High-performance long-acting anticorrosive waterborne epoxy glass flake coating and preparation method thereof

Abstract

The invention discloses a high-performance long-acting anticorrosive waterborne epoxy glass flake coating and a preparation method thereof, and belongs to the field of coatings. The coating comprises a component A and a component B, wherein the component A comprises water-based novolac epoxy resin, quick-drying water-based bisphenol A epoxy dispersion, double modified glass flakes, antirust slow-release water slurry, tinting pigment and other auxiliaries. And the component B comprises a water-based amine epoxy curing agent, an anti-flash-rust auxiliary agent and the like. The corrosion resistance and chemical medium resistance of the waterborne epoxy coating can be greatly improved through double modification of the glass flakes and matching of the optimized anti-rust materials, and the coating plays a crucial role in long-acting corrosion prevention of the coating.

Description

Technical Field

[0001] The present invention relates to a water-based epoxy glass flake coating, in particular to a high-performance, long-lasting anti-corrosion water-based epoxy glass flake coating having high hardness, high wear resistance, high flexibility, excellent corrosion resistance and super acid and alkali resistance, and a preparation method thereof. Background Art

[0002] With increasing environmental protection requirements, traditional solvent-based coatings are gradually being replaced by water-based coatings due to their high levels of volatile organic compounds (VOCs), which are harmful to the environment and human health. In response to this opportunity and environment, water-based epoxy glass flake coatings have emerged. As a high-performance anti-corrosion coating, they are gradually demonstrating their unique advantages in various industries. They not only inherit the excellent anti-corrosion properties of traditional epoxy coatings, but also utilize innovative water-based technology to meet the anti-corrosion needs of special environments, achieving a perfect combination of environmental protection and performance. For example, they are used in heavy-duty anti-corrosion applications such as the inner walls of storage tanks, deep coal mines, pipeline valves, and offshore platforms.

[0003] In practical applications, water-based epoxy glass flake coatings demonstrate strong corrosion protection. Their unique glass flake structure effectively isolates corrosive media from the substrate, forming a solid barrier. Furthermore, the staggered arrangement of the flakes further enhances the coating's anti-penetration properties, ensuring long-term protection in harsh corrosive environments.

[0004] Like most water-based epoxy coatings, water-based epoxy glass flake coatings also have some shortcomings in terms of application and effectiveness. For example, in terms of chemical resistance, while the glass flakes' scaly structure provides a shield against most corrosive chemicals, their molecular structure is easily damaged by highly corrosive chemicals such as strong acids and alkalis, resulting in a decrease in the coating's protective properties and the occurrence of blistering and shedding. Furthermore, wear resistance is insufficient. For example, in the spray area of ​​an absorption tower or in areas subject to severe slurry abrasion, the coating's internal structure and composition can easily scratch and peel under long-term use, affecting its appearance and protective effectiveness. Glass flakes are also a brittle material, and application during cold winters can lead to cracking or poor impact resistance due to uneven stress. Furthermore, water-based epoxy glass flake coatings are typically used in heavy-duty corrosion protection applications, so thick film thicknesses are applied. Due to their slow drying time during cold weather, thick applications can result in poor sag resistance and severe sag. Therefore, how to balance the waterborne epoxy glass flakes' resistance to strong corrosive media, long-term wear resistance, high strength and toughness, and anti-sagging during construction is an urgent problem that needs to be solved. The current new research direction shows that in order to address these problems and shortcomings, the use of glass flakes that are double-modified with super acid and alkali resistant polytetrafluoroethylene and high-toughness and high-wear-resistant graphene oxide in waterborne epoxy glass flake coatings, supplemented by various high-performance anti-rust pigments and functional fillers, and combined with the preferred anti-sagging additives, is one of the effective means and ways to solve the above shortcomings and problems. Summary of the Invention

[0005] The purpose of this invention is to provide a high-performance, long-lasting, corrosion-resistant water-based epoxy glass flake coating. This coating is environmentally friendly and non-toxic, boasting excellent flexibility and impact resistance. The resulting coating film exhibits strong barrier properties and excellent resistance to water, oil, strong acids, and alkalis, effectively preventing the penetration of corrosive media. It also exhibits superior corrosion resistance, providing long-lasting corrosion protection for applications such as the inner walls of storage tanks, chemical containers, pipeline valves, and offshore platforms.

[0006] Another object of the present invention is to provide a method for preparing the above-mentioned high-performance, long-lasting anti-corrosion water-based epoxy glass flake coating.

[0007] The purpose of the present invention can be achieved by the following measures:

[0008] A high-performance, long-lasting anti-corrosion water-based epoxy glass flake coating, comprising component A and component B, wherein component A comprises the following components in parts by weight:

[0009]

[0010]

[0011] The ingredients of component B are as follows:

[0012]

[0013] In some preferred technical solutions, the coating is composed of the following components and parts by weight:

[0014] The ingredients of component B are as follows:

[0015]

[0016] In the technical solution of the present invention, the water-based phenolic epoxy resin in component A is one or more of the following: American Hansen water-based epoxy resin Epikote 6006-W-68A, Bass Synthetic New Materials water-based phenolic epoxy dispersion BS-2155F, and Huntsman water-based epoxy phenolic resin ARADUR ECN 1400.

[0017] In the technical solution of the present invention, the quick-drying water-based bisphenol A epoxy dispersion in component A is Fuqisen New Materials water-based epoxy resin AQUAER-3012, Huayi Jinghua water-based epoxy emulsion STW602, Hansen water-based epoxy resin Epikote TM One or more of 7520-WD-52A.

[0018] In the technical solution of the present invention, the double-modified glass flakes of component A are prepared by the following steps:

[0019] S1: Add isopropanol and deionized water to the reactor, adjust the pH to 4-5 with acetic acid, then add polytetrafluoroethylene powder to the reactor, heat to 50-60°C, add silane coupling agent KH-560, and then use acetone as a catalyst for ultrasonic dispersion for 2-3 hours. Transfer to a magnetic dispersion kettle and continue to add 100-300 mesh glass flakes to the reactor, heat to 70-80°C and perform magnetic dispersion for 3-6 hours to obtain a polytetrafluoroethylene-modified glass flake suspension, take out and filter it, wash it with ethanol, place it to dry, and after the ethanol evaporates, send it into a 50-60°C oven for drying for 1-3 hours to obtain polytetrafluoroethylene-modified glass flakes;

[0020] Preferably, the dosage of each component in S1 is as follows:

[0021]

[0022] S2: After adding toluene and graphene oxide powder to the reactor, the temperature is heated to 70-80°C, tetraisopropyl titanate is used as a catalyst, and ultrasonic dispersion is performed for 2-3 hours; the mixture is transferred to a magnetic dispersion kettle, and the polytetrafluoroethylene-modified glass flakes in step S1 are added, the reaction temperature is controlled to 100-110°C, and magnetic dispersion is performed for 10-12 hours to obtain a suspension of glass flakes dual-modified with graphene oxide and polytetrafluoroethylene, which is filtered, washed with ethanol, and dried to obtain graphene oxide-polytetrafluoroethylene dual-modified glass flake powder;

[0023] Preferably, the amount of each component in S2 is as follows:

[0024]

[0025] In the technical solution of the present invention, the substrate wetting agent in component A is Digo Twin-4100, Shenzhu Chemical SN-4741, Digo One or more of WET KL 245; the defoaming agent is Digo One or more of Airex902W, BYK-024, and SN-6710 from Shenzhu Chemical; the fungicide is KATHONLXE from Dow Chemical, SN-B9725 from Shenzhu Chemical, and Mycan Biotechnology. 210 one or more; the dispersant is Digo One or more of Dispers 760W, BYK-190, and Shenzhen Bamboo Chemical SN-1790.

[0026] In the technical solution of the present invention, the anti-rust slow-release slurry of component A is prepared by the following steps: mixing an inorganic corrosion inhibitor, zinc phosphomolybdate and hexagonal boron nitride powder and adding deionized water; Dispers 760W dispersant is prepared into a water-based compound slurry. The slurry is transferred to a sand mill and fumed silica A200 is added. After grinding for 4 to 6 hours, the material is discharged and ground to a fineness of less than 25 μm. After cooling, fungicide LXE is added and mixed evenly to obtain a rust-proof slow-release water slurry.

[0027] Optimum: The components in the rust-proof slow-release slurry are as follows:

[0028]

[0029] Further preferably, the inorganic corrosion inhibitor is Junjiang Technology's JP-B803 inorganic high-efficiency corrosion inhibitor, and the zinc phosphomolybdate is Junjiang Technology's JP-B900 zinc phosphomolybdate.

[0030] In the technical solution of the present invention, the fumed silica in component A is Evonik Degussa A200; the polyamide wax rheological additive is Fenghong New Material PA-630; the rutile titanium dioxide is one or more of Jiangxi Tianguang TR-33, Nanjing Titanium Dioxide NR-960, and Longbai Group R-996; the iron oxide black powder is Bayer of Lanxess Black 4330 iron oxide black; the low shear associative thickener is American Ashland Aquaflow TM XLS-525, Puwei Coadd TM U601, Wanhua Chemical One or more of U905.

[0031] In the technical solution of the present invention, the water-based amine epoxy curing agent in component B is at least one of the following: American Hansen water-based epoxy curing agent Epikore 8530-W-75, Huntsman water-based epoxy curing agent Aradur38-1, and Fuqisen new material water-based epoxy curing agent AQUAEPO-3126; the anti-flash rust additive is Puwei Coadd TM One or more of FR-333, Shenzhu Chemical SN-9779A, and NALZIN FA-179.

[0032] The above-mentioned high-performance long-lasting anti-corrosion water-based epoxy glass flake coating is prepared in the following steps:

[0033] Preparation of component A: adding water-based phenolic epoxy resin and quick-drying water-based bisphenol A epoxy dispersion into a paint mixing kettle and mixing them evenly; then adding dipropylene glycol butyl ether, substrate wetting agent, defoamer, fungicide, dispersant, rust-proof slow-release slurry and deionized water into a mixing kettle, pre-dispersing at a speed of 400-600 r / min for 10-20 minutes to obtain a first mixed material; then adding double-modified glass flakes, rutile titanium dioxide, iron oxide black powder and fumed silica into the paint mixing kettle and mixing and stirring with the first mixed material evenly, and high-speed dispersing at 1000-1200 r / min for 0.5-1 hour to prepare a second mixed material; then adding a polyamide wax rheological additive and a low-shear associative thickener to adjust the viscosity to 100KU-120KU to obtain component A of a water-based epoxy glass flake coating;

[0034] Preparation of component B: Disperse a waterborne amine epoxy curing agent and propylene glycol methyl ether in proportion at a rotation speed of 600 to 800 r / min for 5 to 10 minutes; then add an anti-flash rust additive and deionized water and disperse at a rotation speed of 400 to 600 r / min for 5 to 10 minutes to obtain component B of a waterborne epoxy glass flake coating;

[0035] During construction, component A and component B are mixed evenly at a mass ratio of 4 to 6:1 to obtain the target product.

[0036] (1) Using a mixture of water-based epoxy phenolic resin and quick-drying water-based bisphenol A epoxy dispersion as the main film-forming material: Compared with ordinary epoxy resin, the water-based epoxy phenolic resin selected has a high cross-linking density after curing because it contains more than two epoxy groups in its molecular structure. The heat resistance, solvent resistance and chemical resistance of the product will be greatly improved. At the same time, it also has high hardness and wear resistance. In addition, its excellent water resistance and corrosion resistance can greatly extend the service life of the coating and is particularly suitable for application in heavy corrosion environments. The introduction of a quick-drying water-based bisphenol A epoxy dispersion with a softening point greater than 50°C and an epoxy equivalent greater than 1000g / mol can, on the one hand, improve the drying property of the overall coating and avoid a series of construction defects such as sagging and non-curing caused by the slow drying of a single water-based epoxy phenolic resin at low temperatures in winter. On the other hand, it can also increase the flexibility of the coating film, because the material using only water-based epoxy phenolic resin is brittle after curing, prone to cracking, and has poor tolerance to impact and deformation. When mixed in an optimal proportion, the two complement each other, achieve complementary performance, and significantly improve overall performance.

[0037] (2) The strategy of using graphene oxide and polytetrafluoroethylene to double modify glass flakes: one end of the silane coupling agent is connected to the organic chain segment of polytetrafluoroethylene, and the other end is hydrolyzed into silanol groups, which then form hydrogen bonds with some hydroxyl groups on the surface of the glass flakes and undergo condensation and dehydration reactions to form stable Si-O-Si bonds, thus completing the modification of the glass flakes with polytetrafluoroethylene in the first step; then, under the action of titanate catalysts, the hydroxyl groups on the graphene oxide and the remaining unreacted hydroxyl groups on the glass flakes condense to obtain graphene oxide-polytetrafluoroethylene double modified glass flakes. Polytetrafluoroethylene is a polymer compound with many excellent properties. It has extremely high chemical stability and can withstand the effects of almost all strong acids, strong bases, strong oxidants and organic solvents. In addition, polytetrafluoroethylene has extremely low surface tension, high smoothness and low friction coefficient. Therefore, using polytetrafluoroethylene to modify glass flakes can be very useful in reducing friction and wear. At the same time, combined with the "maze" shielding properties of the glass flakes, it can also effectively prevent the erosion of corrosive media for a long time, greatly improving the service life of the coating. Graphene oxide is a nanomaterial with a unique two-dimensional structure. Using it to modify glass flakes can improve the bonding between the glass flakes and the resin matrix, enhance the tensile strength and flexibility of the coating, and improve the brittleness of the coating. It can also help disperse the stress of the coating. When the coating is subjected to external forces and generates stress, it can disperse the stress over a larger area, avoiding concentration at a single point, thereby reducing the risk of damage such as cracking and peeling caused by stress concentration, making the coating more durable. At the same time, graphene oxide itself has a high aspect ratio and large specific surface area lamellar structure, which can tightly bind the fish-scale structure of the glass flakes to form a dense film, significantly improving the salt spray resistance and corrosion resistance of the coating. In addition, graphene oxide also has the functions of heat dissipation and flame retardancy, and has a strong heat resistance effect, further enhancing the functionality of the coating, making it very suitable for special industrial needs.

[0038] (3) Use anti-rust slow-release slurry as a means to improve the anti-corrosion performance: the inorganic corrosion inhibitor is a modified silicate corrosion inhibitor. When the corrosion stimulus ion H + After entering the coating and coming into contact with it, it will release its own alkaline components and H +Neutralization effectively reduces foaming and permeability, improving the coating's early water resistance while also preventing rust spread and sub-film corrosion at locations where the paint film is damaged. Zinc phosphomolybdate is a highly effective rust-inhibiting pigment with a strong hydrophobic nature. Upon contact with corrosive media, it immediately forms a sticky compound film, passivating the metal surface and enhancing adhesion and corrosion resistance between the coating and the metal. Boron nitride, with its low coefficient of friction and exceptional chemical stability, not only improves the coating's toughness and adhesion but also provides a degree of resistance to acid, alkali, and solvent attack. Its insulating properties inhibit electron transport, reducing the likelihood of galvanic corrosion on the metal substrate and thus providing additional corrosion protection. Furthermore, boron nitride itself possesses a layered structure similar to graphene. When combined with silicate corrosion inhibitors and zinc phosphomolybdate, it can reduce free volume in the coating, lowering the bubble rate and further enhancing the coating's anti-penetration capabilities. Under the synergistic effect of the three, through the dual means of physical anti-corrosion and chemical anti-corrosion, the coating adhesion and wet adhesion properties are improved, the early protection of the substrate is enhanced, and the coating has long-term anti-corrosion performance.

[0039] (4) The preferred rheological additives work synergistically to achieve the purpose of anti-sagging; the silanol groups on the surface of the fumed silica interact through hydrogen bonds, and the amide groups in the polyamide wax molecules form macromolecular entanglements through hydrogen bonds. Under the mutual influence of the two, a stronger and more uniform cross-type three-dimensional network structure is formed. This structure plays a supporting role in the coating, increasing the viscosity and cohesion of the coating to prevent sagging. The molecular structure of the low-shear associative thickener contains hydrophilic segments and hydrophobic segments. The hydrophobic groups aggregate to form micelles through hydrophobic effects, and associate with the particles of the emulsion or pigment filler to increase the viscosity of the system. This structure is destroyed by shear force during construction, which increases the fluidity of the coating; after the shear force disappears, the viscosity rises and the super-strong three-dimensional network structure produced by the synergistic effect of the fumed silica and polyamide wax is restored, thereby preventing the coating from flowing. The three rheological additives work together synergistically, and even when the facade is constructed at low temperatures in winter, the coating will have strong anti-sagging properties. DETAILED DESCRIPTION

[0040] The present invention will be further described below with reference to the embodiments, but the protection scope of the present invention is not limited thereto.

[0041] The water-based phenolic epoxy resin in component A is one or more of the following: American Hansen water-based epoxy resin Epikote 6006-W-68A, Bass Synthetic New Materials water-based phenolic epoxy dispersion BS-2155F, Huntsman water-based epoxy phenolic resin ARADUR ECN 1400.

[0042] The quick-drying water-based bisphenol A epoxy dispersion in component A is AQUAER-3012 water-based epoxy resin from Fuqisen New Materials, STW602 water-based epoxy emulsion from Huayi Jinghua, and Epikote water-based epoxy resin from Hansen. TM One or more of 7520-WD-52A.

[0043] The substrate wetting agent in component A is Digo Twin-4100, Shenzhu Chemical SN-4741, Digo One or more of WET KL 245; the defoaming agent is Digo One or more of Airex902W, BYK-024, and Shenzhu Chemical SN-6710; the fungicide is Dow KATHON LXE, Shenzhu Chemical SN-B9725, and Maiken Biotechnology. 210 one or more; the dispersant is Digo One or more of Dispers 760W, BYK-190, and Shenzhen Bamboo Chemical SN-1790.

[0044] The inorganic corrosion inhibitor in the anti-rust slow-release slurry of component A is Junjiang Technology's JP-B803 inorganic high-efficiency corrosion inhibitor, and the zinc phosphomolybdate is Junjiang Technology's JP-B900 zinc phosphomolybdate; the fumed silica is Evonik Degussa A200; the polyamide wax rheological additive is Fenghong New Material PA-630; the rutile titanium dioxide is one or more of Jiangxi Tianguang TR-33, Nanjing Titanium Dioxide NR-960, and Longbai Group R-996; the iron oxide black powder is Bayer's Black4330 iron oxide black; the low shear associative thickener is American Ashland Aquaflow TM XLS-525, Puwei Coadd TM U601, Wanhua Chemical One or more of U905.

[0045] The water-based amine epoxy curing agent in component B is at least one of the following: American Hansen water-based epoxy curing agent Epikore8530-W-75, Huntsman water-based epoxy curing agent Aradur38-1, and Fuqisen New Materials water-based epoxy curing agent AQUAEPO-3126; the anti-flash rust additive is Puwei Coadd TM One or more of FR-333, Shenzhu Chemical SN-9779A, and NALZIN FA-179.

[0046] The above-listed products are commercially available products, including but not limited to the following purchase sources:

[0047] American Hexion water-based epoxy resin Epikote 6006-W-68A, purchase website is as follows:

[0048] http: / / 951224.cn.makepolo.com / product / 101001590174.html

[0049] Bass Synthetic New Materials Waterborne Phenolic Epoxy Dispersion BS-2155F, available for purchase at:

[0050] https: / / china.guidechem.com / trade / pdetail21517204.html

[0051] Huntsman waterborne epoxy phenolic resin ARADUR ECN 1400, purchase website is as follows:

[0052] https: / / b2b.baidu.com / land?id=97de9f344fc43d9e757f7a24d1adfcc010

[0053] Fuqisen New Materials Water-Based Epoxy Resin AQUAER-3012, purchase from the following website:

[0054] http: / / www.fuqisen.com / productinfo / 856272.html

[0055] Huayi Refining Waterborne Epoxy Emulsion STW602, purchase from the following website:

[0056] https: / / www.chinascc.com / cn / product_details_1e.html

[0057] Hexion waterborne epoxy resin Epikote TM 7520-WD-52A, purchase link is as follows:

[0058] https: / / www.4006787252.com / article_read_5934.html

[0059] Di Gao Twin-4100 wetting agent, purchase from the following website:

[0060] https: / / www.boochem.com / runshiji / tego / 4100.html

[0061] Shenzhu Chemical SN-4741 wetting agent, purchase from the following website:

[0062] http: / / www.snyto.com / product-detail.html?tabId=471565615333642240& name=4700%E7%B3%BB%E5%88%97-%E6%9C%89%E6%9C%BA%E7%A1%85 / % E6%B0%9F%E5%9F%BA%E6%9D%90%E6%B6%A6%E6%B9%BF%E5%89%82&id= 490679527312199680

[0063] Di Gao WET KL 245 wetting agent, purchase from the following website:

[0064] https: / / b2b.baidu.com / land?id=ddcdea5c9ae717659dfb75875473fb9a10

[0065] Di Gao Airex 902W defoamer, purchase from:

[0066] https: / / b2b.baidu.com / land?id=67971cf371f309ddcb504690fb4ed45e10& jybtf=5&iid=67971cf371f309ddcb504690fb4ed45e&prod_type=7

[0067] BYK-024 defoamer, available for purchase at:

[0068] https: / / www.boochem.com / xiaopaoji / byk / 024.html

[0069] Shenzhu Chemical SN-6710 defoamer, purchase from the following website:

[0070] http: / / www.snyto.com / product-detail.html?tabId=471565615333642240& name=6700%E7%B3%BB%E5%88%97-%E6%9C%89%E6%9C%BA%E7%A1%85%E6% B6%88%E6%B3%A1%E5%89%82&id=490666943481647104

[0071] American Dow KATHON LXE fungicide, purchase website is as follows:

[0072] <h2 style=";text-align:left;direction:ltr">https: / / b2b.baidu.com / land?id=6769020590806a7b70fd0722c2d4684110

[0073] Shenzhu Chemical SN-B9725 fungicide, purchase from the following website:

[0074] <h2 style=";text-align:left;direction:ltr"> http: / / www.snyto.com / product-detail.html?tabId=471565615333642240& <h2 style=";text-align:left;direction:ltr"> name=B9700%E7%B3%BB%E5%88%97-%E6%9D%80%E8%8F%8C%E9%98%B2% <h2 style=";text-align:left;direction:ltr"> E8%85%90%E5%89%82&id=488528367851671552

[0075] Mycan Bio 210 fungicide, purchase website is as follows:

[0076] <h2 style=";text-align:left;direction:ltr"> https: / / www.mikenchem.com / index.do?product

[0077] Di Gao Dispers 760W dispersant, purchase from the following website:

[0078] <h2 style=";text-align:left;direction:ltr"> https: / / b2b.baidu.com / land?id=184d80d2cc4d6ce3895638a6fd632e4010

[0079] BYK-190 dispersant can be purchased from the following website:

[0080] <h2 style=";text-align:left;direction:ltr"> https: / / b2b.baidu.com / land?id=75b60556ccf3a2dafa148a2ab2c9923110

[0081] Shenzhu Chemical SN-1790 dispersant, purchase from the following website:

[0082] <h2 style=";text-align:left;direction:ltr"> http: / / www.snyto.com / product-detail.html?tabId=471565615333642240& <h2 style=";text-align:left;direction:ltr"> name=1300-1700%E7%B3%BB%E5%88%97--%E8%B6%85%E5%88%86%E6%95% <h2 style=";text-align:left;direction:ltr"> A3%E5%89%82&id=488127412459016192

[0083] Junjiang Technology JP-B803 inorganic high-efficiency corrosion inhibitor, purchase website is as follows:

[0084] <h2 style=";text-align:left;direction:ltr"> http: / / www.junjiangtech.com / h-pd-231.html

[0085] Junjiang Technology JP-B900 zinc phosphomolybdate, purchase from the following website:

[0086] <h2 style=";text-align:left;direction:ltr"> http: / / www.junjiangtech.com / h-pd-240.html

[0087] Evonik Degussa A200 fumed silica, available for purchase at:

[0088] <h2 style=";text-align:left;direction:ltr"> https: / / www.jingyichina.net / h-pd-119.html?sdclkid= <h2 style=";text-align:left;direction:ltr"> ALfi15fsb6D6bLgpA5fD&bd_vid=8351200287251058050

[0089] Fenghong New Materials PA-630 polyamide wax rheological additive, purchase website is as follows:

[0090] <h2 style=";text-align:left;direction:ltr"> https: / / www.gys.cn / fangchenji / 4678401092.html

[0091] Ashland Aquaflow TM XLS-525 low shear associative thickener, purchase from the following website:

[0092] <h2 style=";text-align:left;direction:ltr"> https: / / aiqicha.baidu.com / productdetail?pid=35908152249177&productId <h2 style=";text-align:left;direction:ltr"> =4f5bfe60c929d06bdb3f1b4e5fc4376f

[0093] Puwei Coadd TM U601 low shear associative thickener, purchase website is as follows:

[0094] <h2 style=";text-align:left;direction:ltr"> http: / / www.polywill.com / page105?_l=zh_CN

[0095] Wanhua Chemical U905 low shear associative thickener, purchase website is as follows:

[0096] <h2 style=";text-align:left;direction:ltr"> https: / / video.ceultimate.com / 100009_2007175034 / Vesmody_U905-TDS-CH_ <h2 style=";text-align:left;direction:ltr"> v1.2.pdf

[0097] American Hexion Epikore 8530-W-75 water-based epoxy curing agent can be purchased from the following website:

[0098] <h2 style=";text-align:left;direction:ltr">https: / / b2b.baidu.com / land?id=8cec842fcbafc87e9daee0240ead2fc810

[0099] Huntsman Aradur 38-1 waterborne epoxy curing agent, purchase website is as follows:

[0100] <h2 style=";text-align:left;direction:ltr"> https: / / b2b.baidu.com / land?id=12ce59c868660f9939891af9e6ba97a510

[0101] Fuqisen New Materials AQUAEPO-3126 water-based epoxy curing agent, purchase website is as follows:

[0102] <h2 style=";text-align:left;direction:ltr"> http: / / www.fuqisen.com / productinfo / 911600.html

[0103] Puwei Coadd TM FR-333 water-based anti-flash rust additive, purchase website is as follows:

[0104] <h2 style=";text-align:left;direction:ltr"> http: / / www.polywill.com / page130?_l=zh_CN

[0105] Shenzhu Chemical SN-9779A water-based anti-flash rust additive, purchase website is as follows:

[0106] <h2 style=";text-align:left;direction:ltr"> http: / / www.snyto.com / product-detail.html?tabId=471565615333642240& <h2 style=";text-align:left;direction:ltr"> name=9000%E7%B3%BB%E5%88%97-%E7%89%B9%E7%A7%8D%E5%8A%A9%E5% <h2 style=";text-align:left;direction:ltr"> 89%82&id=490681006223790080

[0107] NALZIN FA-179 water-based anti-flash rust additive from Haiming Si Deqian can be purchased from the following website:

[0108] <h2 style=";text-align:left;direction:ltr"> https: / / aiqicha.baidu.com / productdetail?pid=32497583134710&productId <h2 style=";text-align:left;direction:ltr"> =1d223b90e676eb8178fd07ed0583a954

[0109] The preparation steps of the water-based epoxy glass flake coatings of Examples 1 to 4 (see Table 1 for material ratios) and Comparative Examples 1 to 5 are as follows:

[0110] (1) Preparation of double-modified glass flakes

[0111] 80 parts by mass of isopropanol and 20 parts by mass of deionized water were added to the reactor, and the pH was adjusted to 4 with acetic acid. Then, 20 parts by mass of polytetrafluoroethylene powder was added to the reactor. After heating to 60°C, 12 parts by mass of silane coupling agent KH-560 was added. Then, 30 parts by mass of acetone was used as a catalyst for ultrasonic dispersion for 2 hours. The reactor was transferred to a magnetic dispersion kettle and 50 parts by mass of 200-mesh glass flakes were added to the reactor. The reactor was heated to 80°C and magnetically dispersed for 5 hours to obtain a polytetrafluoroethylene-modified glass flake suspension. The suspension was taken out, filtered, washed with ethanol, dried, and then sent to a 60°C oven for drying for 2 hours after the ethanol evaporated to obtain polytetrafluoroethylene-modified glass flakes.

[0112] Add 50 parts by mass of toluene solution to the reactor, add 40 parts by mass of graphene oxide powder and heat to 80°C, use 20 parts by mass of tetraisopropyl titanate as a catalyst, and ultrasonically disperse for 2 hours; transfer to a magnetic dispersion kettle, add 70 parts by mass of polytetrafluoroethylene-modified glass flakes in the previous step, control the reaction temperature to 110°C, and magnetically disperse for 10 hours to obtain a suspension of glass flakes dual-modified with graphene oxide and polytetrafluoroethylene. After filtering, washing with ethanol and drying, obtain graphene oxide-polytetrafluoroethylene dual-modified glass flake powder.

[0113] (2) Preparation of rust-proof slow-release slurry

[0114] 3 parts by mass of inorganic corrosion inhibitor, 40 parts by mass of zinc phosphomolybdate and 10 parts by mass of hexagonal boron nitride powder were mixed and 30 parts by mass of deionized water were added. Dispers 760W aqueous dispersant was prepared into an aqueous composite slurry, which was transferred to a sand mill and 1 part by mass of fumed silica A200 was added. The material was ground for 5 hours and then discharged. The fineness was ground to 20 μm. After cooling, 0.5 parts by mass of fungicide LXE was added and mixed evenly to obtain an anti-rust slow-release slurry. Among them, the inorganic corrosion inhibitor was JP-B803 inorganic high-efficiency corrosion inhibitor from Junjiang Technology, and the zinc phosphomolybdate was JP-B900 zinc phosphomolybdate from Junjiang Technology.

[0115] (3) Preparation of high-performance, long-lasting anti-corrosion water-based epoxy glass flake coating

[0116] Component A: Add water-based phenolic epoxy resin and quick-drying water-based bisphenol A epoxy dispersion into the paint mixing kettle and mix evenly. Then, add dipropylene glycol butyl ether, substrate wetting agent, defoamer, bactericide, dispersant, anti-rust slow-release slurry and deionized water into the mixing kettle, and pre-disperse at a speed of 600r / min for 20 minutes to obtain a first mixed material; then add double-modified glass flakes, rutile titanium dioxide, iron oxide black powder and fumed silica into the paint mixing kettle and mix with the first mixed material, and disperse at a high speed of 1200r / min for 1h until the fineness is qualified to prepare the second mixed material; then add polyamide wax rheological additive and low-shear associative thickener to adjust the viscosity to 110KU to obtain component A of water-based epoxy glass flake coating.

[0117] Component B: Disperse the waterborne amine epoxy curing agent and propylene glycol methyl ether in proportion at a speed of 600 r / min for 10 minutes; then add the anti-flash rust additive and deionized water and disperse at a speed of 600 r / min for 10 minutes to obtain component B of the waterborne epoxy glass flake coating;

[0118] During construction, evenly mix component A and component B in a mass ratio of 5:1 to obtain the target product.

[0119] Table 1 Addition amount of component A in Examples 1 to 4 (parts by mass)

[0120]

[0121]

[0122] Table 2 Addition amount of component B materials in Examples 1 to 4 (parts by mass)

[0123]

[0124] Material ratios of Comparative Examples 1 to 5:

[0125] (1) Comparative Example 1

[0126] 10 parts by mass of waterborne epoxy novolac resin and 25 parts by mass of quick-drying waterborne bisphenol A epoxy dispersion in Example 1 were used to replace 35 parts by mass of waterborne epoxy novolac resin Epikote 6006-W-68A, and the remaining material proportions were the same as in Example 1.

[0127] (2) Comparative Example 2

[0128] The 12 parts by mass of waterborne epoxy novolac resin and the 30 parts by mass of quick-drying waterborne bisphenol A epoxy dispersion in Example 2 were replaced with the 42 parts by mass of quick-drying waterborne bisphenol A epoxy dispersion AQUAER-3012, and the remaining material proportions were the same as in Example 2.

[0129] (3) Comparative Example 3

[0130] The 28 parts by mass of double-modified glass flakes in Example 3 were replaced with 28 parts by mass of unmodified 200-mesh glass flakes, and the remaining material ratios were the same as in Example 3.

[0131] (4) Comparative Example 4

[0132] The 15 parts by mass of the anti-rust slow-release slurry in Example 4 were replaced with 15 parts by mass of the anti-rust slurry of zinc phosphate compounded with aluminum tripolyphosphate, and the proportions of other materials were the same as those in Example 4.

[0133] (5) Comparative Example 5

[0134] The 0.5 parts by mass of fumed silica, 0.5 parts by mass of polyamide wax rheological additive, and 0.5 parts by mass of low shear associative thickener in Example 1 were replaced with 1.5 parts by mass of medium shear associative thickener Wanhua Chemical U605, and the proportions of other materials are the same as those in Example 1.

[0135] Performance Testing

[0136] Test panels are fabricated, maintained, and tested according to the methods specified in the respective implementation standards. Additional performance test parameters may be added based on actual usage. Standard test conditions are a temperature of (23±2)°C and a relative humidity of (50±5)%. The specimens are left under these conditions for 24 hours before testing.

[0137] The main technical indicators of the coating are listed as follows (Table 3):

[0138] Table 3 Conventional performance indicators of Examples 1 to 4

[0139]

[0140]

[0141] Note: The coating thickness for hot water resistance, gasoline resistance, salt spray resistance and chemical medium resistance test is 250um to 350um dry film (two coats).

[0142] Table 4 Conventional performance indicators of comparative examples 1 to 5

[0143]

[0144] Note: The coating thickness for hot water resistance, gasoline resistance, salt spray resistance and chemical medium resistance test is 250um to 350um dry film (two coats).

[0145] Test result description:

[0146] Comparison between Example 1 and Comparative Example 1: In the comparative example, the compound of water-based epoxy novolac resin and quick-drying water-based bisphenol A epoxy dispersion was replaced with a single water-based epoxy novolac resin. Although the water-based novolac epoxy resin has a higher cross-linking density and more cross-linking points, and the resulting coating film has stronger resistance and outstanding high temperature resistance, it has the disadvantage of being slow to dry. During winter, low-temperature construction, the risk of film sagging will increase. At the same time, in terms of initial water resistance, since the coating film has not yet been fully cross-linked in the short term, it cannot block H in time. + The erosion of water-based epoxy phenolic resin and quick-drying water-based bisphenol A epoxy resin is not outstanding. And the cohesive force is large and the shrinkage volume is large after the water-based epoxy phenolic resin is cured, and the paint film is relatively brittle, is difficult to absorb and disperse energy when bearing impact, and cracks and peels off easily.It can be seen from this that the embodiment can not only improve its dryness by the composite preferred ratio of water-based epoxy phenolic resin and quick-drying water-based bisphenol A epoxy, but also can keep its excellent anti-corrosion performance.

[0147] Example 2 is compared with Comparative Example 2: In the Comparative Example, a compound of a water-based epoxy novolac resin and a quick-drying water-based bisphenol A epoxy dispersion is replaced with a single quick-drying water-based bisphenol A epoxy dispersion. As the main film-forming substance, quick-drying water-based bisphenol A epoxy dispersion is a macromolecular epoxy with fast drying, good flexibility, and strong anti-sagging properties. However, due to its lower crosslinking density compared to phenolic epoxy, its chemical resistance and salt spray resistance after curing are average, and its heat resistance is biased. This comprehensive performance does not guarantee long-term and durable corrosion protection. In contrast, by compounding quick-drying water-based bisphenol A epoxy and water-based epoxy novolac in the preferred ratio in the Example, the heat resistance and corrosion resistance of the coating can be greatly improved, effectively providing long-term protection.

[0148] Example 3 is compared with Comparative Example 3: In the comparative example, the double-modified glass flakes are replaced with unmodified 200-mesh glass flakes. The unmodified glass flakes have poor adhesion to the resin, are brittle, have poor wear resistance, and have low adhesion and impact resistance. Moreover, their chemical structure is simple and their arrangement is loose, resulting in a large number of pores in the coating film, which has limited effect in shielding the penetration of chemical media and ions, and is not effective in blocking high-concentration strong acids and alkalis. The formed coating is easily eroded by corrosive media and mechanically damaged, and has a short service life. The modified glass flakes in the embodiment have good flexibility and can form a dense structure of multi-layer barriers, effectively enhancing the coating's anti-penetration ability and chemical resistance.

[0149] Example 4 is compared with Comparative Example 4: In the comparative example, the anti-rust slow-release slurry is replaced by zinc phosphate compounded with aluminum tripolyphosphate anti-rust slurry. Zinc phosphate and aluminum tripolyphosphate are common anti-rust pigment combinations in anti-corrosion coatings and have a wide range of uses. However, because zinc phosphate and aluminum tripolyphosphate need time to decompose to form an oxide film on the substrate, the effect is delayed, so the early anti-rust performance of the substrate is not obvious and "flash rust" is prone to occur in humid and low-temperature weather; secondly, zinc phosphate and aluminum tripolyphosphate have low solubility, large product particle size, wide particle size distribution, and irregular morphology, and cannot form a dense lamellar structure shielding effect, and the anti-penetration ability is weak, and there is almost no "physical anti-corrosion" anti-rust performance, which greatly reduces the ability of long-term protective coatings. In the embodiment, by compounding inorganic corrosion inhibitors, zinc phosphomolybdate and hexagonal boron nitride, early contact with metal ions and H + It reacts quickly, effectively reducing the bubble rate of the coating and isolating it from water vapor intrusion. It can also form a multi-layer overlapping dense structure with glass flakes, effectively implementing physical and chemical dual anti-corrosion measures to provide long-term protection for the coating.

[0150] Example 1 is compared with Comparative Example 5: In the comparative example, the fumed silica, polyamide wax rheological additive, and low-shear associative thickener are replaced with a single medium-shear associative thickener. First, the storage period is short, and precipitation or even hard precipitation will appear in the tank, making it difficult to stir evenly, seriously affecting the coating's properties such as solid content and viscosity. Secondly, as a heavy-duty anti-corrosion coating, there are certain regulatory requirements for the thickness of the coating film, and thick coating is usually required, which places strong demands on the coating's anti-sagging performance. A single medium-shear associative thickener has limited anti-sagging properties for the coating, and the wet film's sag limit thickness is low, and the dry film thickness after film formation is even lower. Multiple construction operations are required to achieve the ideal film thickness, which greatly affects the construction period and labor costs, and brings many inconveniences to the project progress. The embodiment forms a powerful super network structure through the three-in-one effect of fumed silica, polyamide wax rheological additive and low-shear associative thickener, which effectively prevents the flow of coating and greatly improves the anti-sagging ability of the coating. It not only enables long-term stable storage, but also ensures the uniformity of coating thickness during construction, thereby avoiding the coating from being too thin and affecting the long-term anti-corrosion performance.

Claims

1. A high-performance, long-lasting anti-corrosion water-based epoxy glass flake coating, characterized in that: The coating comprises component A and component B, wherein component A comprises the following components in parts by weight: The ingredients of component B are as follows:

2. A high-performance, long-lasting anti-corrosion water-based epoxy glass flake coating according to claim 1, characterized in that It is composed of the following components and parts by weight: The ingredients of component B are as follows:

3. A high-performance, long-lasting anti-corrosion water-based epoxy glass flake coating according to claim 1 or 2, characterized in that The water-based phenolic epoxy resin in component A is one or more of the following: American Hansen water-based epoxy resin Epikote 6006-W-68A, Bass Synthetic New Materials water-based phenolic epoxy dispersion BS-2155F, Huntsman water-based epoxy phenolic resin ARADUR ECN 1400.

4. A high-performance, long-lasting anti-corrosion water-based epoxy glass flake coating according to claim 1 or 2, characterized in that The quick-drying water-based bisphenol A epoxy dispersion in component A is AQUAER-3012 water-based epoxy resin from Fuqisen New Materials, STW602 water-based epoxy emulsion from Huayi Jinghua, and Epikote water-based epoxy resin from Hansen. TM One or more of 7520-WD-52A.

5. A high-performance, long-lasting anti-corrosion water-based epoxy glass flake coating according to claim 1 or 2, characterized in that The double-modified glass flakes of component A are prepared by the following steps: S1: Add isopropanol and deionized water to the reactor, adjust the pH to 4-5 with acetic acid, then add polytetrafluoroethylene powder to the reactor, heat to 50-60°C, add silane coupling agent KH-560, and then use acetone as a catalyst for ultrasonic dispersion for 2-3 hours. Transfer to a magnetic dispersion kettle and continue to add 100-300 mesh glass flakes to the reactor, heat to 70-80°C and perform magnetic dispersion for 3-6 hours to obtain a polytetrafluoroethylene-modified glass flake suspension, take out and filter it, wash it with ethanol, place it to dry, and after the ethanol evaporates, send it into a 50-60°C oven for drying for 1-3 hours to obtain polytetrafluoroethylene-modified glass flakes; Preferably, the dosage of each component in S1 is as follows: S2: After adding toluene and graphene oxide powder to the reactor, the temperature is heated to 70-80°C, tetraisopropyl titanate is used as a catalyst, and ultrasonic dispersion is performed for 2-3 hours; the mixture is transferred to a magnetic dispersion kettle, and the polytetrafluoroethylene-modified glass flakes in step S1 are added, the reaction temperature is controlled to 100-110°C, and magnetic dispersion is performed for 10-12 hours to obtain a suspension of glass flakes dual-modified with graphene oxide and polytetrafluoroethylene, which is filtered, washed with ethanol, and dried to obtain graphene oxide-polytetrafluoroethylene dual-modified glass flake powder; Preferably, the amount of each component in S2 is as follows:

6. A high-performance, long-lasting anti-corrosion water-based epoxy glass flake coating according to claim 1 or 2, characterized in that The substrate wetting agent in component A is Digo Twin-4100, Shenzhu Chemical SN-4741, Digo One or more of WETKL 245; the defoaming agent is Digo One or more of Airex 902W, BYK-024, and Shenzhu Chemical SN-6710; the fungicide is Dow KATHON LXE, Shenzhu Chemical SN-B9725, and Mycan Bio 210 one or more; the dispersant is Digo One or more of Dispers 760W, BYK-190, and Shenzhen Bamboo Chemical SN-1790.

7. A high-performance, long-lasting anti-corrosion water-based epoxy glass flake coating according to claim 1 or 2, characterized in that The anti-rust slow-release slurry of component A is prepared by the following steps: mixing inorganic corrosion inhibitor, zinc phosphomolybdate and hexagonal boron nitride powder and adding deionized water; Dispers760W dispersant was prepared into a water-based compound slurry. The slurry was transferred to a sand mill and fumed silica A200 was added. After grinding for 4 to 6 hours, the material was discharged and ground to a fineness of less than 25 μm. After cooling, fungicide LXE was added and mixed evenly to obtain a rust-proof slow-release water slurry. Optimum: The components in the rust-proof slow-release slurry are as follows: Further preferably, the inorganic corrosion inhibitor is Junjiang Technology's JP-B803 inorganic high-efficiency corrosion inhibitor, and the zinc phosphomolybdate is Junjiang Technology's JP-B900 zinc phosphomolybdate.

8. A high-performance, long-lasting anti-corrosion water-based epoxy glass flake coating according to claim 1 or 2, characterized in that The fumed silica in component A is Evonik Degussa A200; the polyamide wax rheological additive is Fenghong New Material PA-630; the rutile titanium dioxide is one or more of Jiangxi Tianguang TR-33, Nanjing Titanium Dioxide NR-960, and Longbai Group R-996; the iron oxide black powder is LANXESS Bayer Black 4330 iron oxide black; the low shear associative thickener is American Ashland Aquaflow TM XLS-525, Puwei Coadd TM U601, Wanhua Chemical One or more of U905.

9. A high-performance, long-lasting anti-corrosion water-based epoxy glass flake coating according to claim 1 or 2, characterized in that The water-based amine epoxy curing agent in component B is at least one of the following: American Hansen water-based epoxy curing agent Epikore8530-W-75, Huntsman water-based epoxy curing agent Aradur38-1, and Fuqisen New Materials water-based epoxy curing agent AQUAEPO-3126; the anti-flash rust additive is Puwei Coadd TM One or more of FR-333, Shenzhu Chemical SN-9779A, and NALZIN FA-179.

10. A high-performance, long-lasting anti-corrosion water-based epoxy glass flake coating according to claim 1 or 2, characterized in that The preparation steps of this method are as follows: Preparation of component A: adding water-based phenolic epoxy resin and quick-drying water-based bisphenol A epoxy dispersion into a paint mixing kettle and mixing them evenly; then adding dipropylene glycol butyl ether, substrate wetting agent, defoamer, fungicide, dispersant, rust-proof slow-release slurry and deionized water into a mixing kettle, pre-dispersing at a speed of 400-600 r / min for 10-20 minutes to obtain a first mixed material; then adding double-modified glass flakes, rutile titanium dioxide, iron oxide black powder and fumed silica into the paint mixing kettle and mixing and stirring with the first mixed material evenly, and high-speed dispersing at 1000-1200 r / min for 0.5-1 hour to prepare a second mixed material; then adding a polyamide wax rheological additive and a low-shear associative thickener to adjust the viscosity to 100KU-120KU to obtain component A of a water-based epoxy glass flake coating; Preparation of component B: Disperse a waterborne amine epoxy curing agent and propylene glycol methyl ether in proportion at a rotation speed of 600 to 800 r / min for 5 to 10 minutes; then add an anti-flash rust additive and deionized water and disperse at a rotation speed of 400 to 600 r / min for 5 to 10 minutes to obtain component B of a waterborne epoxy glass flake coating; During construction, evenly mix component A and component B at a mass ratio of 4 to 6:1 to obtain the target product.

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