PBC bio-based heavy-duty anticorrosive coating and preparation process thereof

Abstract

The application relates to the technical field of anticorrosive coatings, and particularly discloses a PBC bio-based heavy-duty anticorrosive coating and a preparation process thereof. The PBC bio-based heavy-duty anticorrosive coating comprises a primer, an intermediate paint and a topcoat; the coating takes bio-based epoxy resin as a main film-forming material, and a composite fiber prepared by using raw materials including pretreated hydroxyapatite, polymethyl methacrylate and chitosan is added in the preparation process of the coating. The PBC bio-based heavy-duty anticorrosive coating prepared by the application has the advantages of high corrosion resistance, impact resistance and wear resistance.

Description

Technical Field

[0001] This application relates to the field of anti-corrosion coating technology, and more specifically, to a PBC bio-based heavy-duty anti-corrosion coating and its preparation process. Background Technology

[0002] In modern industrial systems, metallic materials and infrastructure face severe challenges from complex corrosive environments. Metal components in energy, transportation, marine engineering, and chemical industries are exposed to harsh conditions such as salt spray, acids and alkalis, and high temperatures for extended periods, leading to structural failures and safety hazards that cause significant economic losses. Heavy-duty anti-corrosion coatings, as a core technology for metal surface protection, achieve physical isolation and electrochemical protection against corrosive media by forming highly durable coatings. They are widely used in critical facilities such as offshore platforms, petrochemical storage tanks, bridges, and ships, effectively extending the service life of steel structures and ensuring the safety of major projects. With the increasing sophistication of industrial protection standards, the development of heavy-duty anti-corrosion coating systems that combine high performance and environmental friendliness has become an urgent need in the field of materials protection.

[0003] Current mainstream heavy-duty anti-corrosion coatings use petroleum-based resins as their base material. Although the technology is mature, it has several problems: 1. It releases a large amount of VOCs, such as benzene compounds and isocyanates, during the production and construction process; 2. It relies on non-renewable petroleum resources, resulting in high energy consumption during production. In contrast, bio-based heavy-duty anti-corrosion coatings use renewable biomass as raw materials, combining environmental friendliness with functional designability. Its research and application are of great significance for promoting the upgrading of industrial anti-corrosion technology.

[0004] Patent application CN113045955A discloses a low-surface-treatment heavy-duty anti-corrosion coating, its preparation method, and its application. The coating of this invention is prepared from the following raw materials: Component A: first film-forming resin, second film-forming resin, epoxy diluent, hydrocarbon resin, titanium dioxide, mineral powder, and additives; Component B: first curing agent and second curing agent. The coating of this invention uses bio-based resin as the main film-forming substance, which has environmental protection properties, low requirements for substrate treatment, long anti-corrosion effect, good adhesion, and salt spray resistance.

[0005] In the aforementioned document, inorganic additives were added to improve the anti-corrosion and mechanical properties of the coating. However, due to the poor compatibility between inorganic particles and organic resins, the interfacial bonding force is weak. During friction or impact, stress cannot be effectively transferred from the resin matrix, which easily leads to cracks and interfacial delamination, thus preventing the coating from maintaining its anti-corrosion performance. Therefore, it is very important to solve the above problems in order to maintain the anti-corrosion performance of the coating. Summary of the Invention

[0006] To further improve the anti-corrosion performance of coatings, this application provides a PBC bio-based heavy-duty anti-corrosion coating and its preparation process.

[0007] In the first aspect, this application provides a PBC bio-based heavy-duty anti-corrosion coating, which adopts the following technical solution:

[0008] A PBC bio-based heavy-duty anti-corrosion coating includes a primer, an intermediate coat, and a topcoat;

[0009] The primer comprises bio-epoxy resin, modified vegetable oil, composite fiber, filler one, and curing agent;

[0010] The intermediate varnish includes bio-epoxy resin, modified vegetable oil, composite fiber, filler II, and curing agent;

[0011] The topcoat comprises bio-epoxy resin, modified vegetable oil, composite fiber, filler three, and curing agent;

[0012] The bio-epoxy resin in the primer, intermediate coat and topcoat is made from raw materials including carboxylic acid derivatives, polyols, eugenol, guaiacol and epichlorohydrin.

[0013] The modified vegetable oil in the primer, intermediate coat and topcoat is made from maleic anhydride modified soybean oil;

[0014] The composite fibers in the primer, intermediate coat, and topcoat are made from raw materials including pretreated hydroxyapatite, polymethyl methacrylate, and chitosan.

[0015] Preferably, the preparation method of the bio-epoxy resin includes the following steps:

[0016] 1) Mix carboxylic acid derivatives, polyols and toluene, and carry out a polymerization reaction to obtain the precursor;

[0017] 2) Mix the precursor and tetrahydrofuran, then add syringaldehyde solution to carry out esterification reaction to obtain intermediate M;

[0018] 3) Mix intermediate M and guaiacol, then add a catalyst to carry out a condensation reaction to obtain intermediate N;

[0019] 4) Mix intermediate N and epichlorohydrin, add tetrabutylammonium bromide, react for a period of time, then add sodium hydroxide aqueous solution and continue the reaction to obtain bio-epoxy resin.

[0020] Preferably, the method for preparing the composite fiber includes the following steps: mixing polymethyl methacrylate and an aqueous solution of acetic acid, adding chitosan, heating to dissolve, then adding pretreated hydroxyapatite, and sonicating to obtain a spinning solution; electrospinning the spinning solution to obtain a fiber matrix, and impregnating the fiber matrix with a mixed solution of formic acid and acetic acid to obtain the composite fiber.

[0021] By adopting the above technical solution, the composite fiber, as a reinforcing phase, transfers energy to the entire coating when the coating is subjected to stress, avoiding local stress concentration that could lead to coating cracking. At the same time, the addition of the composite fiber reduces the brittleness of the resin matrix, giving the coating good flexibility and ductility, inhibiting the generation of microcracks caused by curing shrinkage or external stress, and preventing the substrate from being directly exposed to the corrosive environment. In addition, the porous structure of the pretreated hydroxyapatite surface extends the path of corrosive media to the substrate, thereby improving the anti-corrosion performance of the coating. Furthermore, the pretreated hydroxyapatite in the composite fiber can withstand frictional stress, reducing direct wear of the resin matrix and improving the wear resistance of the coating.

[0022] Preferably, the pretreated hydroxyapatite is obtained by ammoniation of hydroxyapatite with an ammoniation reagent.

[0023] By adopting the above technical solution, the amino groups on the surface of hydroxyapatite undergo chemical cross-linking with the epoxy groups of epoxy resin to form covalent bonds, which enhances the interfacial bonding between the composite fiber and the resin matrix. Furthermore, the pretreated hydroxyapatite fills the pores of the resin matrix to form a reinforcing network, thereby improving the density and mechanical properties of the coating and thus enhancing the corrosion resistance of the coating.

[0024] Preferably, the mass ratio of polymethyl methacrylate, chitosan, and pretreated hydroxyapatite is (4-6):1:(2.5-3).

[0025] Preferably, the electrospinning process is as follows: voltage 18-20kV, receiving distance 14-17cm, and feeding rate 1-2mL / h.

[0026] Preferably, the average particle size of the hydroxyapatite is 150-200 nm.

[0027] Preferably, the amination reagent is 3-aminopropyltriethoxysilane or 3-aminopropyltrimethoxysilane.

[0028] Preferably, by weight, the primer comprises the following components: 35-40 parts of bio-epoxy resin, 2-3 parts of modified vegetable oil, 5-8 parts of composite fiber, 31-47 parts of filler, and 28-36 parts of curing agent.

[0029] The intermediate paint comprises the following components: 40-45 parts of bio-epoxy resin, 1-3 parts of modified vegetable oil, 3-5 parts of composite fiber, 24-38 parts of filler, and 25-35 parts of curing agent.

[0030] The topcoat comprises the following components: 45-50 parts of bio-epoxy resin, 1-2 parts of modified vegetable oil, 5-10 parts of composite fiber, 18-26 parts of filler, and 27-38 parts of curing agent.

[0031] Preferably, in step 1), the carboxylic acid derivative is 2-phosphonosuccinic acid or phosphonobutane tricarboxylic acid.

[0032] Preferably, in step 1), the polyol is composed of glycerol and ethylene glycol in a mass ratio of (2-3):1.

[0033] Preferably, the filler is composed of zinc phosphate, mica iron oxide, barium sulfate and silicon dioxide;

[0034] And / or, the filler two is composed of glass flakes, mica powder and barium sulfate;

[0035] And / or, the filler three is composed of titanium dioxide, carbon black and montmorillonite.

[0036] Secondly, this application provides a preparation process for a PBC bio-based heavy-duty anti-corrosion coating, including the preparation of the primer, the intermediate coat and the topcoat;

[0037] The preparation method of the primer includes the following steps: mixing bio-epoxy resin, modified vegetable oil, composite fiber and filler to prepare component A; using curing agent as component B; mixing component A and component B to obtain the primer;

[0038] The preparation method of the intermediate paint includes the following steps: mixing bio-epoxy resin, modified vegetable oil, composite fiber and filler to form component C; using curing agent as component D; mixing component C and component D to obtain the intermediate paint;

[0039] The preparation method of the topcoat includes the following steps: mixing bio-epoxy resin, modified vegetable oil, composite fiber and filler to form component E; using curing agent as component F; and mixing component E and component F to obtain the topcoat.

[0040] In summary, this application has the following beneficial effects:

[0041] 1. The composite fibers form a three-dimensional network reinforcement skeleton inside the coating, which effectively inhibits the initiation and propagation of cracks, thereby improving the coating's impact resistance and crack resistance. In addition, the hydroxyapatite protruding from the surface of the composite fibers increases the frictional resistance inside the coating. When subjected to external forces, the fibers absorb energy through deformation, further enhancing the coating's toughness and durability.

[0042] 2. Aminated hydroxyapatite undergoes a chemical cross-linking reaction with the epoxy groups of epoxy resin through its surface-modified amino groups, forming a stable covalent bond network. This enhances the interfacial compatibility and bonding force between the composite fiber and the resin matrix, further improving the toughness and wear resistance of the coating. At the same time, its insertion into the voids of epoxy resin increases the density of the coating, hinders the penetration of corrosive media, and enhances the corrosion resistance of the coating.

[0043] 3. The porous structure of hydroxyapatite forms a physical barrier in the coating. When corrosive media penetrate into the coating, the tortuous path of the porous structure can significantly slow down the diffusion rate of the media and increase its penetration resistance, thereby reducing the probability of contact between the corrosive media and the substrate and improving the anti-corrosion performance of the coating.

[0044] 4. Introducing phosphonoyl groups into bio-epoxy resins enhances the bonding strength between the bio-epoxy resin and the substrate, thus improving the adhesion of the coating. Simultaneously, the introduction of phosphonoyl groups also strengthens the bonding strength between the bio-epoxy resin and hydroxyapatite, thereby improving the stability of the composite fibers in the resin and further enhancing the wear resistance, toughness, and corrosion resistance of the coating. Attached Figure Description

[0045] Figure 1 These are photographs of the coatings prepared from the paints of Examples 1-3 and Comparative Examples 1-2 of this application after a 6500-hour salt spray test.

[0046] Figure 2 These are scanning electron microscope images of the composite fibers prepared in Examples 1-3 of this application. Detailed Implementation

[0047] The present application will be further described in detail below with reference to the embodiments.

[0048] Unless otherwise specified, the raw materials used in the embodiments and comparative examples of this application are all commercially available.

[0049] Example 1

[0050] The PBC bio-based heavy-duty anti-corrosion coating of this embodiment includes a primer, an intermediate coat, and a topcoat;

[0051] The primer consists of component A and component B;

[0052] Component A consists of the following components: 35g bio-epoxy resin, 2g modified vegetable oil, 5g composite fiber, 15g zinc phosphate, 5g mica iron oxide, 10g barium sulfate, 1g silica, 0.5g dispersant Kaysalor DS 7996, 0.5g defoamer Anjeka-5680A, 1g leveling agent Kaysalor Glide 1645, and 2g propylene glycol methyl ether acetate; Component B is 28g HG-8003T curing agent.

[0053] The preparation method of the primer is as follows: Weigh 35g of bio-epoxy resin and 2g of modified vegetable oil into a 250mL three-necked flask, add 2g of propylene glycol methyl ether acetate, heat to 45℃, stir at 400rpm for 15min, then add 5g of composite fiber, 15g of zinc phosphate, 5g of mica iron oxide, 10g of barium sulfate, 1g of silica, 0.5g of dispersant Kaysalor DS 7996, 0.5g of defoamer Anjeka-5680A, and 1g of leveling agent Kaysalor Glide 1645, sonicate for 30min, stir at 1000rpm for 40min, then add 28g of HG-8003T curing agent, stir at 600rpm for 15min to obtain the primer.

[0054] The intermediate paint consists of component C and component D;

[0055] Component C consists of the following components: 40g of bio-epoxy resin, 1g of modified vegetable oil, 3g of composite fiber, 5g of glass flakes, 15g of mica powder, 4g of barium sulfate, 0.5g of thixotropic agent Anjeka 4410, 0.2g of defoamer Anjeka-5680A, and 2g of propylene glycol methyl ether acetate; Component D is 25g of HG-8003T curing agent.

[0056] The preparation method of intermediate paint is as follows: Weigh 40g of bio-epoxy resin and 1g of modified vegetable oil into a 250mL three-necked flask, add 2g of propylene glycol methyl ether acetate, heat to 40℃, stir at 400rpm for 15min, then add 3g of composite fiber, 5g of glass flakes, 15g of mica powder, 4g of barium sulfate, 0.5g of thixotropic agent Anjeka 4410, and 0.2g of defoamer Anjeka-5680A, sonicate for 40min, stir at 800rpm for 1h, then add 25g of HG-8003T curing agent, stir at 600rpm for 20min to obtain intermediate paint.

[0057] The topcoat consists of components E and F;

[0058] Component E consists of the following components: 45g of bio-epoxy resin, 1g of modified vegetable oil, 5g of composite fiber, 15g of titanium dioxide, 2g of carbon black, 1g of montmorillonite, 1g of UV absorber BASF Chimassorb 81, 0.3g of leveling agent Kaysalor Glide 1645, and 1g of propylene glycol methyl ether acetate; Component F is 27g of HG-8003T curing agent.

[0059] The preparation method of the topcoat is as follows: Weigh 45g of bio-epoxy resin and 1g of modified vegetable oil into a 250mL three-necked flask, add 1g of propylene glycol methyl ether acetate, stir at 500rpm for 15min, then add 5g of composite fiber, 15g of titanium dioxide, 2g of carbon black, 1g of montmorillonite, 1g of UV absorber BASF Chimassorb 81, and 0.3g of leveling agent Kaysalor Glide 1645, sonicate for 50min, stir at 1000rpm for 40min, then add 27g of HG-8003T curing agent, stir at 600rpm for 20min to obtain the topcoat.

[0060] The preparation method of the bio-epoxy resin in this embodiment is as follows:

[0061] 1) Weigh 39g of 2-phosphonosuccinic acid, 6g of glycerol, 3g of ethylene glycol and 80g of toluene into a 250mL three-necked flask. Heat to 140℃ under a nitrogen atmosphere, then add 0.15g of p-toluenesulfonic acid. React for 7h. After the reaction is completed, perform vacuum distillation to obtain the precursor.

[0062] 2) Take 45g of precursor and 180g of tetrahydrofuran and put them into a 500mL three-necked flask. After stirring evenly, add 45g of 4-dimethylaminopyridine. Under nitrogen atmosphere, cool down to 0℃ and add a mixed solution of 0.6g of dicyclohexylcarbodiimide and 8g of tetrahydrofuran at a rate of 1mL / min. Then add a mixed solution of 45g of syringaldehyde and 13g of tetrahydrofuran at a rate of 0.8mL / min. React for 50min, adjust the temperature to 25℃ and continue to react for 20h. Filter, retain the liquid component, wash with saturated sodium bicarbonate solution and physiological saline in sequence, evaporate by rotary evaporation, and dry to obtain intermediate M.

[0063] 3) Weigh 55g of guaiacol into a 500mL three-necked flask, heat to 50℃, stir for 20min, stop heating, add 80g of intermediate M and mix well, adjust the temperature to 40℃, then add 50g of p-toluenesulfonic acid and 40g of zinc chloride, react for 20h, after the reaction is complete, wash, retain the organic phase, then add 90g of ethanol and mix well, pour into 500g of deionized water for precipitation, filter, collect the solid product, dry, and obtain intermediate N;

[0064] 4) Take 130g of intermediate N and 95g of epichlorohydrin and put them into a 500mL three-necked flask. Heat to 110℃ and stir for 40min. Add 1.8g of tetrabutylammonium bromide and react for 5h. Then cool to 50℃ and add 50g of 30% sodium hydroxide aqueous solution. React for 2h. After the reaction is completed, cool to room temperature, add 200g of dichloromethane and mix well. Wash and retain the organic phase. Add anhydrous magnesium sulfate and dry. Rotary evaporate to obtain bio-epoxy resin.

[0065] The modified vegetable oil in this embodiment is prepared as follows: 25g of soybean oil is weighed and put into a four-necked flask, and then 10g of maleic anhydride is added. Under a nitrogen atmosphere, the temperature is raised to 210°C and reacted for 3 hours to obtain the modified vegetable oil.

[0066] The method for preparing the composite fiber in this embodiment is as follows:

[0067] S1: Weigh 20g of deionized water and 30g of ethanol into a three-necked flask, add glacial acetic acid to adjust the pH to 5, add 2g of hydroxyapatite with an average particle size of 150nm and mix well, then add 0.2g of 3-aminopropyltrimethoxysilane, heat to 50℃ and react for 10h, centrifuge, dry to obtain ammoniated hydroxyapatite.

[0068] S2: Weigh 4g of polymethyl methacrylate and 50g of acetic acid aqueous solution with a mass percentage concentration of 80% and add them to a three-necked flask. Heat to 35℃ and stir until the polymethyl methacrylate is completely dissolved. Add 1g of chitosan and continue stirring for 4h. Then add 2.5g of aminated hydroxyapatite and sonicate for 30min to obtain a spinning solution. Inject the spinning solution into a syringe for electrospinning. During electrospinning, the voltage is 18kV, the receiving distance is 17cm, and the feed rate is 2mL / h to obtain a fiber matrix. Impregnate the fiber matrix with a mixed solution of 75g formic acid and 25g acetic acid for 30min. Filter, wash, dry, and pulverize to obtain composite fibers with an average length of 40μm.

[0069] Example 2

[0070] The PBC bio-based heavy-duty anti-corrosion coating of this embodiment includes a primer, an intermediate coat, and a topcoat;

[0071] The primer consists of component A and component B;

[0072] Component A consists of the following components: 38g of bio-epoxy resin, 3g of modified vegetable oil, 6g of composite fiber, 17g of zinc phosphate, 8g of mica iron oxide, 11g of barium sulfate, 1.5g of silica, 0.6g of dispersant EFKA FA 4610, 0.8g of defoamer EFKAPB 2010, 1.5g of leveling agent EFKA FL 3772, and 3g of propylene glycol methyl ether acetate; Component B is 30g of HG-8003T curing agent.

[0073] The preparation method of the primer is as follows: Weigh 38g of bio-epoxy resin and 3g of modified vegetable oil into a 250mL three-necked flask, add 3g of propylene glycol methyl ether acetate, heat to 45℃, stir at 400rpm for 20min, then add 6g of composite fiber, 17g of zinc phosphate, 8g of mica iron oxide, 11g of barium sulfate, 1.5g of silica, 0.6g of dispersant EFKA FA 4610, 0.8g of defoamer EFKA PB 2010, and 1.5g of leveling agent EFKA FL 3772, sonicate for 35min, stir at 1000rpm for 40min, then add 30g of HG-8003T curing agent, stir at 600rpm for 20min to obtain the primer.

[0074] The intermediate paint consists of component C and component D;

[0075] Component C consists of the following components: 42g of bio-epoxy resin, 3g of modified vegetable oil, 4g of composite fiber, 8g of glass flakes, 16g of mica powder, 5g of barium sulfate, 0.7g of thixotropic agent EFKA RM 1900, 0.3g of defoamer EFKA PB 2010, and 2.5g of propylene glycol methyl ether acetate; Component D is 27g of HG-8003T curing agent.

[0076] The intermediate varnish is prepared as follows: Weigh 42g of bio-epoxy resin and 3g of modified vegetable oil into a 250mL three-necked flask, add 2.5g of propylene glycol methyl ether acetate, heat to 40℃, stir at 400rpm for 15min, then add 4g of composite fiber, 8g of glass flakes, 16g of mica powder, 5g of barium sulfate, 0.7g of thixotropic agent EFKA RM 1900, and 0.3g of defoamer EFKA PB2010, sonicate for 50min, stir at 800rpm for 1h, then add 27g of HG-8003T curing agent, stir at 600rpm for 25min to obtain the intermediate varnish.

[0077] The topcoat consists of components E and F;

[0078] Component E consists of the following components: 49g of bio-epoxy resin, 2g of modified vegetable oil, 7g of composite fiber, 18g of titanium dioxide, 3.5g of carbon black, 1.5g of montmorillonite, 1.8g of UV absorber BASF Tinuvin 328, 0.4g of leveling agent EFKA FL3772, and 1.5g of propylene glycol methyl ether acetate; Component F is 30g of HG-8003T curing agent.

[0079] The preparation method of the topcoat is as follows: Weigh 49g of bio-epoxy resin and 2g of modified vegetable oil into a 250mL three-necked flask, add 1.5g of propylene glycol methyl ether acetate, stir at 500rpm for 15min, then add 7g of composite fiber, 18g of titanium dioxide, 3.5g of carbon black, 1.5g of montmorillonite, 1.8g of UV absorber BASF Tinuvin 328, and 0.4g of leveling agent EFKA FL 3772, sonicate for 50min, stir at 1000rpm for 40min, then add 30g of HG-8003T curing agent, stir at 600rpm for 40min to obtain the topcoat.

[0080] The preparation method of the bio-epoxy resin in this embodiment is as follows:

[0081] 1) Weigh 40g of phosphonobutane tricarboxylic acid, 9g of glycerol, 2g of ethylene glycol and 80g of toluene into a 250mL three-necked flask. Heat to 145℃ under a nitrogen atmosphere, then add 0.15g of p-toluenesulfonic acid. React for 6 hours. After the reaction is completed, perform vacuum distillation to obtain the precursor.

[0082] 2) Take 45g of precursor and 180g of tetrahydrofuran and put them into a 500mL three-necked flask. After stirring evenly, add 40g of 4-dimethylaminopyridine. Under nitrogen atmosphere, cool down to 0℃ and add a mixed solution of 0.6g of dicyclohexylcarbodiimide and 8g of tetrahydrofuran at a rate of 1.5mL / min. Then add a mixed solution of 45g of syringaldehyde and 15g of tetrahydrofuran at a rate of 1mL / min. React for 50min, adjust the temperature to 25℃ and continue to react for 15h. Filter, retain the liquid component, wash with saturated sodium bicarbonate solution and physiological saline in sequence, evaporate by rotary evaporation, and dry to obtain intermediate M.

[0083] 3) Weigh 55g of guaiacol into a 500mL three-necked flask, heat to 50℃, stir for 20min, stop heating, add 70g of intermediate M and mix well, adjust the temperature to 40℃, then add 50g of p-toluenesulfonic acid and 30g of zinc chloride, react for 16h, after the reaction is complete, wash, retain the organic phase, then add 90g of ethanol and mix well, pour into 500g of deionized water for precipitation, filter, collect the solid product, dry, and obtain intermediate N;

[0084] 4) Take 130g of intermediate N and 100g of epichlorohydrin and put them into a 500mL three-necked flask. Heat to 110℃ and stir for 40min. Add 2g of tetrabutylammonium bromide and react for 5h. Then cool to 50℃ and add 50g of 30% sodium hydroxide aqueous solution. React for 2h. After the reaction is completed, cool to room temperature, add 200g of dichloromethane and mix well. Wash and retain the organic phase. Add anhydrous magnesium sulfate and dry. Rotary evaporate to obtain bio-epoxy resin.

[0085] The modified vegetable oil in this embodiment is prepared as follows: 30g of soybean oil is weighed and put into a four-necked flask, and then 10g of maleic anhydride is added. Under a nitrogen atmosphere, the temperature is raised to 210°C and reacted for 4 hours to obtain the modified vegetable oil.

[0086] The method for preparing the composite fiber in this embodiment is as follows:

[0087] S1: Weigh 30g of deionized water and 30g of ethanol into a three-necked flask, add glacial acetic acid to adjust the pH to 5, add 2g of hydroxyapatite with an average particle size of 180nm and mix well, then add 0.2g of 3-aminopropyltriethoxysilane, heat to 50℃ and react for 8h, centrifuge, dry to obtain ammoniated hydroxyapatite.

[0088] S2: Weigh 5g of polymethyl methacrylate and 55g of acetic acid aqueous solution with a mass percentage concentration of 80% and add them to a three-necked flask. Heat to 35℃ and stir until the polymethyl methacrylate is completely dissolved. Add 1g of chitosan and continue stirring for 4 hours. Then add 2.7g of ammoniated hydroxyapatite and sonicate for 30 minutes to obtain a spinning solution. Inject the spinning solution into a syringe for electrospinning. During electrospinning, the voltage is 19kV, the receiving distance is 15cm, and the feed rate is 1.5mL / h to obtain a fiber matrix. Impregnate the fiber matrix with a mixed solution of 75g formic acid and 25g acetic acid for 30 minutes. Filter, wash, dry, and pulverize to obtain composite fibers with an average length of 48μm.

[0089] Example 3

[0090] The PBC bio-based heavy-duty anti-corrosion coating of this embodiment includes a primer, an intermediate coat, and a topcoat;

[0091] The primer consists of component A and component B;

[0092] Component A consists of the following components: 40g of bio-epoxy resin, 2.5g of modified vegetable oil, 8g of composite fiber, 20g of zinc phosphate, 10g of mica iron oxide, 15g of barium sulfate, 2g of silica, 1g of dispersant Anjeka 6110, 1g of defoamer KaysalorDF 4079, 2g of leveling agent Anjeka 7422, and 4g of propylene glycol methyl ether acetate; Component B is 36g of HG-8003T curing agent.

[0093] The preparation method of the primer is as follows: Weigh 40g of bio-epoxy resin and 2.5g of modified vegetable oil into a 250mL three-necked flask, add 4g of propylene glycol methyl ether acetate, heat to 47℃, stir at 400rpm for 15min, then add 8g of composite fiber, 20g of zinc phosphate, 10g of mica iron oxide, 15g of barium sulfate, 2g of silica, 1g of dispersant Anjeka 6110, 1g of defoamer Kaysalor DF 4079, and 2g of leveling agent Anjeka 7422, sonicate for 40min, stir at 1000rpm for 40min, then add 36g of HG-8003T curing agent, stir at 600rpm for 20min to obtain the primer.

[0094] The intermediate paint consists of component C and component D;

[0095] Component C consists of the following components: 45g of bio-epoxy resin, 2g of modified vegetable oil, 5g of composite fiber, 10g of glass flakes, 20g of mica powder, 8g of barium sulfate, 1g of thixotropic agent EFKA RM 1900, 0.5g of defoamer Kaysalor DF 4079, and 3g of propylene glycol methyl ether acetate; Component D is 35g of HG-8003T curing agent.

[0096] The preparation method of intermediate paint is as follows: Weigh 45g of bio-epoxy resin and 2g of modified vegetable oil into a 250mL three-necked flask, add 3g of propylene glycol methyl ether acetate, heat to 45℃, stir at 400rpm for 20min, then add 5g of composite fiber, 10g of glass flakes, 20g of mica powder, 8g of barium sulfate, 1g of thixotropic agent EFKA RM 1900, and 0.5g of defoamer Kaysalor DF4079, sonicate for 50min, stir at 800rpm for 1h, then add 35g of HG-8003T curing agent, stir at 600rpm for 20min to obtain intermediate paint.

[0097] The topcoat consists of components E and F;

[0098] Component E consists of the following components: 50g bio-epoxy resin, 1.5g modified vegetable oil, 10g composite fiber, 20g titanium dioxide, 4g carbon black, 2g montmorillonite, 2g UV absorber BASF Tinuvin 328, 0.5g leveling agent Anjeka 7422, and 2g propylene glycol methyl ether acetate; Component F is 38g HG-8003T curing agent.

[0099] The preparation method of the topcoat is as follows: Weigh 50g of bio-epoxy resin and 1.5g of modified vegetable oil into a 250mL three-necked flask, add 2g of propylene glycol methyl ether acetate, stir at 500rpm for 25min, then add 10g of composite fiber, 20g of titanium dioxide, 4g of carbon black, 2g of montmorillonite, 2g of UV absorber BASF Tinuvin 328, and 0.5g of leveling agent Anjeka 7422, sonicate for 50min, stir at 1000rpm for 50min, then add 38g of HG-8003T, stir at 600rpm for 30min to obtain the topcoat.

[0100] The preparation method of the bio-epoxy resin in this embodiment is as follows:

[0101] 1) Weigh 35g of 2-phosphonosuccinic acid, 6g of glycerol, 2g of ethylene glycol and 80g of toluene into a 250mL three-necked flask. Heat to 130℃ under a nitrogen atmosphere, then add 0.15g of p-toluenesulfonic acid. React for 6 hours. After the reaction is completed, perform vacuum distillation to obtain the precursor.

[0102] 2) Take 40g of precursor and 180g of tetrahydrofuran and put them into a 500mL three-necked flask. After stirring evenly, add 42g of 4-dimethylaminopyridine. Under nitrogen atmosphere, cool down to 0℃ and add a mixed solution of 0.5g of dicyclohexylcarbodiimide and 10g of tetrahydrofuran at a rate of 1.2mL / min. Then add a mixed solution of 45g of syringaldehyde and 15g of tetrahydrofuran at a rate of 1mL / min. React for 50min, adjust the temperature to 25℃ and continue to react for 16h. Filter, retain the liquid component, wash with saturated sodium bicarbonate solution and physiological saline in sequence, evaporate by rotary evaporation, and dry to obtain intermediate M.

[0103] 3) Weigh 60g of guaiacol and put it into a 500mL three-necked flask. Heat to 50℃ and stir for 30min. Stop heating and add 80g of intermediate M and mix well. Adjust the temperature to 40℃, then add 40g of p-toluenesulfonic acid and 42g of zinc chloride. React for 22h. After the reaction is complete, wash and retain the organic phase. Add 100g of ethanol and mix well. Pour into 500g of deionized water for precipitation, filter, collect the solid product, and dry to obtain intermediate N.

[0104] 4) Take 110g of intermediate N and 90g of epichlorohydrin and put them into a 500mL three-necked flask. Heat to 120℃ and stir for 40min. Add 1.5g of tetrabutylammonium bromide and react for 6h. Then cool to 50℃ and add 50g of 30% sodium hydroxide aqueous solution. React for 2h. After the reaction is completed, cool to room temperature, add 200g of dichloromethane and mix well. Wash and retain the organic phase. Add anhydrous magnesium sulfate and dry. Rotary evaporate to obtain bio-epoxy resin.

[0105] The modified vegetable oil in this embodiment is prepared as follows: 35g of soybean oil is weighed and put into a four-necked flask, and then 10g of maleic anhydride is added. Under a nitrogen atmosphere, the temperature is raised to 200°C and reacted for 4 hours to obtain the modified vegetable oil.

[0106] The method for preparing the composite fiber in this embodiment is as follows:

[0107] S1: Weigh 30g of deionized water and 25g of ethanol into a three-necked flask, add glacial acetic acid to adjust the pH to 6, add 2g of hydroxyapatite with an average particle size of 200nm and mix well, then add 0.2g of 3-aminopropyltrimethoxysilane, heat to 50℃ and react for 8h, centrifuge, dry to obtain ammoniated hydroxyapatite.

[0108] S2: Weigh 6g of polymethyl methacrylate and 60g of acetic acid aqueous solution with a mass percentage concentration of 80% and add them to a three-necked flask. Heat to 35℃ and stir until the polymethyl methacrylate is completely dissolved. Add 1g of chitosan and continue stirring for 4h. Then add 3g of aminated hydroxyapatite and sonicate for 40min to obtain a spinning solution. Inject the spinning solution into a syringe for electrospinning. During electrospinning, the voltage is 20kV, the receiving distance is 14cm, and the feed rate is 1mL / h to obtain a fiber matrix. Impregnate the fiber matrix with a mixed solution of 75g formic acid and 25g acetic acid for 30min. Filter, wash, dry, and pulverize to obtain composite fibers with an average length of 50μm.

[0109] Comparative Example 1

[0110] This comparative example of PBC bio-based heavy-duty anti-corrosion coating includes a primer, intermediate coat, and topcoat.

[0111] The primer consists of component A and component B;

[0112] Component A consists of the following components: 35g bio-epoxy resin, 2g modified vegetable oil, 5g composite fiber, 15g zinc phosphate, 5g mica iron oxide, 10g barium sulfate, 1g silica, 0.5g dispersant Kaysalor DS 7996, 0.5g defoamer Anjeka-5680A, 1g leveling agent Kaysalor Glide 1645, and 2g propylene glycol methyl ether acetate; Component B is 28g HG-8003T curing agent.

[0113] The preparation method of the primer is as follows: Weigh 35g of bio-epoxy resin and 2g of modified vegetable oil into a 250mL three-necked flask, add 2g of propylene glycol methyl ether acetate, heat to 45℃, stir at 400rpm for 15min, then add 5g of composite fiber, 15g of zinc phosphate, 5g of mica iron oxide, 10g of barium sulfate, 1g of silica, 0.5g of dispersant Kaysalor DS 7996, 0.5g of defoamer Anjeka-5680A, and 1g of leveling agent Kaysalor Glide 1645, sonicate for 30min, stir at 1000rpm for 40min, then add 28g of HG-8003T curing agent, stir at 600rpm for 15min to obtain the primer.

[0114] The intermediate paint consists of component C and component D;

[0115] Component C consists of the following components: 40g of bio-epoxy resin, 1g of modified vegetable oil, 3g of composite fiber, 5g of glass flakes, 15g of mica powder, 4g of barium sulfate, 0.5g of thixotropic agent Anjeka 4410, 0.2g of defoamer Anjeka-5680A, and 2g of propylene glycol methyl ether acetate; Component D is 25g of HG-8003T curing agent.

[0116] The preparation method of intermediate paint is as follows: Weigh 40g of bio-epoxy resin and 1g of modified vegetable oil into a 250mL three-necked flask, add 2g of propylene glycol methyl ether acetate, heat to 40℃, stir at 400rpm for 15min, then add 3g of composite fiber, 5g of glass flakes, 15g of mica powder, 4g of barium sulfate, 0.5g of thixotropic agent Anjeka 4410, and 0.2g of defoamer Anjeka-5680A, sonicate for 40min, stir at 800rpm for 1h, then add 25g of HG-8003T curing agent, stir at 600rpm for 20min to obtain intermediate paint.

[0117] The topcoat consists of components E and F;

[0118] Component E consists of the following components: 45g of bio-epoxy resin, 1g of modified vegetable oil, 5g of composite fiber, 15g of titanium dioxide, 2g of carbon black, 1g of montmorillonite, 1g of UV absorber BASF Chimassorb 81, 0.3g of leveling agent Kaysalor Glide 1645, and 1g of propylene glycol methyl ether acetate; Component F is 27g of HG-8003T curing agent.

[0119] The preparation method of the topcoat is as follows: Weigh 45g of bio-epoxy resin and 1g of modified vegetable oil into a 250mL three-necked flask, add 1g of propylene glycol methyl ether acetate, stir at 500rpm for 15min, then add 5g of composite fiber, 15g of titanium dioxide, 2g of carbon black, 1g of montmorillonite, 1g of UV absorber BASF Chimassorb 81, and 0.3g of leveling agent Kaysalor Glide 1645, sonicate for 50min, stir at 1000rpm for 40min, then add 27g of HG-8003T curing agent, stir at 600rpm for 20min to obtain the topcoat.

[0120] The preparation method of the bio-epoxy resin in this comparative example is as follows:

[0121] 1) Weigh 39g of 2-phosphonosuccinic acid, 6g of glycerol, 3g of ethylene glycol and 80g of toluene into a 250mL three-necked flask. Heat to 140℃ under a nitrogen atmosphere, then add 0.15g of p-toluenesulfonic acid. React for 7h. After the reaction is completed, perform vacuum distillation to obtain the precursor.

[0122] 2) Take 45g of precursor and 180g of tetrahydrofuran and put them into a 500mL three-necked flask. After stirring evenly, add 45g of 4-dimethylaminopyridine. Under nitrogen atmosphere, cool down to 0℃ and add a mixed solution of 0.6g of dicyclohexylcarbodiimide and 8g of tetrahydrofuran at a rate of 1mL / min. Then add a mixed solution of 45g of syringaldehyde and 13g of tetrahydrofuran at a rate of 0.8mL / min. React for 50min, adjust the temperature to 25℃ and continue to react for 20h. Filter, retain the liquid component, wash with saturated sodium bicarbonate solution and physiological saline in sequence, evaporate by rotary evaporation, and dry to obtain intermediate M.

[0123] 3) Weigh 55g of guaiacol into a 500mL three-necked flask, heat to 50℃, stir for 20min, stop heating, add 80g of intermediate M and mix well, adjust the temperature to 40℃, then add 50g of p-toluenesulfonic acid and 40g of zinc chloride, react for 20h, after the reaction is complete, wash, retain the organic phase, then add 90g of ethanol and mix well, pour into 500g of deionized water for precipitation, filter, collect the solid product, dry, and obtain intermediate N;

[0124] 4) Take 130g of intermediate N and 95g of epichlorohydrin and put them into a 500mL three-necked flask. Heat to 110℃ and stir for 40min. Add 1.8g of tetrabutylammonium bromide and react for 5h. Then cool to 50℃ and add 50g of 30% sodium hydroxide aqueous solution. React for 2h. After the reaction is completed, cool to room temperature, add 200g of dichloromethane and mix well. Wash and retain the organic phase. Add anhydrous magnesium sulfate and dry. Rotary evaporate to obtain bio-epoxy resin.

[0125] The modified vegetable oil in this embodiment is prepared as follows: 25g of soybean oil is weighed and put into a four-necked flask, and then 10g of maleic anhydride is added. Under a nitrogen atmosphere, the temperature is raised to 210°C and reacted for 3 hours to obtain the modified vegetable oil.

[0126] The preparation method of the composite fiber in this comparative example is as follows: 4g of polymethyl methacrylate and 50g of acetic acid aqueous solution with a mass percentage concentration of 80% were weighed and added to a three-necked flask. The temperature was raised to 35℃ and stirred until the polymethyl methacrylate was completely dissolved. 1g of chitosan was added and stirring was continued for 4 hours. Then, 2.5g of hydroxyapatite with an average particle size of 150nm was added and ultrasonicated for 30 minutes to obtain a spinning solution. The spinning solution was injected into a syringe for electrospinning. During electrospinning, the voltage was 18kV, the receiving distance was 17cm, and the feed rate was 2mL / h to obtain a fiber matrix. The fiber matrix was impregnated with a mixed solution of 75g formic acid and 25g acetic acid for 30 minutes. After filtration, washing, drying, and pulverization, composite fibers with an average length of 40μm were obtained.

[0127] Comparative Example 2

[0128] This comparative example of PBC bio-based heavy-duty anti-corrosion coating includes a primer, intermediate coat, and topcoat.

[0129] The primer consists of component A and component B;

[0130] Component A consists of the following components: 35g bio-epoxy resin, 2g modified vegetable oil, 5g composite fiber, 15g zinc phosphate, 5g mica iron oxide, 10g barium sulfate, 1g silica, 0.5g dispersant Kaysalor DS 7996, 0.5g defoamer Anjeka-5680A, 1g leveling agent Kaysalor Glide 1645, and 2g propylene glycol methyl ether acetate; Component B is 28g HG-8003T curing agent.

[0131] The preparation method of the primer is as follows: Weigh 35g of bio-epoxy resin and 2g of modified vegetable oil into a 250mL three-necked flask, add 2g of propylene glycol methyl ether acetate, heat to 45℃, stir at 400rpm for 15min, then add 5g of composite fiber, 15g of zinc phosphate, 5g of mica iron oxide, 10g of barium sulfate, 1g of silica, 0.5g of dispersant Kaysalor DS 7996, 0.5g of defoamer Anjeka-5680A, and 1g of leveling agent Kaysalor Glide 1645, sonicate for 30min, stir at 1000rpm for 40min, then add 28g of HG-8003T curing agent, stir at 600rpm for 15min to obtain the primer.

[0132] The intermediate paint consists of component C and component D;

[0133] Component C consists of the following components: 40g of bio-epoxy resin, 1g of modified vegetable oil, 3g of composite fiber, 5g of glass flakes, 15g of mica powder, 4g of barium sulfate, 0.5g of thixotropic agent Anjeka 4410, 0.2g of defoamer Anjeka-5680A, and 2g of propylene glycol methyl ether acetate; Component D is 25g of HG-8003T curing agent.

[0134] The preparation method of intermediate paint is as follows: Weigh 40g of bio-epoxy resin and 1g of modified vegetable oil into a 250mL three-necked flask, add 2g of propylene glycol methyl ether acetate, heat to 40℃, stir at 400rpm for 15min, then add 3g of composite fiber, 5g of glass flakes, 15g of mica powder, 4g of barium sulfate, 0.5g of thixotropic agent Anjeka 4410, and 0.2g of defoamer Anjeka-5680A, sonicate for 40min, stir at 800rpm for 1h, then add 25g of HG-8003T curing agent, stir at 600rpm for 20min to obtain intermediate paint.

[0135] The topcoat consists of components E and F;

[0136] Component E consists of the following components: 45g of bio-epoxy resin, 1g of modified vegetable oil, 5g of composite fiber, 15g of titanium dioxide, 2g of carbon black, 1g of montmorillonite, 1g of UV absorber BASF Chimassorb 81, 0.3g of leveling agent Kaysalor Glide 1645, and 1g of propylene glycol methyl ether acetate; Component F is 27g of HG-8003T curing agent.

[0137] The preparation method of the topcoat is as follows: Weigh 45g of bio-epoxy resin and 1g of modified vegetable oil into a 250mL three-necked flask, add 1g of propylene glycol methyl ether acetate, stir at 500rpm for 15min, then add 5g of composite fiber, 15g of titanium dioxide, 2g of carbon black, 1g of montmorillonite, 1g of UV absorber BASF Chimassorb 81, and 0.3g of leveling agent Kaysalor Glide 1645, sonicate for 50min, stir at 1000rpm for 40min, then add 27g of HG-8003T curing agent, stir at 600rpm for 20min to obtain the topcoat.

[0138] The preparation method of the bio-epoxy resin in this comparative example is as follows:

[0139] 1) Weigh 39g of 2-phosphonosuccinic acid, 6g of glycerol, 3g of ethylene glycol and 80g of toluene into a 250mL three-necked flask. Heat to 140℃ under a nitrogen atmosphere, then add 0.15g of p-toluenesulfonic acid. React for 7h. After the reaction is completed, perform vacuum distillation to obtain the precursor.

[0140] 2) Take 45g of precursor and 180g of tetrahydrofuran and put them into a 500mL three-necked flask. After stirring evenly, add 45g of 4-dimethylaminopyridine. Under nitrogen atmosphere, cool down to 0℃ and add a mixed solution of 0.6g of dicyclohexylcarbodiimide and 8g of tetrahydrofuran at a rate of 1mL / min. Then add a mixed solution of 45g of syringaldehyde and 13g of tetrahydrofuran at a rate of 0.8mL / min. React for 50min, adjust the temperature to 25℃ and continue to react for 20h. Filter, retain the liquid component, wash with saturated sodium bicarbonate solution and physiological saline in sequence, evaporate by rotary evaporation, and dry to obtain intermediate M.

[0141] 3) Weigh 55g of guaiacol into a 500mL three-necked flask, heat to 50℃, stir for 20min, stop heating, add 80g of intermediate M and mix well, adjust the temperature to 40℃, then add 50g of p-toluenesulfonic acid and 40g of zinc chloride, react for 20h, after the reaction is complete, wash, retain the organic phase, then add 90g of ethanol and mix well, pour into 500g of deionized water for precipitation, filter, collect the solid product, dry, and obtain intermediate N;

[0142] 4) Take 130g of intermediate N and 95g of epichlorohydrin and put them into a 500mL three-necked flask. Heat to 110℃ and stir for 40min. Add 1.8g of tetrabutylammonium bromide and react for 5h. Then cool to 50℃ and add 50g of 30% sodium hydroxide aqueous solution. React for 2h. After the reaction is completed, cool to room temperature, add 200g of dichloromethane and mix well. Wash and retain the organic phase. Add anhydrous magnesium sulfate and dry. Rotary evaporate to obtain bio-epoxy resin.

[0143] The modified vegetable oil in this embodiment is prepared as follows: 25g of soybean oil is weighed and put into a four-necked flask, and then 10g of maleic anhydride is added. Under a nitrogen atmosphere, the temperature is raised to 210°C and reacted for 3 hours to obtain the modified vegetable oil.

[0144] The preparation method of the composite fiber in this comparative example is as follows: 4g of polymethyl methacrylate and 50g of acetic acid aqueous solution with a mass percentage concentration of 80% were weighed and added to a three-necked flask, heated to 35℃, and stirred until the polymethyl methacrylate was completely dissolved. 1g of chitosan was added, and stirring was continued for 4h to obtain a spinning solution. The spinning solution was injected into a syringe for electrospinning. During the electrospinning process, the voltage was 18kV, the receiving distance was 17cm, and the feed rate was 2mL / h. The fiber was washed, dried, and pulverized to obtain a composite fiber with an average length of 40μm.

[0145] Performance testing

[0146] 1. Preparation of substrate: Use a wire EDM machine to cut Q235B sheet into substrates with dimensions of 150mm in length, 70mm in width, and 1.5mm in height. Grind the substrate to 1000 grit using a polishing machine. Ultrasonically clean with acetone for 30 minutes, then ultrasonically clean with anhydrous ethanol for 30 minutes to remove grease from the substrate. Finally, rinse with anhydrous ethanol and dry in a vacuum drying oven at 60℃ for 1 hour for later use.

[0147] 2. Coating application and sample preparation: The primer was applied to the substrate surface by spraying, with the thickness of the primer film controlled at 80±5μm. It was then cured at room temperature for 24 hours. Next, the intermediate coat was applied to the cured primer film by spraying, with the thickness of the intermediate coat film controlled at 150±10μm. It was then cured at room temperature for 24 hours. Finally, the topcoat was applied to the cured intermediate coat film by spraying, with the thickness of the topcoat film controlled at 90±5μm. It was then cured at room temperature for 24 hours, forming a smooth and even paint film, which was then used to obtain the sample. The performance of the paint film was tested, and the test results are shown in Table 1.

[0148] 3. Salt Spray Resistance Test: A neutral salt spray corrosion test was conducted according to standard GB / 1771-2007. An "×" was marked on the sample surface. The experimental apparatus was a neutral salt spray test chamber. The corrosion solution was a 5% (w / w) NaCl aqueous solution with a pH of 7.0 ± 0.5. The temperature inside the salt spray chamber was (35 ± 2)℃, and the sample was placed at a 30° angle perpendicular to the salt spray rack. A photograph of the sample after 6500 hours of corrosion is shown below. Figure 1 As shown.

[0149] 4. The composite fibers prepared in Examples 1-3 were observed using a scanning electron microscope, and the obtained images are as follows: Figure 2 As shown.

[0150] Table 1 shows the test data of various properties of the paint films prepared from the coatings in Examples 1-3 and Comparative Examples 1-2.

[0151]

[0152] Analysis of Examples 1-3 and Comparative Example 1, in conjunction with Table 1 and Figure 1 It can be seen that due to the enhanced bonding force between amination-treated hydroxyapatite and resin, the coating exhibits superior wear resistance, corrosion resistance, and impact resistance. Analysis of Examples 1-3 and Comparative Example 2, combined with Table 1 and... Figure 1 It can be seen that adding pretreated hydroxyapatite-doped composite fibers to the coating significantly improves the coating's wear resistance, corrosion resistance, and impact resistance.

[0153] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A PBC bio-based heavy duty coating characterized in that, The primer, the intermediate paint and the topcoat; The primer comprises bio-epoxy resin, modified vegetable oil, composite fiber, filler one and curing agent; The intermediate paint comprises bio-epoxy resin, modified vegetable oil, composite fiber, filler two and curing agent; The topcoat comprises bio-epoxy resin, modified vegetable oil, composite fiber, filler three and curing agent; The bio-epoxy resin in the primer, the intermediate paint and the topcoat is made of raw materials comprising carboxylic acid derivative, polyhydric alcohol, syringaldehyde, guaiacol and epichlorohydrin; The carboxylic acid derivative is 2-phosphonosuccinic acid or phosphonobutane tricarboxylic acid; The modified vegetable oil in the primer, the intermediate paint and the topcoat is made of soybean oil modified by maleic anhydride; The composite fiber in the primer, the intermediate paint and the topcoat is made of raw materials comprising pretreated hydroxyapatite, polymethyl methacrylate and chitosan; The preparation method of the composite fiber comprises the following steps: mixing polymethyl methacrylate and aqueous acetic acid solution, adding chitosan, heating and dissolving, then adding pretreated hydroxyapatite, and ultrasonic treatment to obtain a spinning solution; electrospinning the spinning solution to obtain a fiber matrix, and then immersing the fiber matrix in a mixed solution of formic acid and acetic acid to obtain the composite fiber; The pretreated hydroxyapatite is obtained by ammoniating hydroxyapatite with an ammoniating agent; The ammoniating agent is 3-aminopropyl triethoxysilane or 3-aminopropyl trimethoxysilane.

2. The PBC bio-based heavy-duty coating of claim 1, wherein, The preparation method of the bio-epoxy resin comprises the following steps: 1) mixing the carboxylic acid derivative, the polyhydric alcohol and toluene, and performing polymerization reaction to obtain a precursor; 2) mixing the precursor and tetrahydrofuran, then adding a syringaldehyde solution, and performing esterification reaction to obtain an intermediate M; 3) mixing the intermediate M and guaiacol, then adding a catalyst and performing condensation reaction to obtain an intermediate N; 4) mixing the intermediate N and epichlorohydrin, adding tetrabutylammonium bromide, reacting for a period of time, then adding aqueous sodium hydroxide solution, and continuing to react to obtain the bio-epoxy resin.

3. The PBC bio-based heavy-duty coating of claim 1, wherein, The process of electrospinning is as follows: voltage 18-20 kV, receiving distance 14-17 cm, and feeding rate 1-2 mL / h.

4. The PBC bio-based heavy-duty coating of claim 1, wherein, The average particle size of the hydroxyapatite is 150-200 nm.

5. The PBC bio-based heavy-duty coating of claim 1, wherein, The primer comprises the following components in parts by weight: bio-epoxy resin 35-40 parts, modified vegetable oil 2-3 parts, composite fiber 5-8 parts, filler one 31-47 parts, and curing agent 28-36 parts; The intermediate paint comprises the following components: bio-epoxy resin 40-45 parts, modified vegetable oil 1-3 parts, composite fiber 3-5 parts, filler two 24-38 parts, and curing agent 25-35 parts; The topcoat comprises the following components: bio-epoxy resin 45-50 parts, modified vegetable oil 1-2 parts, composite fiber 5-10 parts, filler three 18-26 parts, and curing agent 27-38 parts.

6. The PBC bio-based heavy-duty coating of claim 2, wherein, In step 1), the polyhydric alcohol is composed of glycerol and ethylene glycol in a mass ratio of (2-3):

1.

7. A preparation process for the PBC bio-based heavy-duty anti-corrosion coating as described in claim 1, characterized in that, Preparation of the primer, the intermediate paint and the topcoat; The preparation method of the primer comprises the following steps: mixing bio-epoxy resin, modified vegetable oil, composite fiber and filler one to prepare A component; curing agent as B component; mixing A component and B component to prepare the primer; The preparation method of the intermediate paint comprises the following steps: mixing bio-epoxy resin, modified vegetable oil, composite fiber and filler two to prepare C component; curing agent as D component; mixing C component and D component to prepare the intermediate paint; The preparation method of the topcoat comprises the following steps: mixing bio-epoxy resin, modified vegetable oil, composite fiber and filler three to prepare E component; curing agent as F component; mixing E component and F component to prepare the topcoat.

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