Preparation method and application of a two-component in-situ self-generated filler coating

Abstract

This invention relates to the technical field of pipeline anti-corrosion materials, and in particular to a method for preparing and applying a two-component in-situ self-generating filler-type coating, comprising the following steps: S1, dissolving a certain mass of zinc metal salt in a solvent to prepare component A; S2, dissolving a certain mass of cyclodextrin-like substances and various organic molecules with corrosion inhibition or antibacterial functions in a solvent, and adding polymer materials as film-forming aids to prepare component B; S3, mixing components A and B in a certain proportion, coating the inside of pipes with large length-to-diameter ratios using a filling and coating method, and curing at 25-150℃ to obtain an in-situ self-generating nanofiller-type anti-corrosion and antibacterial dual-function coating; components A and B are nearly homogeneous solution phases, and the coating viscosity is low when initially mixed, which is convenient for filling and coating pipes with large length-to-diameter ratios, and the nanofiller can achieve in-situ self-generation, ensuring excellent adhesion and corrosion resistance of the coating, while improving the antibacterial performance of the pipeline.

Description

Technical Field

[0001] This invention relates to the technical field of pipeline anti-corrosion materials, and in particular to a method for preparing and applying a two-component in-situ self-generating filler-type coating. Background Technology

[0002] Pipes with a large length-to-diameter ratio, such as heat exchanger pipes, water pipes, and gas transmission pipes, are generally made of various metal materials such as copper-nickel alloys and galvanized cast iron. Under harsh service environments such as continuous erosion and alternating hot and cold temperatures, the oxide film layer on the surface of the pipe is prone to defects and damage, leading to the risk of corrosion and even perforation, posing a significant threat to service safety.

[0003] Therefore, for large-diameter pipeline equipment operating under harsh conditions, such as oil grease traps, heavy-duty anti-corrosion coatings are the primary protection method. Traditional anti-corrosion coatings, such as the zinc-aluminum-magnesium composite anti-corrosion coating for cast iron pipelines and its preparation method disclosed in invention patent CN103375658B, and the bipolar anti-corrosion coating and its preparation method disclosed in invention patent CN101463200B, can all achieve anti-corrosion effects.

[0004] However, during use, it has been found that traditional heavy-duty anti-corrosion coatings often incorporate two-dimensional sheet materials (such as mica iron oxide, glass flakes, and graphene) and three-dimensional particulate materials (such as zinc powder) as fillers as heterogeneous particles in the coating. This density difference makes it difficult for the solution to present a homogeneous phase. Stability is typically maintained by adding stabilizers and increasing the viscosity of the coating system. High-viscosity heavy-duty anti-corrosion systems are difficult to apply using simple methods such as filling to the interior of pipes with large length-to-diameter ratios. Furthermore, the high viscosity of the coating results in excessively thick coatings, which negatively impacts heat exchange performance, especially for heat exchange pipes. Additionally, existing coatings have poor antibacterial properties. Therefore, there is an urgent need for a method for preparing and applying a two-component, in-situ self-generating filler-type coating to address these issues. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides a method for preparing and applying a two-component in-situ self-generating filler-type coating. The coating consists of nearly homogeneous solution phases A and B, exhibits low viscosity upon initial mixing, facilitating its application in filling and coating pipes with large aspect ratios. Furthermore, the nanofiller can achieve in-situ self-generation, ensuring excellent adhesion and corrosion resistance of the coating while simultaneously improving the antibacterial properties of the pipe.

[0006] The present invention discloses a method for preparing a two-component in-situ self-generating filler coating, comprising the following steps:

[0007] S1. Prepare component A by dissolving a certain mass of zinc metal salt in a solvent;

[0008] S2. A certain mass of cyclodextrin-like substances and various organic molecules with corrosion-inhibiting or antibacterial functions are dissolved in a solvent, and a polymer material is added as a film-forming aid to prepare component B.

[0009] S3. Mix components A and B in a certain proportion and apply them to the inside of pipes with a large length-to-diameter ratio using a filling and coating method. Then cure at 25-150℃ to obtain an in-situ self-generated nanofiller type anti-corrosion and antibacterial dual-function coating.

[0010] Components A and B are nearly homogeneous solution phases. The coating viscosity is low when initially mixed, which is convenient for filling and coating pipes with large length-to-diameter ratios. Furthermore, the nanofiller can be generated in situ, ensuring excellent adhesion and corrosion resistance of the coating, while also improving the antibacterial properties of the pipe.

[0011] Preferably, the zinc metal salt in S1 is zinc phytate and zinc gluconate alone or in any proportion, and the mass ratio of zinc metal salt to solvent is 1:100-1:10.

[0012] Preferably, the cyclodextrin-like substance in S2 is one or more of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin.

[0013] Preferably, the organic molecules with corrosion-inhibiting or antibacterial functions in S2 are one or more of benzimidazole, benzotriazole, 2-aminobenzimidazole, 2-mercaptobenzothiazole, triclosan, and cytosyl acetamiprid, and the total mass ratio of cyclodextrin and organic molecules to solvent is 1:100-1:10.

[0014] Preferably, the solvent is one or more selected from water, ethanol, xylene, n / isopropanol, ethyl acetate, butyl acetate, tetrahydrofuran, and acetonitrile.

[0015] Preferably, the polymer material in S2 is one or more of water-based Teflon resin, epoxy resin, modified acrylic resin, polysilane resin, and water-based polyurethane resin.

[0016] Preferably, the polymer material in S2 accounts for 5 wt.% to 30 wt.% of the solvent by mass.

[0017] Preferably, the mixing ratio of components A and B in S3 is 1:1 to 1:5.

[0018] The present invention relates to an application of a two-component in-situ self-generating filler-type coating, which is applied to the interior of pipes with large length-to-diameter ratios, including copper-nickel alloy pipes, galvanized cast iron pipes, and aluminum alloy pipes, among others.

[0019] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0020] 1. Components A and B are nearly homogeneous solution phases. The coating viscosity is low when initially mixed, which can be used for filling and coating of pipes with large length-to-diameter ratio, improving the ease of coating.

[0021] 2. Nanofillers can achieve in-situ self-generation, resulting in excellent coating adhesion and corrosion resistance;

[0022] 3. The prepared coating not only has excellent anti-corrosion and coating effects, but also has good antibacterial effects. Attached Figure Description

[0023] Figure 1 This is a schematic diagram of the internal bonding mechanism of the antibacterial and anti-corrosion dual-function coating of the present invention;

[0024] Figure 2 This is a TEM image of the self-generated nanofiller in Example 1 of the present invention;

[0025] Figure 3 This is the XRD pattern of the self-generated nanofiller in Example 1 of the present invention;

[0026] Figure 4 This is a TEM image of the self-generated nanofiller in Example 2 of the present invention;

[0027] Figure 5 This is the XRD pattern of the self-generated nanofiller in Example 2 of the present invention. Detailed Implementation

[0028] To facilitate understanding of the present invention, a more complete description will be given below with reference to the accompanying drawings. The present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

[0029] like Figures 1 to 5 As shown, a method for preparing and applying a two-component in-situ self-generating filler coating includes the following steps:

[0030] S1. Prepare component A by dissolving a certain mass of zinc metal salt in a solvent;

[0031] S2. A certain mass of cyclodextrin-like substances and various organic molecules with corrosion-inhibiting or antibacterial functions are dissolved in a solvent, and a polymer material is added as a film-forming aid to prepare component B.

[0032] S3. Mix components A and B in a certain proportion and apply them to the inside of pipes with a large length-to-diameter ratio using a filling and coating method. Then cure at 25-150℃ to obtain an in-situ self-generated nanofiller type anti-corrosion and antibacterial dual-function coating.

[0033] The zinc metal salt in S1 is zinc phytate and zinc gluconate alone or in any proportion, and the mass ratio of zinc metal salt to solvent is 1:100-1:10.

[0034] The cyclodextrin-like substance in S2 is one or more of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin;

[0035] The organic molecules with corrosion-inhibiting or antibacterial functions in S2 are one or more of benzimidazole, benzotriazole, 2-aminobenzimidazole, 2-mercaptobenzothiazole, triclosan, and cymoxanil, and the total mass ratio of cyclodextrin and organic molecules to solvent is 1:100-1:10.

[0036] The solvent is one or more selected from water, ethanol, xylene, n / isopropanol, ethyl acetate, butyl acetate, tetrahydrofuran, and acetonitrile.

[0037] The polymer material in S2 is one or more of the following: waterborne Teflon resin, epoxy resin, modified acrylic resin, polysilane resin, and waterborne polyurethane resin.

[0038] The polymer material in S2 accounts for 5 wt.%-30 wt.% of the solvent by mass;

[0039] The mixing ratio of components A and B in S3 is 1:1 to 1:5;

[0040] The application scope is the interior of pipes with large length-to-diameter ratios, including copper-nickel alloy pipes, galvanized cast iron pipes, and aluminum alloy pipes.

[0041] Example 1

[0042] A method for preparing and applying a two-component in-situ self-generating filler coating includes the following steps:

[0043] Component A: Dissolve 0.25g of zinc phytate and 0.25g of zinc gluconate in a mixed solvent of 30mL ethanol and 70mL water, and set aside for later use;

[0044] Component B: Dissolve 0.3g of β-cyclodextrin, 0.15g of benzimidazole, 0.15g of 2-aminobenzimidazole, and 0.3g of triclosan in a mixed solvent of 20mL ethanol and 80mL water, add 20mL of water-based Teflon resin, and set aside for use.

[0045] Mix components A and B in a 1:1 ratio, fill and coat the inside of B30 copper-nickel alloy pipes, and dry and cure at 30°C.

[0046] TEM observation revealed that the in-situ self-generated nanofillers exhibited various morphologies, including small particle clusters, strips, and large particles, as shown in the attached image. Figure 2 As shown in the attached figure, the XRD test results of the in-situ self-generated nanofiller are as follows. Figure 3 As shown, the coating is clearly amorphous and non-crystalline. After cutting the pipe, the coating thickness was measured to be 4.3 ± 0.2 micrometers using a thickness gauge. Antibacterial rate tests showed a 91% inhibition rate against Escherichia coli and a 93% inhibition rate against Staphylococcus aureus, demonstrating excellent antibacterial effects. Electrochemical impedance spectroscopy (EIS) tests revealed that the |Z| value of the bare B30 pipe at 0.01 Hz was 10385 Ω·cm. 2 After coating, the B30 pipe has a |Z| of 256930 Ω·cm at 0.01 Hz. 2 This represents an increase of an order of magnitude.

[0047] Example 2

[0048] A method for preparing and applying a two-component in-situ self-generating filler coating includes the following steps:

[0049] Component A: Dissolve 0.3g of zinc phytate and 0.20g of zinc gluconate in a mixed solvent of 40mL ethanol and 60mL water, and set aside for later use;

[0050] Component B: Dissolve 0.7g of β-cyclodextrin, 0.15g of benzimidazole, 0.1g of benzotriazole, 0.20g of 2-aminobenzimidazole, and 0.5g of triclosan in a mixed solvent of 35mL ethanol and 65mL water, add 15mL of water-based organosilicon-modified acrylic resin, and set aside for use.

[0051] Mix components A and B in a 1:2 ratio, fill and coat the inside of B10 copper-nickel alloy pipes, and dry and cure at 50°C.

[0052] TEM observation revealed that the in-situ self-generated nanofillers exhibited various morphologies, including small particles, sheets, and down-like structures, as shown in the attached image. Figure 4 As shown in the attached figure, the XRD test results of the in-situ self-generated nanofiller are as follows. Figure 5 As shown, the coating is predominantly amorphous, but exhibits crystalline peaks at 10° and 18° at 2θ. The coating thickness, measured using a thickness gauge, is 3.9 ± 0.3 micrometers after the pipe is cut open. Antibacterial performance tests show a 95% inhibition rate against Escherichia coli and a 90% inhibition rate against Staphylococcus aureus, demonstrating excellent antibacterial effects. Electrochemical impedance spectroscopy (EIS) tests revealed that the |Z| value of the bare B10 pipe at 0.01 Hz is 10132 Ω·cm. 2 After coating, the B10 pipe has a |Z| of 432641 Ω·cm at 0.01 Hz. 2 This represents an increase of an order of magnitude.

[0053] Example 3

[0054] Component A: Dissolve 0.1g of zinc phytate and 0.40g of zinc gluconate in a mixed solvent of 10mL ethanol and 90mL water, and set aside for later use;

[0055] Component B: Dissolve 0.2g of γ-cyclodextrin, 0.1g of benzimidazole, 0.2g of benzotriazole, 0.1g of 2-aminobenzimidazole, 0.4g of triclosan, and 0.1g of cyazofamid in a mixed solvent of 40mL ethanol, 20mL water, and 20mL xylene. Add 20mL of aqueous one-component epoxy resin and set aside for use.

[0056] Mix components A and B in a 1:3 ratio, fill and coat the inside of B30 copper-nickel alloy pipes, and dry and cure at 150°C.

[0057] The pipe was cut open, and the coating thickness was measured to be 4.1 ± 0.1 micrometers using a thickness gauge. Antibacterial rate tests showed a 98% inhibition rate against Escherichia coli and a 99% inhibition rate against Staphylococcus aureus, demonstrating excellent antibacterial effects. Electrochemical impedance spectroscopy (EIS) tests revealed that the |Z| value of the bare B30 pipe at 0.01 Hz was 10245 Ω·cm. 2 After coating, the B10 pipe has a |Z| of 613253 Ω·cm at 0.01 Hz. 2 This represents an increase of an order of magnitude.

[0058] Example 4

[0059] Component A: Dissolve 0.5g of zinc phytate in 100mL of aqueous solution and set aside for later use;

[0060] Component B: Dissolve 0.6g of α-cyclodextrin, 0.3g of benzimidazole, 0.1g of benzotriazole, and 0.3g of cyazofamid in a mixed solvent of 40mL ethanol, 10mL water, 10mL ethyl acetate, and 20mL xylene. Add 30mL of waterborne polyurethane resin and set aside for use.

[0061] Mix components A and B in a 1:4 ratio, fill and coat the inside of galvanized cast iron water pipes, and dry and cure at 60°C.

[0062] The pipe was cut open, and the coating thickness was measured to be 4.8 ± 0.15 micrometers using a thickness gauge. Antibacterial rate tests showed a 90% inhibition rate against Escherichia coli and a 92% inhibition rate against Staphylococcus aureus, demonstrating excellent antibacterial effects. Electrochemical impedance spectroscopy (EIS) tests revealed that the |Z| value of the bare galvanized cast iron pipe at 0.01 Hz was 1038 Ω·cm. 2 After coating, the galvanized cast iron pipe has a |Z| of 83691 Ω·cm at 0.01 Hz. 2 The increase was significant.

[0063] Example 5

[0064] Component A: Dissolve 0.5g of zinc gluconate in 100mL of water and set aside for later use;

[0065] Component B: Dissolve 0.5g of β-cyclodextrin, 0.1g of benzimidazole, 0.5g of benzotriazole, 0.1g of cyazofamid, and 0.4g of triclosan in a mixed solvent of 20mL ethanol, 10mL acetonitrile, 10mL butyl acetate, and 20mL xylene. Add 10mL of aqueous fluorinated acrylic resin and set aside for use.

[0066] Mix components A and B in a 1:5 ratio, fill and coat the inside of aluminum alloy pipes, and dry and cure at 100°C.

[0067] The pipe was cut open, and the coating thickness was measured to be 5.3 ± 0.2 micrometers using a thickness gauge. Antibacterial rate tests showed an inhibition rate of 91% against both *Escherichia coli* and *Staphylococcus aureus*, demonstrating excellent antibacterial effects. Electrochemical impedance spectroscopy (EIS) tests revealed that the |Z| value of the bare aluminum alloy pipe at 0.01 Hz was 20461 Ω·cm. 2 After coating, the galvanized cast iron pipe has a |Z| of 956784 Ω·cm at 0.01 Hz. 2 The increase was significant.

[0068] The present invention relates to an application of a two-component in-situ self-generating filler-type coating, which is applied to the interior of pipes with large length-to-diameter ratios, including copper-nickel alloy pipes, galvanized cast iron pipes, and aluminum alloy pipes, among others.

[0069] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the technical principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a two-component in-situ self-generating filler coating, characterized in that, The following steps are involved: S1. Prepare component A by dissolving a certain mass of zinc metal salt in a solvent; S2. A certain mass of cyclodextrin-like substances and various organic molecules with corrosion-inhibiting or antibacterial functions are dissolved in a solvent, and a polymer material is added as a film-forming aid to prepare component B. S3. Mix components A and B in a certain proportion and apply them to the inside of pipes with a large length-to-diameter ratio using a filling and coating method. Then cure at 25-150℃ to obtain an in-situ self-generated nanofiller type anti-corrosion and antibacterial dual-function coating. The zinc metal salt in S1 is zinc phytate and zinc gluconate alone or in any proportion, and the mass ratio of zinc metal salt to solvent is 1:100-1:

10. The organic molecules with corrosion-inhibiting or antibacterial functions in S2 are one or more of benzimidazole, benzotriazole, 2-aminobenzimidazole, 2-mercaptobenzothiazole, triclosan, and cytosyl acetamiprid, and the total mass ratio of cyclodextrin and organic molecules to solvent is 1:100-1:

10.

2. The method for preparing a two-component in-situ self-generating filler coating as described in claim 1, characterized in that, The cyclodextrin-like substances in S2 are one or more of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin.

3. The method for preparing a two-component in-situ self-generating filler coating as described in claim 1, characterized in that, The solvent is one or more of water, ethanol, xylene, n / isopropanol, ethyl acetate, butyl acetate, tetrahydrofuran, and acetonitrile.

4. The method for preparing a two-component in-situ self-generating filler coating as described in claim 1, characterized in that, The polymer material in S2 is one or more of the following: waterborne Teflon resin, epoxy resin, modified acrylic resin, polysilane resin, and waterborne polyurethane resin.

5. The method for preparing a two-component in-situ self-generating filler coating as described in claim 4, characterized in that, The polymer material in S2 accounts for 5 wt.%-30 wt.% of the solvent by mass.

6. The method for preparing a two-component in-situ self-generating filler coating as described in claim 1, characterized in that, The mixing ratio of components A and B in S3 is 1:1 to 1:

5.

7. An application of a two-component in-situ self-generating filler coating, characterized in that, The two-component in-situ self-generating filler coating prepared by the preparation method of any one of claims 1 to 6 is applicable to the interior of pipes with large length-to-diameter ratios, including copper-nickel alloy pipes, galvanized cast iron pipes, and aluminum alloy pipes.

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