich primer according to claim 9, wherein: In step S1, the resin is a bisphenol A liquid epoxy resin and a styrene-maleic anhydride resin in a weight ratio of 8:1-2, and the two are sequentially placed in a dispersion kettle for dispersion; in step S3, the nanomaterial and titanium ditelluride are placed in a ball mill at a weight ratio of 7-9:1 and mixed and ball-milled for 0.5-1 hour to obtain a composite; in step S5, the coupling agent is a mixed solution obtained by uniformly dispersing a triaminosilane coupling agent and succinic acid mono-2-(2-acryloyloxy)hydroxyethanol in a weight ratio of 1:0.5-1.5; in step S7, the modified amine curing agent is a mixture obtained by uniformly dispersing a modified alicyclic amine curing agent and a modified polyetheramine curing agent in a weight ratio of 3-4:1; the ratio of the defoaming agent in step S2 to the defoaming agent in step S5 is 2-3:3.

Images