Hydrophobic anticorrosive epoxy vinyl ester resin based on organic fluorine modification as well as preparation method and application of hydrophobic anticorrosive epoxy vinyl ester resin
Through UV curing system and fluorine-containing segment modification, the defects of epoxy vinyl ester resin during the curing process are solved, low-energy consumption, efficient corrosion and hydrophobic performance are achieved, and the protection ability of the coating is improved.
Patent Information
- Application Number
- CN202510763214.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-09
- Publication Date
- 2025-08-08
AI Technical Summary
During the curing process, traditional epoxy vinyl ester resins have high crosslink density and rearrangement of molecular chain segments, and their hydrophilic properties accelerate media penetration in a high humidity environment, affecting the protection effect. The traditional thermal curing process has high energy consumption and is not suitable for industrial applications.
UV curing system combined with hydrophobic functional modification is adopted to achieve rapid curing by free radical polymerization of vinyl and photoinitiator, and the fluorine-containing chain segment is introduced to form a dense hydrophobic layer, reducing the surface energy of the coating and avoiding defects caused by thermal stress.
It achieves low energy consumption curing, improves the anticorrosion and hydrophobic properties of the coating, reduces water molecules adsorption and capillary penetration, and enhances the protective effect of the coating.
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Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of polymer materials, and in particular relates to a hydrophobic anticorrosive epoxy vinyl ester resin modified based on organic fluorine, and a preparation method and application thereof. Background Art
[0002] Epoxy vinyl ester resin is the base resin of anti-corrosion coatings. It can effectively block the metal substrate from corrosive media (such as Cl - , H2O, O2, etc.), significantly slowing metal corrosion. However, during the curing process, the resin shrinks in volume due to its high cross-linking density and rearrangement of molecular segments. This leads to the formation of micron-sized holes, microcracks and other defects within the coating, which serve as channels for the penetration of corrosive media and seriously affect the long-term protection effect. Especially in high-humidity environments such as the ocean, the hydrophilic properties of traditional coatings accelerate the penetration of media, further shortening the protection life. In addition, conventional thermal curing processes require high energy consumption at high temperatures for several hours, which not only exacerbates the resin shrinkage defects but also restricts industrial application. Therefore, the development of new resin systems that combine low shrinkage properties, hydrophobic functions and energy-saving curing processes has become a key direction to break through the bottleneck of existing technologies.
[0003] The present invention adopts a UV curing system combined with hydrophobic functional modification, realizes rapid curing through free radical polymerization of vinyl and photoinitiator, effectively reduces energy consumption, and avoids coating defects caused by thermal stress; synchronously introduces fluorine-containing chain segments, significantly weakens water molecule adsorption and capillary penetration by reducing the surface energy of the coating, self-enriches on the coating surface to form a dense hydrophobic layer, and forms a gradient protective structure with the resin body, thereby improving the anti-corrosion performance of the epoxy vinyl ester resin. Summary of the Invention
[0004] The first object of the present invention is to provide a hydrophobic anti-corrosion epoxy vinyl ester resin modified based on organic fluorine. The second object of the present invention is to provide a preparation method of the hydrophobic anti-corrosion epoxy vinyl ester resin modified based on organic fluorine. The third object of the present invention is the application of the hydrophobic anti-corrosion epoxy vinyl ester resin modified based on organic fluorine.
[0005] According to a first aspect of the present invention, a hydrophobic anticorrosive epoxy vinyl ester resin based on organic fluorine modification is provided. The raw materials thereof include, in parts by weight: 30-50 parts of epoxy resin, 0.5-10 parts of organic fluorine alcohol, 0.5-10 parts of unsaturated acid anhydride, 9-20 parts of unsaturated carboxylic acid, 0.01-0.1 parts of polymerization inhibitor, 0.05-0.5 parts of catalyst, 15-40 parts of active diluent and 1-20 parts of filler.
[0006] In some embodiments, when preparing the organic fluorine-modified hydrophobic anticorrosive epoxy vinyl ester resin using the above raw materials, the organic fluorine alcohol is first reacted with the unsaturated acid anhydride to prepare the organic fluorine modifier, and then the organic fluorine modifier is reacted with other raw materials.
[0007] In some embodiments, the organic fluoroalcohol is selected from at least one of 2-perfluoroalkylethyl alcohol, 1H,1H,2H,2H-perfluoro-1-ol, perfluorodecanol, 1H,1H,2H,2H-perfluoro-1-decanol, perfluorotetradecanol, 1,1,2,2-tetrahydroperfluorotetradecanol, and 1,1,2,2-tetrahydroperfluorododecanol.
[0008] In some embodiments, the unsaturated acid anhydride is selected from at least one of fumaric anhydride, benzoic anhydride, itaconic anhydride, phthalic anhydride, maleic anhydride, and succinic anhydride.
[0009] In some embodiments, the epoxy resin is selected from at least one of diphenol propane epoxy resin, phenol formaldehyde multi-epoxy resin, o-cresol epoxy resin, novolac epoxy resin, resorcinol epoxy resin, resorcinol-formaldehyde epoxy resin, and tetraphenol ethane epoxy resin.
[0010] In some embodiments, the unsaturated carboxylic acid is selected from at least one of acrylic acid, 4-pentenoic acid, undecenoic acid, trans-2-pentenoic acid, and 9-decenoic acid.
[0011] In some embodiments, the catalyst is selected from at least one of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30), benzyldimethylamine, tetrabutylammonium bromide, triethylbenzylammonium chloride, and N-hydroxyphenyldimethylurea.
[0012] In some embodiments, the filler may be nanoparticles used as corrosion-resistant fillers. Specifically, the nanoparticles are selected from at least one of nano-titanium dioxide, nano-silicon dioxide, nano-zinc oxide, nano-graphene oxide, and nano-titanium powder.
[0013] In some embodiments, the polymerization inhibitor is selected from at least one of hydroquinone, p-tert-butylcatechol, catechol, 2,2-diphenyl-1-picrylhydrazyl free radical, p-hydroxyanisole, and cuprous chloride.
[0014] In some embodiments, the reactive diluent is selected from at least one of trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, styrene, α-methylstyrene, ethoxylated pentaerythritol tetraacrylate, ethylene glycol diacrylate, and hydroxyethyl methacrylate.
[0015] According to a second aspect of the present invention, there is provided a method for preparing a hydrophobic anticorrosive epoxy vinyl ester resin modified with organic fluorine, comprising the following steps: (1) reacting an organic fluorine alcohol with an unsaturated acid anhydride at 70-150° C. for 8-12 hours, washing the solid to neutrality after the reaction, and then filtering and drying the obtained solid to obtain an organic fluorine modifier; (2) reacting the organic fluorine modifier with the epoxy resin at 70-120°C for 4-12 hours, then adding unsaturated carboxylic acid, catalyst and polymerization inhibitor, raising the temperature to 100-130°C and reacting for 3-7 hours until the acid value is lower than 15 mg KOH / g, then cooling to 50-90°C, adding active diluent and filler, and mixing evenly to obtain the product.
[0016] Specifically, the preparation method of the hydrophobic anticorrosive epoxy vinyl ester resin based on organic fluorine modification comprises the following steps: (1) melting an organic fluorine alcohol and an unsaturated acid anhydride at 70-150° C. and then performing a cyclic condensation reaction and reflux for 8-12 hours. After the reaction is completed, deionized water is added to the reaction system, and the solid is repeatedly washed until neutral. The obtained solid is then filtered and dried to obtain an organic fluorine modifier; (2) reacting the organic fluorine modifier with the epoxy resin at 70-120°C for 4-12 hours, then adding unsaturated carboxylic acid, catalyst and polymerization inhibitor, raising the temperature to 100-130°C and reacting for 3-7 hours until the acid value is lower than 15 mg KOH / g, then cooling to 50-90°C, adding active diluent and filler, and mixing evenly to obtain the product.
[0017] Specifically, the operation of the cyclic condensation reaction is to install a condenser at one of the ports of the three-necked flask, pass flowing water, and the solution is superheated and converted into gas, which enters the condenser, and then cools down again to become liquid and flows back to the three-necked flask to continue the reaction.
[0018] According to a third aspect of the present invention, there is provided a use of an organic fluorine-modified hydrophobic anticorrosive epoxy vinyl ester resin in the preparation of a coating.
[0019] In some embodiments, the coating can be an anti-corrosion coating. Preferably, the coating can be an atmospheric anti-corrosion coating or a marine anti-corrosion coating.
[0020] Compared with the prior art, the present invention has the following beneficial effects: (1) The present invention first undergoes an esterification reaction between an organic fluorine alcohol and an organic acid anhydride to obtain an organic fluorine modifier, then undergoes a ring-opening reaction between the carboxyl group of the organic fluorine ester modifier and the epoxy group of the epoxy resin to prepare an organic fluorine semi-terminated epoxy resin, and then uses an unsaturated carboxylic acid to undergo a ring-opening reaction with the remaining epoxy groups of the epoxy resin to prepare an organic fluorine-modified hydrophobic anticorrosive epoxy vinyl ester resin. The cured film prepared from the organic fluorine-modified hydrophobic anticorrosive epoxy vinyl ester resin of the present invention has excellent mechanical properties, chemical resistance, hydrophobicity, and anticorrosive properties, and is suitable for use as an anticorrosive coating for metal structures in atmospheric or seawater corrosive environments.
[0021] (2) The present invention introduces organic fluorine chain segments into epoxy vinyl ester resin to prepare hydrophobic anti-corrosion epoxy vinyl ester resin based on organic fluorine modification, thereby improving the crosslinking density, thermal stability, hydrophobic and oleophobic properties, chemical resistance, mechanical properties and anti-corrosion properties of the epoxy vinyl ester resin.
[0022] (3) The organic fluorine modifier prepared by the present invention has a low molecular weight and viscosity and can directly participate in subsequent reactions. No gelation will occur during the subsequent reactions. The final product does not contain organic solvents and is safe and environmentally friendly.
[0023] (4) The organic fluorine-modified hydrophobic anticorrosive epoxy vinyl ester resin of the present invention has the conditions for photocuring and can be UV-cured after adding a photoinitiator. Compared with the traditional thermal curing method, it effectively reduces energy consumption and is more environmentally friendly.
[0024] (5) The present invention grafts the organic fluoride ester monomer onto the epoxy resin by a ring-opening reaction between the carboxyl group of the organic fluorine modifier and the epoxy group of the epoxy resin, which can give the resin lower surface energy and anti-corrosion performance, and improve the compatibility of the organic fluoride ester with the epoxy vinyl ester resin, reducing the effect of phase separation on its performance, thereby effectively blocking corrosive substances from entering the interior of the coating.
[0025] (6) The preparation process of the organic fluorine-modified hydrophobic anti-corrosion epoxy vinyl ester resin of the present invention is simple, and no organic solvent is added. The finally obtained organic fluorine-modified hydrophobic anti-corrosion epoxy vinyl ester resin does not contain organic solvent and is safe and environmentally friendly. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Figure 1 This is a Fourier transform infrared spectrum of perfluorotetradecanol, itaconic anhydride and organic fluorine modifier in Example 1 of the present invention. DETAILED DESCRIPTION
[0027] The present invention will be further described in detail below with reference to the accompanying drawings, but the embodiments of the present invention are not limited thereto. The raw materials and reagents involved in the following examples can all be obtained from commercial channels.
[0028] The present invention firstly performs an esterification reaction between an organic fluorine alcohol and an unsaturated acid anhydride to obtain an organic fluorine ester, then performs a ring-opening reaction between the carboxyl group of the organic fluorine ester and the epoxy group of the epoxy resin to prepare an organic fluorine ester semi-capped epoxy resin, and then uses an unsaturated carboxylic acid to perform a ring-opening reaction with the remaining epoxy groups of the epoxy resin to prepare an organic fluorine-modified hydrophobic anticorrosive epoxy vinyl ester resin.
[0029] Example 1 This embodiment provides a method for preparing a hydrophobic anticorrosive epoxy vinyl ester resin based on organic fluorine modification, comprising the following steps: (1) 2 g of perfluorotetradecanol and 5 g of itaconic anhydride were reacted at 130° C. for 5 h, and then repeatedly washed with deionized water until neutral. The resulting solid was filtered and dried to obtain an organic fluorine modifier solid; (2) Add the organic fluorine modifier solid prepared in step (1), 45 g of diphenol propane type epoxy resin and 0.05 g of benzyldimethylamine to a three-necked flask, react at 90° C. for 2 h, then add 14 g of acrylic acid and 0.01 g of hydroquinone to the three-necked flask, heat to 100° C. and react for 4 h until the acid value is lower than 15 mg KOH / g, then cool to 80° C., add 24 g of trimethylolpropane triacrylate and 1.5 g of nano-titanium dioxide to the three-necked flask, mix well, and obtain a hydrophobic anticorrosive epoxy vinyl ester resin based on organic fluorine modification.
[0030] The structures of perfluorotetradecanol, itaconic anhydride and organic fluorine modifier in Example 1 were characterized by using Thermo Fisher Nicolet iS10 Fourier transform infrared spectrometer. Figure 1 shown.
[0031] from Figure 1 It can be seen that in the infrared absorption curve of itaconic anhydride, at 1635 cm -1 The absorption peak at 1237 cm is caused by the stretching vibration of the C=C bond. -1 、1195 cm -1 The absorption peak at 655-703 cm is attributed to the stretching vibration of -CF2 and -CF3. -1 The absorption peak observed in the range corresponds to the stretching vibration peak of -CF. On the infrared absorption curve of the product organic fluorine modifier, 1724 cm -1 and 1635 cm -1 The stretching vibration absorption peaks of C=O and C=C bonds appeared at the positions, respectively, indicating that itaconic anhydride and perfluorotetradecanol successfully underwent esterification to prepare the organic fluorine modifier.
[0032] Example 2 This embodiment provides a method for preparing a hydrophobic anticorrosive epoxy vinyl ester resin based on organic fluorine modification, comprising the following steps: (1) 2 g of 2-perfluoroalkylethyl alcohol and 5 g of benzoic anhydride were reacted at 130° C. for 5 h, and then repeatedly washed with deionized water until neutral. The resulting solid was filtered and dried to obtain an organic fluorine modifier; (2) Add the organic fluorine modifier prepared in step (1), 45 g of diphenol propane type epoxy resin and 0.05 g of benzyldimethylamine to a three-necked flask, react at 90° C. for 2 h, then add 14 g of acrylic acid and 0.01 g of hydroquinone to the three-necked flask, heat to 100° C. and react for 4 h until the acid value is lower than 15 mgKOH / g, then cool to 80° C., add 24 g of trimethylolpropane triacrylate and 1.5 g of nano-silica to the three-necked flask, mix well, and obtain a hydrophobic anticorrosive epoxy vinyl ester resin based on organic fluorine modification.
[0033] Example 3 This embodiment provides a method for preparing a hydrophobic anticorrosive epoxy vinyl ester resin based on organic fluorine modification, comprising the following steps: (1) 2 g of 1H,1H,2H,2H-perfluoro-1-ol was reacted with 5 g of phthalic anhydride at 130°C for 5 h, and then repeatedly washed with deionized water until neutral. The resulting solid was filtered and dried to obtain an organic fluorine modifier; (2) Add the organic fluorine modifier prepared in step (1), 45 g of diphenol propane type epoxy resin and 0.05 g of benzyldimethylamine to a three-necked flask, react at 90° C. for 2 h, then add 14 g of acrylic acid and 0.01 g of hydroquinone to the three-necked flask, heat to 100° C. and react for 4 h until the acid value is lower than 15 mg KOH / g, then cool to 80° C., add 24 g of trimethylolpropane triacrylate and 1.5 g of nano-silica to the three-necked flask, mix well, and obtain a hydrophobic anticorrosive epoxy vinyl ester resin based on organic fluorine modification.
[0034] Example 4 This embodiment provides a method for preparing a hydrophobic anticorrosive epoxy vinyl ester resin based on organic fluorine modification, comprising the following steps: (1) 2 g of perfluorodecanol and 5 g of itaconic anhydride were reacted at 130°C for 5 h, and then repeatedly washed with deionized water until neutral. The resulting solid was filtered and dried to obtain an organic fluorine modifier; (2) Add the organic fluorine modifier prepared in step (1), 45 g of diphenol propane type epoxy resin and 0.05 g of benzyldimethylamine to a three-necked flask, react at 90° C. for 2 h, then add 14 g of acrylic acid and 0.01 g of hydroquinone to the three-necked flask, heat to 100° C. and react for 4 h until the acid value is lower than 15 mg KOH / g, then cool to 80° C., add 24 g of trimethylolpropane triacrylate and 1.5 g of nano-silica to the three-necked flask, mix well, and obtain a hydrophobic anticorrosive epoxy vinyl ester resin based on organic fluorine modification.
[0035] Example 5 This embodiment provides a method for preparing a hydrophobic anticorrosive epoxy vinyl ester resin based on organic fluorine modification, comprising the following steps: (1) 2 g of 1H,1H,2H,2H-perfluoro-1-decanol and 5 g of itaconic anhydride were reacted at 130°C for 5 h, and then repeatedly washed with deionized water until neutral. The resulting solid was filtered and dried to obtain an organic fluorine modifier; (2) Add the organic fluorine modifier prepared in step (1), 45 g of diphenol propane type epoxy resin and 0.05 g of benzyldimethylamine to a three-necked flask, react at 90° C. for 2 h, then add 14 g of acrylic acid and 0.01 g of hydroquinone to the three-necked flask, heat to 100° C. and react for 4 h until the acid value is lower than 15 mg KOH / g, then cool to 80° C., add 24 g of trimethylolpropane triacrylate and 1.5 g of nano-silica to the three-necked flask, mix well, and obtain a hydrophobic anticorrosive epoxy vinyl ester resin based on organic fluorine modification.
[0036] Example 6 This embodiment provides a method for preparing a hydrophobic anticorrosive epoxy vinyl ester resin based on organic fluorine modification, comprising the following steps: (1) 2 g of perfluorotetradecanol and 5 g of maleic anhydride were reacted at 130°C for 5 h, and then repeatedly washed with deionized water until neutral. The resulting solid was filtered and dried to obtain an organic fluorine modifier; (2) Add the organic fluorine modifier prepared in step (1), 45 g of diphenol propane type epoxy resin and 0.05 g of benzyldimethylamine to a three-necked flask, react at 90° C. for 2 h, then add 14 g of acrylic acid and 0.01 g of hydroquinone to the three-necked flask, heat to 100° C. and react for 4 h until the acid value is lower than 15 mgKOH / g, then cool to 80° C., add 24 g of trimethylolpropane triacrylate and 1.5 g of nano-silica to the three-necked flask, mix well, and obtain a hydrophobic anticorrosive epoxy vinyl ester resin based on organic fluorine modification.
[0037] Comparative Example 1 This comparative example provides a method for preparing an epoxy vinyl ester resin, comprising the following steps: To a three-necked flask, 45 g of diphenol propane epoxy resin, 14 g of acrylic acid, 0.05 g of benzyldimethylamine, and 0.01 g of hydroquinone were added. The flask was placed in an oil bath at 110°C and stirred for 3 h until the acid value was lower than 15 mg KOH / g. The temperature was then lowered to 80°C. 26 g of active diluent styrene was added to the flask and mixed well to obtain epoxy vinyl ester resin.
[0038] Next, the organic fluorine-modified hydrophobic anticorrosive epoxy vinyl ester resins prepared in Examples 1-6 and the epoxy vinyl ester resin prepared in Comparative Example 1 were coated on polished tinplate, and UV-cured films were obtained after ultraviolet irradiation. The UV-cured films were then tested for their anticorrosive and mechanical properties.
[0039] 1. Preparation of UV curing film Commercially available tinplate was polished with 300-mesh and 1500-mesh sandpaper, scrubbed with deionized water and anhydrous ethanol, and oven-dried for later use. The resins prepared in Examples 1-6 and Comparative Example 1 were mixed with 3 wt% of the photoinitiator hydroxy-2-methylpropenoate (PI-1173) to obtain samples to be treated. The samples were then placed in a vacuum drying oven, set to a vacuum degree of 0.1 MPa, and treated in a vacuum environment for 30 minutes to effectively remove bubbles in the samples. The samples were then removed and the resin was uniformly coated on glass using a 250 μm four-sided molder. The glass was then placed under a UV curing lamp for 30 seconds at a distance of 10 cm to obtain a UV-cured film.
[0040] 2. Mechanical properties and anti-corrosion performance test (1) Mechanical properties test: The mechanical properties of the cured films coated on the polished tinplate were tested according to the national standard GB / T1040.3-2006. The tensile strength and elongation at break were recorded. The results are shown in Table 1.
[0041] (2) Chemical corrosion resistance test: The UV-cured films coated on the polished tinplate were immersed in a 10 wt% NaOH solution for 7 days. After that, the films were taken out and observed for blistering, rusting, and shedding. The results are shown in Table 1. It should be noted that "none" in Table 1 means that the films did not exhibit blistering, rusting, or shedding.
[0042] From the test results in Table 1, it can be seen that the tensile strength and elongation at break of the cured film prepared from the epoxy vinyl ester resin and the cured film prepared from the organic fluorine-modified hydrophobic anticorrosive epoxy vinyl ester resin of the embodiment are higher than those of the cured film of Comparative Example 1, and the tensile strength thereof is increased by 39.04%-75.99%, indicating that the mechanical properties of the cured film of the organic fluorine-modified hydrophobic anticorrosive epoxy vinyl ester resin of the present invention are significantly improved compared with the cured film of the epoxy vinyl ester resin.
[0043] The cured film made of epoxy vinyl ester resin showed blistering after being treated with 10 wt % NaOH solution for 7 days, while the cured film of Examples 1-6 based on organic fluorine-modified hydrophobic anti-corrosion epoxy vinyl ester resin was not observed to blister, rust or fall off after being treated with 10 wt % NaOH solution for 7 days, and the water contact angles were all greater than 90°, indicating that the cured film made of epoxy vinyl ester resin based on organic fluorine-modified hydrophobic anti-corrosion epoxy vinyl ester resin has better chemical resistance and good hydrophobic effect than the cured film made of epoxy vinyl ester resin.
[0044] Table 1 Performance test results of cured films made from the resins of Examples 1-6 and Comparative Example 1
[0045] To further evaluate the anticorrosion performance of the organic fluorine-modified hydrophobic anticorrosive epoxy vinyl ester resins of the present invention, the resins prepared in Examples 4-6 and Comparative Example 1 were coated onto tinplate to a thickness of 80 ± 5 μm. After curing, the anticorrosion performance of the samples was evaluated using electrochemical impedance spectroscopy.
[0046] A three-electrode system was used, with a platinum electrode as the auxiliary electrode, a saturated calomel electrode as the reference electrode, a coated tinplate as the working electrode, and a 3.5 wt% NaCl aqueous solution as the corrosion medium. The frequency range of the electrochemical impedance spectroscopy (EIS) was 10 5 Hz to 10 -2 Hz, using a sinusoidal perturbation with a 20 mV amplitude at open circuit potential (OCP). Using the low-frequency impedance modulus as a quantitative indicator of corrosion resistance, different samples were tested immediately after being placed in a 3.5wt% NaCl aqueous solution and after being immersed in the NaCl solution for 60 days. The test results are shown in Table 2.
[0047] Table 2 Low-frequency impedance modulus of different samples immersed in 3.5 wt% NaCl aqueous solution for 60 days
[0048] The larger the low-frequency impedance modulus, the better the anti-corrosion performance. As can be seen from Table 2, the initial values of the low-frequency impedance modulus of the organic fluorine-modified hydrophobic anti-corrosion epoxy vinyl ester resin cured films of Examples 4-6 are higher than those of the cured film of Comparative Example 1, indicating that the coating porosity of the obtained cured films is low and the corrosive media (such as water, Cl) are not easily absorbed. - The organic fluorine modifier used in the present invention is prepared from an organic fluorine alcohol and an unsaturated acid anhydride. The hydrogen atoms of the organic fluorine alcohol are replaced by fluorine, which combines hydrophobicity with chemical resistance. Furthermore, the nanoparticles can act as anti-corrosion fillers in the resin voids. When combined with the organic fluorine modifier, they further reduce the resin porosity and form a dense structure that inhibits the penetration of corrosive media. Among them, the cured film of Example 6 showed the best initial low-frequency impedance modulus results.
[0049] After immersion in a 3.5wt% NaCl aqueous solution for 60 days, the low-frequency impedance modulus value of the UV-cured films prepared from the organic fluorine-modified hydrophobic anti-corrosion epoxy vinyl ester resins of Examples 4-6 was increased by four orders of magnitude compared to the UV-cured film prepared from the epoxy vinyl ester resin of Comparative Example 1, indicating that after the organic fluorine modifier is introduced into the epoxy vinyl ester resin of the present invention, the anti-corrosion performance of the resin is greatly improved, and also indicating that the organic fluorine-modified hydrophobic anti-corrosion epoxy vinyl ester resin of the present invention has excellent anti-corrosion performance and long-term protection ability.
[0050] The above are only some embodiments of the present invention. For those skilled in the art, several modifications and improvements can be made without departing from the inventive concept of the present invention, which all fall within the scope of protection of the present invention.
Claims
1. A hydrophobic anticorrosive epoxy vinyl ester resin based on organic fluorine modification, characterized in that: The raw materials include, by weight, 30-50 parts of epoxy resin, 0.5-10 parts of organic fluorine alcohol, 0.5-10 parts of unsaturated acid anhydride, 9-20 parts of unsaturated carboxylic acid, 0.01-0.1 parts of polymerization inhibitor, 0.05-0.5 parts of catalyst, 15-40 parts of active diluent and 1-20 parts of filler.
2. The organic fluorine-modified hydrophobic anticorrosive epoxy vinyl ester resin according to claim 1, characterized in that: The organic fluoroalcohol is selected from at least one of 2-perfluoroalkylethyl alcohol, 1H,1H,2H,2H-perfluoro-1-alcohol, perfluorodecanol, 1H,1H,2H,2H-perfluoro-1-decanol, perfluorotetradecanol, 1,1,2,2-tetrahydroperfluorotetradecanol, and 1,1,2,2-tetrahydroperfluorododecanol.
3. The organic fluorine-modified hydrophobic anticorrosive epoxy vinyl ester resin according to claim 1, characterized in that: The unsaturated acid anhydride is selected from at least one of fumaric anhydride, benzoic anhydride, itaconic anhydride, phthalic anhydride, maleic anhydride and succinic anhydride.
4. The organic fluorine-modified hydrophobic anticorrosive epoxy vinyl ester resin according to any one of claims 1 to 3, characterized in that: The filler is nanoparticles; The nanoparticles are selected from at least one of nano titanium dioxide, nano silicon dioxide, nano zinc oxide, nano graphene oxide, and nano titanium powder.
5. The organic fluorine-modified hydrophobic anticorrosive epoxy vinyl ester resin according to claim 1, characterized in that: The epoxy resin is selected from at least one of diphenol propane epoxy resin, phenol formaldehyde multi-epoxy resin, o-cresol epoxy resin, novolac epoxy resin, resorcinol epoxy resin, resorcinol-formaldehyde epoxy resin, and tetraphenol ethane epoxy resin; The unsaturated carboxylic acid is selected from at least one of acrylic acid, 4-pentenoic acid, undecenoic acid, trans-2-pentenoic acid, and 9-decenoic acid.
6. The organic fluorine-modified hydrophobic anticorrosive epoxy vinyl ester resin according to claim 1, characterized in that: The polymerization inhibitor is selected from at least one of hydroquinone, p-tert-butylcatechol, catechol, 2,2-diphenyl-1-picrylhydrazyl free radical, p-hydroxyanisole, and cuprous chloride.
7. The organic fluorine-modified hydrophobic anticorrosive epoxy vinyl ester resin according to claim 1, characterized in that: The catalyst is selected from at least one of 2,4,6-tris(dimethylaminomethyl)phenol, benzyldimethylamine, tetrabutylammonium bromide, triethylbenzylammonium chloride, and N-hydroxyphenyldimethylurea.
8. The organic fluorine-modified hydrophobic anticorrosive epoxy vinyl ester resin according to claim 1, characterized in that: The reactive diluent is selected from at least one of trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, styrene, α-methylstyrene, ethoxylated pentaerythritol tetraacrylate, ethylene glycol diacrylate, and hydroxyethyl methacrylate.
9. The method for preparing the organic fluorine-modified hydrophobic anticorrosive epoxy vinyl ester resin according to any one of claims 1 to 8, characterized in that: The following steps are involved: (1) reacting an organic fluorine alcohol with an unsaturated acid anhydride at 70-150° C. for 8-12 hours, washing the solid to neutrality after the reaction, and then filtering and drying the obtained solid to obtain an organic fluorine modifier; (2) reacting the organic fluorine modifier with the epoxy resin at 70-120°C for 4-12 hours, then adding unsaturated carboxylic acid, catalyst and polymerization inhibitor, raising the temperature to 100-130°C and reacting for 3-7 hours until the acid value is lower than 15 mg KOH / g, then cooling to 50-90°C, adding active diluent and filler, and mixing evenly to obtain the product.
10. Use of the organic fluorine-modified hydrophobic anticorrosive epoxy vinyl ester resin according to any one of claims 1 to 8 in the preparation of coatings.