Preparation method of kerosene-resistant antibacterial static conductive coating

Abstract

The invention relates to the technical field of coating preparation, in particular to a preparation method of kerosene-resistant antibacterial static conductive coating. The invention relates to a preparation method of a kerosene-resistant antibacterial static conductive coating. The kerosene-resistant antibacterial static conductive coating comprises a component A raw material and a component B raw material, the component A is prepared from the following raw materials: novolac epoxy resin, toughened modified resin, a reactive diluent, an auxiliary agent, polyhexamethylene biguanide, an anti-rust filler and a solvent; and the component B comprises the following raw materials: a toughening phenolic aldehyde amine curing agent and an alicyclic amine curing agent. The preparation method of the kerosene-resistant antibacterial static conductive coating has the advantages that the phenomena of bubbling and shedding are avoided, the coating has a protection effect and stable salt spray resistance and surface resistivity, and the static conductive requirement is met. The antibacterial rate is increased, the surface pollution is effectively inhibited, the green chemical industry standard is met, the adhesive force of the coating is improved, the wear resistance is improved, and high toughness can be kept in a low-temperature state.

Description

Technical Field

[0001] This invention relates to the field of coating preparation technology, and in particular to a method for preparing a kerosene-resistant, antibacterial, and electrostatic conductive coating. Background Technology

[0002] When fuel storage tanks and similar facilities are always full of fuel, the inner walls of the tanks will not experience severe corrosion. However, when the fuel is emptied or not fully filled, moisture in the air will condense on the tank surface, leading to corrosion. Furthermore, bacterial growth within fuel storage tanks and compartments will cause fuel degradation and increased impurities, affecting fuel purity and combustion performance. Therefore, anti-corrosion and antibacterial treatment is necessary for fuel storage tanks and kerosene storage compartments, and coating protection is the most economical and effective corrosion protection solution. Kerosene is ultimately used in aerospace and precision instrument applications. Contamination may lead to the formation of insoluble colloidal substances under specific conditions (such as heating, evaporation, and oxidation). This will further lead to scale buildup and blockage of engine components, causing safety issues. Therefore, coatings protecting equipment used for kerosene storage, transportation, and use must possess excellent corrosion resistance and impermeability to ensure fuel quality and safe use.

[0003] Chinese invention patent CN115109502A discloses a production method for a solvent-resistant, conductive, and anti-corrosion coating, belonging to the field of conductive coating technology. It uses a blend of thermosetting polycarbonate with benzocyclobutene groups and polyvinyl chloride resin, and prepares conductive fillers by chemically reducing zinc to graphitized carbon black. The coating has a low potential, providing cathodic protection, and low production cost. The blend of chlorinated polyether and polycarbonate results in a hard, wear-resistant film that is resistant to long-term immersion in various oils. It is resistant to various solvents, including strong solvents such as aromatics, alcohols, aldehydes, esters, and ketones. Its conductivity is unaffected by temperature, pressure, or humidity, exhibiting permanent conductivity. Its surface conductivity and volume conductivity meet the requirements of relevant domestic and international standards such as GB13348 "Electrostatic Safety Regulations for Liquid Petroleum Products," and it possesses excellent conductive and anti-corrosion properties, effectively addressing the anti-corrosion and conductive design needs of the inner walls of strong solvent storage tanks. However, the coating preparation technology and construction conditions have obvious limitations: the production process requires high-temperature plasticization (300℃) and quenching treatment, which places high demands on equipment, and the construction requires precise control of the spraying temperature, making the operation difficult; in addition, the preparation of the conductive filler depends on sodium cyanide, which poses a large risk of toxicity and does not conform to the trend of green chemistry; it involves precious metal plating solutions and complex chemical plating processes, and the cost of large-scale production is high. Summary of the Invention

[0004] In view of this, the present invention aims to provide a method for preparing a kerosene-resistant, antibacterial, and conductive coating, developing a kerosene-resistant coating that meets various technical indicators, ensuring corrosion protection of kerosene and corresponding crude oil products during storage and transportation. The development process utilizes a multi-resin system and conductive formulation design to achieve long-term corrosion protection of the inner wall of storage tanks. Simultaneously, it achieves coating impurity exudation control and antibacterial synergy, overcoming the problems of coating dissolution and microbial growth caused by long-term kerosene storage in tanks, effectively ensuring the quality of kerosene, and guaranteeing the safety of kerosene during use. It is suitable for corrosion protection of the inner walls of kerosene storage tanks, transportation equipment, and oil tanks.

[0005] To address the above problems, this invention provides a method for preparing a kerosene-resistant antibacterial conductive coating, wherein the kerosene-resistant antibacterial conductive coating comprises component A and component B.

[0006] Component A raw materials include: 18-22 parts by weight of phenolic epoxy resin, 14-16 parts by weight of toughening modified resin, 2.4-3.0 parts by weight of reactive diluent, 1.8-2.4 parts by weight of additives, 1.0-1.5 parts by weight of polyhexamethylene biguanide, 50-54 parts by weight of rust-inhibiting filler, and 6.4-8.0 parts by weight of solvent;

[0007] Component B raw materials include: 7.5~8.5 parts by weight of toughening phenolic amine curing agent and 4.0~5.0 parts by weight of alicyclic amine curing agent.

[0008] Furthermore, the phenolic epoxy resin is selected as F51 type phenolic epoxy resin, which is composed of benzene rings, aldehyde groups and epoxy groups.

[0009] Furthermore, the toughening modified resin is based on bisphenol A and epichlorohydrin as raw materials, and a hyperbranched polyester structure is introduced during the synthesis process.

[0010] Furthermore, the additive system includes silicone defoamer, silicone rheology modifier and thixotropic agent, formed in a ratio of 0.4:0.3:0.6 respectively;

[0011] The composition includes 0.3-0.5 parts of silicone defoamer, 0.3-0.5 parts of silicone rheology modifier, and 0.5-0.8 parts of thixotropic agent. The thixotropic agent is selected from polyamide wax thixotropic agents.

[0012] Furthermore, the rust-preventive filler is composed of conductive mica powder, feldspar powder, iron-titanium powder and titanium dioxide, mixed in a mass ratio of 1:0.9:1:0.2.

[0013] Furthermore, the solvent is selected from xylene and n-butanol in a 2:1 ratio to form a solvent system.

[0014] Furthermore, the preparation method of the kerosene-resistant antibacterial conductive coating includes:

[0015] S100, Preparation of modified epoxy resin;

[0016] S200, Preparation of component A raw material;

[0017] S300, Prepare component B raw materials.

[0018] Furthermore, in step S100, the method for preparing the modified epoxy resin includes:

[0019] Bisphenol A epoxy resin and hydroxyl-terminated hyperbranched polyester were added to a vacuum reactor and reacted at 80±2℃ with triphenylphosphine as a catalyst under nitrogen protection at 300~500 rpm for 1.5 hours to synthesize a tough epoxy resin through polycondensation reaction.

[0020] Furthermore, in step S200, the method for preparing component A raw material includes:

[0021] S210, add phenolic epoxy resin, resin modifier, solvent and additive system in proportion, and stir at high speed of 1200~1500r / min for 15~20 minutes to initially disperse the resin raw materials evenly.

[0022] S220, add conductive mica powder, and disperse at high speed for 15-20 minutes at 3000-3200 r / min;

[0023] S230, add feldspar powder, iron-titanium powder and titanium dioxide to the rust-inhibiting filler, and continue to disperse for 20-30 minutes under the condition of 3000~3200r / min;

[0024] S240, add thixotropic agent, disperse at 1200~1500r / min for 10-15 minutes.

[0025] S250, testing fineness and viscosity, filtration and packaging.

[0026] Furthermore, in step S300, the method for preparing component B raw material includes:

[0027] S310. Add toughening phenolic amine and modified alicyclic amine curing agent according to the curing agent ratio, and disperse the curing agent evenly in 600~800r / min for 15~20 minutes using a high-speed disperser.

[0028] S320, check viscosity and density, packaging complete.

[0029] Compared with existing technologies, the preparation method of the kerosene-resistant antibacterial conductive coating of the present invention has the following advantages:

[0030] The advantages of this technical solution are that the coating produced by the components and preparation method of this invention avoids blistering and peeling, while also providing protection against both gasoline and diesel fuel; it has strong salt spray resistance, stable surface resistivity, and meets the requirements for electrostatic conductivity. It improves the antibacterial rate, effectively inhibiting microbial contamination of the coating surface by oil products, conforming to green chemical standards, improving coating adhesion, enhancing wear resistance, and maintaining high toughness at low temperatures. Attached Figure Description

[0031] Figure 1 This is a schematic diagram of the toughening and modifying resin reaction of the present invention. Detailed Implementation

[0032] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0033] In this invention, the terms "first," "second," "upper," and "lower," etc., are used for descriptive purposes only and should not be construed as indicating or implying their relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined with "first," "second," "upper," or "lower" may explicitly or implicitly include at least one of those features. Furthermore, the technical solutions of the various embodiments can be combined with each other, but this must be based on the ability of those skilled in the art to implement them. Where the technical solutions of the embodiments can be combined, they are all within the scope of protection claimed by this invention.

[0034] The present invention will now be described in detail with reference to the accompanying drawings and embodiments.

[0035] like Figure 1 As shown, a method for preparing a kerosene-resistant antibacterial conductive coating is disclosed, wherein the kerosene-resistant antibacterial conductive coating comprises component A and component B.

[0036] Component A raw materials include: 18-22 parts by weight of phenolic epoxy resin, 14-16 parts by weight of toughening modified resin, 2.4-3.0 parts by weight of reactive diluent, 1.8-2.4 parts by weight of additives, 1.0-1.5 parts by weight of polyhexamethylene biguanide, 50-54 parts by weight of rust-inhibiting filler, and 6.4-8.0 parts by weight of solvent;

[0037] Component B raw materials include: 7.5~8.5 parts by weight of toughening phenolic amine curing agent and 4.0~5.0 parts by weight of alicyclic amine curing agent.

[0038] Furthermore, the phenolic epoxy resin is selected as F51 type phenolic epoxy resin, which is composed of benzene rings, aldehyde groups and epoxy groups, and has the characteristics of high crosslinking density and high hardness.

[0039] Furthermore, the toughening modified resin is based on bisphenol A and epichlorohydrin as raw materials, and a hyperbranched polyester structure is introduced during the synthesis process. It has good compatibility with the phenolic epoxy resin in the system. The stress concentration points of the molecular-level voids of the hyperbranched polymer are dispersed to enhance the intermolecular forces of the resin, thereby improving toughness.

[0040] Reactive diluents are compounds containing benzyl glycidyl ether. They effectively disperse the interactions between epoxy resin molecular chains by utilizing the benzyl and ether groups in the molecule, thereby reducing the overall viscosity of the system and reducing the amount of solvent used.

[0041] Furthermore, the additive system includes silicone defoamer, silicone rheology modifier and thixotropic agent, formed in a ratio of 0.4:0.3:0.6 respectively.

[0042] The composition includes 0.3-0.5 parts of silicone defoamer, 0.3-0.5 parts of silicone rheology modifier, and 0.5-0.8 parts of thixotropic agent. The thixotropic agent is selected from polyamide wax thixotropic agents.

[0043] Polyhexamethylene biguanide is a high-molecular-weight broad-spectrum bactericide that destroys bacteria by dissolving their cell membranes. It is non-toxic and non-corrosive, and has excellent antibacterial and bactericidal effects on protective coatings for long-term storage and transportation of kerosene.

[0044] Furthermore, the rust-preventive filler is composed of conductive mica powder, feldspar powder, iron-titanium powder, and titanium dioxide, mixed in a mass ratio of 1:0.9:1:0.2. The conductive mica powder forms a conductive layer functional filler through nanotechnology and doping technology, creating a conductive network in the coating that effectively prevents static electricity buildup. The iron-titanium powder possesses excellent corrosion resistance, high specific gravity, and environmental advantages. The addition of titanium dioxide improves the coating's coloring power, heat resistance, and chemical stability, and is particularly non-toxic. The feldspar powder has a framework-like silicon-oxygen skeleton structure, which helps to solidify and form a dense coating, enhancing its wear resistance, weather resistance, and mechanical strength.

[0045] Furthermore, the solvent is selected from xylene and n-butanol in a 2:1 ratio to form a solvent system.

[0046] Toughened phenolic amine curing agents are mainly composed of phenolic skeletons and amine groups, combining the high crosslinking density of phenolic resins with the low-temperature reactivity of amine curing agents, effectively solving the problem of incomplete low-temperature curing of conventional amine curing agents.

[0047] Alicyclic amine curing agents use cyclic aliphatic hydrocarbons as a backbone and combine them with amine active groups. They possess both the rigidity of alicyclic structures and the reactive properties of amines. The cyclic structure endows the cured system with advantages such as salt spray resistance and acid and alkali resistance.

[0048] Kerosene-resistant conductive coatings are widely used in corrosion-resistant and anti-static applications such as crude oil storage tanks, refining equipment, and oil pipelines. Technically, they require excellent oil resistance, conductivity, temperature resistance, adhesion, and corrosion protection, while minimizing the impact on the kerosene itself during long-term contact and inhibiting the adhesion and erosion of microorganisms in the kerosene. Compared to common epoxy and acrylic resins, this solution uses phenolic epoxy resin as the main film-forming material. The resulting tightly cross-linked network can stably support conductive fillers and provides better heat resistance and oil immersion resistance. Compared to common water-based epoxy resins and silicone resins, the phenolic epoxy system has superior hardness and abrasion resistance, preventing mechanical wear and conductivity degradation caused by long-term kerosene storage and transportation. The main resin selected in this invention combines the characteristics of phenolic epoxy and modified resins: abrasion resistance and high toughness, improving the coating's oil resistance, corrosion resistance, and conductivity safety, meeting the needs of kerosene or crude oil storage and transportation scenarios. Furthermore, in response to the antibacterial properties and oil quality control (leaking control) required in actual oil storage and transportation, the non-toxic polyhexamethylene biguanide bactericide added in this invention can inhibit the growth of microorganisms on the coating surface. The resin system provides excellent coating rigidity and scratch resistance, effectively reducing the leaching of the coating when in contact with fuel oil, without affecting the quality of the oil.

[0049] Furthermore, the preparation method of the kerosene-resistant antibacterial conductive coating includes:

[0050] S100, Preparation of modified epoxy resin;

[0051] Using bisphenol A epoxy resin and hydroxyl-terminated hyperbranched polyester (such as Boltorn™ H30) as raw materials, they were added to a vacuum reactor (model: FZG-50L, with anchor stirrer). The reactor was stirred at 300~500 rpm for 1.5 hours at 80±2℃ with triphenylphosphine as a catalyst under nitrogen protection, and the reaction was carried out through a polycondensation reaction to synthesize a strong and tough epoxy resin (see...). Figure 1 It retains the basic structure of bisphenol A epoxy resin, introduces a hyperbranched polyester structure, and utilizes the molecular-level voids of the hyperbranched polymer to disperse stress concentration points, inhibit crack propagation, and achieve improved toughness.

[0052] S200, Preparation of component A raw material;

[0053] S210, add phenolic epoxy resin, resin modifier, solvent and additive system in proportion, and stir at high speed of 1200~1500r / min for 15~20 minutes to initially disperse the resin raw materials evenly.

[0054] S220, add conductive mica powder, and disperse at high speed for 15-20 minutes at 3000-3200 r / min;

[0055] S230, add feldspar powder, iron-titanium powder and titanium dioxide to the rust-inhibiting filler, and continue to disperse for 20-30 minutes under the condition of 3000~3200r / min;

[0056] S240, add thixotropic agent, disperse at 1200~1500r / min for 10-15 minutes.

[0057] S250, testing fineness and viscosity, filtration and packaging.

[0058] S300, Prepare component B raw materials.

[0059] S310. Add toughening phenolic amine and modified alicyclic amine curing agent according to the curing agent ratio, and disperse the curing agent evenly in 600~800r / min for 15~20 minutes using a high-speed disperser.

[0060] S320, check viscosity and density, packaging complete.

[0061] Example

[0062] The preparation method of the kerosene-resistant antibacterial conductive coating of the present invention is described below with specific embodiments and comparative examples.

[0063] The components of the kerosene-resistant antibacterial conductive coating in this embodiment are shown in Table 1.

[0064] Table 1

[0065]

[0066] The performance test results of the coatings containing the above components are shown in Table 2 below.

[0067] Table 2

[0068]

[0069] in conclusion:

[0070] 1. The key role of toughening modified resin: In Examples 1-3, the toughening resin (14-16 parts) significantly improved the coating toughness. The gum content of the coating after kerosene immersion was less than 7 mg / 100mL, effectively reducing the coating's contamination of the oil and meeting the requirements of EI1541 standard. The bond strength was >9.3MPa. In Comparative Example 1, due to the lack of toughening resin, the coating exudate increased, and the bond strength decreased by 25% (only 7.0MPa), and the salt spray resistance deteriorated (edge ​​corrosion). The toughening resin improved stress polymerization through its hyperbranched polyester structure, reducing coating loss.

[0071] 2. The necessity of antibacterial properties of polyhexamethylene biguanide: The antibacterial rates of Examples 1-3 are all >99%, while the antibacterial rate of Comparative Example 2 drops to 85% without antibacterial agent, proving that long-term and highly effective antibacterial effect cannot be achieved without antibacterial agent.

[0072] 3. Synergistic effect of toughening phenolic amine curing agent: Examples 1-3 use toughening curing agent (7.5~8.5 parts) and toughening resin in synergistic effect, and the coating still maintains high toughness after low temperature (-10℃) curing; Comparative Example 3 uses a single alicyclic curing agent, which leads to incomplete curing reaction, decreased salt spray resistance of coating, and weaker resistance to kerosene and other oils.

[0073] This invention achieves significant technical effects:

[0074] ① Oil resistance and corrosion resistance: Tests showed that the antibacterial conductive coating exhibited no blistering or peeling after immersion in No. 3 aviation kerosene for 90 days, and also provided protection against gasoline and diesel fuel. Its salt spray resistance reached 2000 hours, and its surface resistivity remained stable at 10^10, meeting the requirements for conductive properties. ② Antibacterial properties and environmental friendliness: The addition of polyhexamethylene biguanide as an antibacterial agent resulted in an antibacterial rate of over 99% against Staphylococcus aureus, effectively inhibiting microbial contamination of the coating surface. The conductive coating uses pollution-free rust-preventive fillers and a low-solvent formula (VOC < 200g / L), meeting green chemical standards. ③ Mechanical properties: The synergistic effect of the toughened modified resin and toughened phenolic amine curing agent resulted in a coating adhesion of over 9MPa, a 40% improvement in wear resistance, and high toughness even after low-temperature (-10℃) curing.

[0075] While the present invention has been disclosed above, it is not limited thereto. Any person skilled in the art can make various modifications and alterations without departing from the spirit and scope of the invention; therefore, the scope of protection of the present invention should be determined by the scope defined in the claims.

Claims

1. A method for preparing a kerosene-resistant, antibacterial, and conductive coating, characterized in that, The kerosene-resistant, antibacterial, and electrostatic conductive coating comprises component A and component B. Component A raw materials include: 18-22 parts by weight of phenolic epoxy resin, 14-16 parts by weight of toughening modified resin, 2.4-3.0 parts by weight of reactive diluent, 1.8-2.4 parts by weight of additives, 1.0-1.5 parts by weight of polyhexamethylene biguanide, 50-54 parts by weight of rust-inhibiting filler, and 6.4-8.0 parts by weight of solvent; Component B raw materials include: 7.5~8.5 parts by weight of toughening phenolic amine curing agent and 4.0~5.0 parts by weight of alicyclic amine curing agent.

2. The preparation method of the kerosene-resistant antibacterial conductive coating according to claim 1, characterized in that, The phenolic epoxy resin used is F51 type phenolic epoxy resin, which is composed of benzene rings, aldehyde groups and epoxy groups.

3. The method for preparing the kerosene-resistant antibacterial conductive coating according to claim 1, characterized in that, The toughening modified resin is based on bisphenol A and epichlorohydrin as raw materials, and a hyperbranched polyester structure is introduced during the synthesis process.

4. The preparation method of the kerosene-resistant antibacterial conductive coating according to claim 1, characterized in that, The additive system includes silicone defoamer, silicone rheology modifier and thixotropic agent, which are formed in a ratio of 0.4:0.3:0.6 respectively; The composition includes 0.3-0.5 parts of silicone defoamer, 0.3-0.5 parts of silicone rheology modifier, and 0.5-0.8 parts of thixotropic agent. The thixotropic agent is selected from polyamide wax thixotropic agents.

5. The method for preparing the kerosene-resistant antibacterial conductive coating according to claim 1, characterized in that, The rust-preventive filler is composed of conductive mica powder, feldspar powder, iron-titanium powder and titanium dioxide, mixed in a mass ratio of 1:0.9:1:0.

2.

6. The method for preparing the kerosene-resistant antibacterial conductive coating according to claim 1, characterized in that, The solvent is a mixture of xylene and n-butanol in a 2:1 ratio.

7. The method for preparing the kerosene-resistant antibacterial conductive coating according to claim 1, characterized in that, The preparation method of the kerosene-resistant antibacterial conductive coating includes: S100, Preparation of modified epoxy resin; S200, Preparation of component A raw material; S300, Prepare component B raw materials.

8. The method for preparing the kerosene-resistant antibacterial conductive coating according to claim 7, characterized in that, In step S100, the method for preparing the modified epoxy resin includes: Bisphenol A epoxy resin and hydroxyl-terminated hyperbranched polyester were added to a vacuum reactor and reacted at 80±2℃ with triphenylphosphine as a catalyst under nitrogen protection at 300~500 rpm for 1.5 hours to synthesize a tough epoxy resin through polycondensation reaction.

9. The method for preparing the kerosene-resistant antibacterial conductive coating according to claim 7, characterized in that, In step S200, the method for preparing component A raw material includes: S210, add phenolic epoxy resin, resin modifier, solvent and additive system in proportion, and stir at high speed of 1200~1500r / min for 15~20 minutes to initially disperse the resin raw materials evenly. S220, add conductive mica powder, and disperse at high speed for 15-20 minutes at 3000-3200 r / min; S230, add feldspar powder, iron-titanium powder and titanium dioxide to the rust-inhibiting filler, and continue to disperse for 20-30 minutes under the condition of 3000~3200r / min; S240, add thixotropic agent, disperse at 1200~1500r / min for 10-15 minutes. S250, testing fineness and viscosity, filtration and packaging.

10. The method for preparing the kerosene-resistant antibacterial conductive coating according to claim 7, characterized in that, In step S300, the method for preparing component B raw material includes: S310. Add toughening phenolic amine and modified alicyclic amine curing agent according to the curing agent ratio, and disperse the curing agent evenly in 600~800r / min for 15~20 minutes using a high-speed disperser. S320, check viscosity and density, packaging complete.

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