Marine corrosion-resistant semi-conductive water-resistant hose and preparation method thereof

Abstract

The application discloses a kind of seawater-resistant anticorrosive semi-conductive water-blocking hose and preparation method thereof, and relates to the technical field of semi-conductive water-blocking material.The seawater-resistant anticorrosive semi-conductive water-blocking hose is sequentially arranged from top to bottom as a substrate layer, an inner semi-conductive glue layer, a salt-resistant water-absorbing layer, an outer semi-conductive glue layer and a cover layer.The salt-resistant water-absorbing layer is a salt-resistant polymer water-absorbing material.The inner semi-conductive glue layer and the outer semi-conductive glue layer are both modified acrylate emulsion.The seawater-resistant anticorrosive semi-conductive water-blocking hose provided by the application has excellent seawater resistance and corrosion resistance, obvious water-blocking effect, and good electrical conductivity, and can be applied in submarine cable to meet the water-blocking demand.The water-blocking hose is treated with acrylate emulsion to give it excellent hydrophobicity, which can effectively prevent water molecules from entering.The introduction of bifunctional Ni-MOF gives it good electrical conductivity and seawater resistance and corrosion resistance.

Description

Technical Field

[0001] This invention relates to the field of semiconducting resistive water materials technology, specifically to a seawater-resistant and corrosion-resistant semiconducting resistive water strip and its preparation method. Background Technology

[0002] Semiconducting water-resistant tape consists of two layers of semiconducting substrate with a middle layer of superabsorbent polymer. This tape is directly coated onto the conductor surface to achieve shielding and water blocking. While superabsorbent polymers have a high water absorption rate in pure water, their absorption rate in seawater is only one-tenth that of pure water. Therefore, they barely expand in seawater and cannot meet the water-blocking requirements of submarine cables. Furthermore, direct application to the conductor can easily corrode copper conductors, reducing their strength and significantly increasing their resistance. In addition, the adhesives used to bond the semiconducting substrate and the superabsorbent polymer are easily affected by the salinity and high pH of seawater, which has a strong destructive effect on the adhesive, leading to hydration, dissolution, and failure of the adhesive.

[0003] Acrylic emulsions possess excellent bonding properties and good water resistance; however, their application in cable water-blocking tapes is limited by the cable's operating environment. For example, cables used in seawater must consider the corrosiveness of seawater due to its high salt content. Furthermore, the water-blocking tape also needs to possess a certain degree of conductivity. Therefore, there is a need to develop a semi-conductive water-blocking tape with excellent seawater and corrosion resistance, significant water-blocking effect, and good conductivity, suitable for use in submarine cables. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a seawater-resistant and corrosion-resistant semiconducting resistive water strip and its preparation method.

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] A seawater-resistant and corrosion-resistant semiconducting water-absorbing tape comprises, from top to bottom, a substrate layer, an inner semiconducting adhesive layer, a salt-resistant absorbent layer, an outer semiconducting adhesive layer, and a cover layer; the salt-resistant absorbent layer is a salt-resistant polymer absorbent material; the inner and outer semiconducting adhesive layers are both modified acrylic emulsions; the substrate layer is made of adhesive fabric; and the cover layer is made of nylon.

[0007] The modified acrylate emulsion is prepared by the following steps:

[0008] Step A1: Add cyanuric chloride and acetone to a flask and stir until homogeneous. Add 2-decyltetradecyl-1-amine and sodium hydroxide to a beaker containing deionized water and stir until homogeneous to obtain mixture A. Then transfer mixture A to a flask and react at -5 to -5℃ for 2 to 3 hours. After the reaction is complete, intermediate product 1 can be obtained.

[0009] In step A1, the nucleophilic substitution reaction between the chlorine atom on cyanuric chloride and the amino group is used to synthesize intermediate product 1 with a long-chain alkyl structure, which improves the hydrophobicity of the matrix. This is because the long-chain alkyl group can form a weak interaction with water molecules in the matrix, thus making the matrix surface hydrophobic. In addition, the presence of the triazine structure improves the alkali resistance of the matrix. This is because the unique structure of the triazine group makes it less susceptible to damage in acidic and alkaline environments and can remain stable.

[0010] Furthermore, the ratio of cyanuric chloride, acetone and mixture A is 0.01-0.02 mol: 40 mL: 20 mL, and the ratio of 2-decyltetradecyl-1-amine, sodium hydroxide and deionized water in mixture A is 0.01-0.02 mol: 0.4-0.8 g: 20 mL.

[0011] Step A2: Add 3-buten-1-ol and sodium hydroxide to a beaker containing deionized water and stir until homogeneous to obtain mixture B. Then add mixture B to a flask containing intermediate product 1 and react at 40-50℃ for 2-3 hours. After the reaction is complete, raise the system temperature to 60℃ to remove acetone, then raise the system temperature to 80-90℃, add mixture B, and reflux continuously for 8-10 hours. After the reaction is complete, cool to room temperature, filter, wash, and dry at 60℃ for 12 hours to obtain the hydrophobic monomer with terminal double bonds.

[0012] In step A2, the hydroxyl group on 3-buten-1-ol can undergo a nucleophilic substitution reaction with the chlorine atom on intermediate product 1, thereby introducing a terminal double bond, which enables it to participate in the copolymerization reaction of acrylate, thus introducing a long-chain hydrophobic alkyl structure into the acrylate and achieving the hydrophobic properties of the acrylate.

[0013] Furthermore, the ratio of the amount of cyanuric chloride used in mixture B to that used in step A1 is 20-40 mL: 0.01-0.02 mol, and the ratio of the amount of 3-buten-1-ol, sodium hydroxide and deionized water used in mixture B is 0.02-0.04 mol: 0.8-0.16 g: 20-40 mL.

[0014] Step A3: Mix methacrylic acid, methyl methacrylate, perfluorooctyl propyl acrylate, hydrophobic monomers with terminal double bonds, and xylene to obtain mixture C. Add half of mixture C to one-third of sodium dodecyl sulfate solution and stir to obtain a pre-emulsion. Then add the remaining half of mixture C and the bifunctionalized Ni-MOF to the remaining two-thirds of sodium dodecyl sulfate solution and stir to obtain a seed emulsion. Then add the seed emulsion and one-half of 2'2-azobisisobutyronitrile xylene solution to the reactor and react at 75°C under nitrogen for 30 minutes. Raise the temperature to 80-90°C, and then add the pre-emulsion and the remaining half of 2'2-azobisisobutyronitrile xylene solution dropwise to the reactor over 2 hours. Then keep the reaction at this temperature for 3-5 hours. After the reaction is complete, remove the unreacted monomers and solvents by rotary evaporation to obtain the acrylate emulsion.

[0015] The acrylate emulsion prepared by emulsion polymerization of crosslinking monomers in step A3 exhibits excellent hydrophobic properties. This is because the hydrophobic monomers with terminal double bonds and the fluorinated monomers work synergistically to improve the hydrophobicity of the matrix. In particular, the fluorinated monomers generate fluorinated polyacrylate oligomers during the polymerization reaction, which contain more low surface energy -CF and -CF3 segments, making them easier to migrate to the latex surface, thereby improving the hydrophobicity of the matrix. In addition, the addition of bifunctionalized Ni-MOF improves the salt resistance of the matrix.

[0016] Furthermore, the ratio of methacrylic acid, methyl methacrylate, perfluorooctyl propyl acrylate, hydrophobic monomer with terminal double bonds, xylene, 2'2-azobisisobutyronitrile xylene solution, sodium dodecyl sulfate solution, and difunctionalized Ni-MOF is 8-12g:5-8g:1-3g:2-4g:10-15g:8-10g:10mL:0.1-0.3g. The 2'2-azobisisobutyronitrile xylene solution is prepared by mixing 2'2-azobisisobutyronitrile and xylene in a ratio of 0.1-0.15g:8-10g. The sodium dodecyl sulfate solution is prepared by mixing sodium dodecyl sulfate and deionized water in a ratio of 0.5-0.8g:10mL.

[0017] The bifunctionalized Ni-MOF is prepared by the following steps:

[0018] Step B1: Add nickel nitrate hexahydrate to a beaker containing a mixture of N,N-dimethylformamide, ethanol and deionized water, and stir at room temperature for 30 min. Then add 2-amino-5-sulfobenzoic acid and continue stirring for 30 min. Next, add carbon quantum dots and stir until homogeneous. Finally, transfer the mixture in the beaker to a hydrothermal reactor and react at 100 °C for 24 h. After the reaction is complete, filter, wash, and vacuum dry at 50 °C for 24 h to obtain MOF-74.

[0019] In step B1, 2-amino-5-sulfobenzoic acid was used as the organic ligand for the MOF material. The synthesized MOF-74 exhibited good salt resistance because the sulfonic acid groups on its surface were insensitive to salt, thereby improving the salt resistance of the matrix and allowing it to maintain good performance in seawater. Its surface also contained amino groups, which could participate in the introduction of double bonds. In addition, the metal-organic framework formed by using Ni as the metal ion and doping with carbon quantum dots had good conductivity because carbon quantum dots, as a conductive agent, could improve the electronic conductivity of MOF-74. The emulsion formed after introducing it into acrylate had good conductivity.

[0020] Furthermore, the ratio of nickel nitrate hexahydrate, N,N-dimethylformamide, ethanol, deionized water, 2-amino-5-sulfobenzoic acid and carbon quantum dots is 0.5-1.0g:75mL:5mL:5mL:0.1-0.2g:2-5mL.

[0021] Step B2: Disperse MOF-74 in dichloromethane using ultrasound, then add methacrylic anhydride to the resulting solution, and stir at 300 rpm for 24-48 h. After the reaction is complete, filter, wash three times, and dry in a vacuum drying oven at 45℃ for 24 h to obtain bifunctionalized Ni-MOF.

[0022] In step B2, the active amino groups on the surface of MOF-74 can react with methacrylic anhydride, thereby introducing double bonds on its surface. When MOF-74 containing double bonds is added to the acrylate monomer, the initiator decomposes upon heating to form active free radicals. The acrylate monomers or growing polymers that capture these free radicals collide with the MOF-74 containing double bonds. At this time, the free radicals react with the C=C double bonds on the surface of MOF-74, thereby forming chemical bonds between MOF-74 and the acrylate. As a result, more and more monomers accumulate on its surface, thus encapsulating MOF-74 to form a core structure, which improves the stability of the acrylate emulsion.

[0023] Furthermore, the ratio of MOF-74, dichloromethane, and methacrylic anhydride is 0.2-0.5g: 40-100mL: 2-5mL.

[0024] A method for preparing a seawater-resistant and corrosion-resistant semiconducting resistive water strip includes the following steps:

[0025] Step S1: A modified acrylic emulsion and a salt-resistant superabsorbent polymer are uniformly coated sequentially on one side of the substrate layer to form a composite layer A; a modified acrylic emulsion is uniformly coated on one side of the cover layer to form a composite layer B; the side of composite layer A coated with the salt-resistant superabsorbent polymer is combined with the side of composite layer B coated with the modified acrylic emulsion to obtain the pretreated water-blocking tape.

[0026] Step S2: Dry the pretreated water-blocking tape at 120-180℃ to obtain a seawater-resistant and corrosion-resistant semi-conductive water-blocking tape.

[0027] The salt-resistant superabsorbent polymer is synthesized using butyl acrylate, acrylic acid, methacrylate and 2-methyl-2-acrylate-2-sulfoethyl ester as monomers, xylene as solvent and tert-butyl peroxide as initiator.

[0028] The beneficial effects of this invention are:

[0029] The seawater-resistant and corrosion-resistant semi-conductive water-blocking tape provided by this invention exhibits excellent seawater and corrosion resistance, significant water-blocking effect, and good conductivity, making it suitable for use in submarine cables to meet water-blocking requirements. This water-blocking tape is made by treating an acrylic emulsion, giving it excellent hydrophobicity and effectively preventing the entry of water molecules; the introduction of a bifunctionalized Ni-MOF imparts good conductivity and seawater and corrosion resistance.

[0030] In the modification of acrylate emulsions, the monomers used to synthesize the acrylate emulsions are first modified: 1) The hydrophobicity of the matrix is ​​improved by utilizing the synergistic effect of long-chain alkyl groups and -CF and -CF3 segments containing more low surface energy; 2) Triazine groups with unique structures are introduced, and their stability in acidic and alkaline environments is utilized to improve the alkali resistance of the matrix, so that the matrix still has good performance in seawater; 3) Terminal double bonds are introduced to enable them to participate in the copolymerization reaction of acrylates, thereby introducing long-chain hydrophobic alkyl structures and triazine groups into acrylates to achieve the hydrophobic properties of acrylates. Secondly, the introduction of bifunctional Ni-MOF improves the seawater resistance, corrosion resistance, and conductivity of the matrix: 1) Using 2-amino-5-sulfobenzoic acid as the organic ligand of the MOF material, the synthesized MOF-74 has good salt resistance. This is because the sulfonic acid groups on its surface are insensitive to salt, thus improving the salt resistance of the matrix; 2) The double bond structure introduced on its surface can participate in the polymerization of acrylate, thereby forming a core structure and improving the stability of the acrylate emulsion; 3) The metal-organic framework formed by using Ni as a metal ion and doping with carbon quantum dots has good conductivity. This is because carbon quantum dots, as a conductive agent, can improve the electronic conductivity of MOF-74, and the emulsion formed after introducing them into acrylate has good conductivity. Detailed Implementation

[0031] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0032] Example 1

[0033] 1) The modified acrylate emulsion is prepared by the following steps:

[0034] Step A1: Add cyanuric chloride and acetone to a flask and stir until homogeneous. Add 2-decyltetradecyl-1-amine and sodium hydroxide to a beaker containing deionized water and stir until homogeneous to obtain mixture A. Then transfer mixture A to a flask and react at -5℃ for 2 hours. After the reaction is complete, intermediate product 1 is obtained. The ratio of cyanuric chloride, acetone and mixture A is 0.01 mol: 40 mL: 20 mL. The ratio of 2-decyltetradecyl-1-amine, sodium hydroxide and deionized water in mixture A is 0.01 mol: 0.4 g: 20 mL.

[0035] Step A2: Add 3-buten-1-ol and sodium hydroxide to a beaker containing deionized water and stir until homogeneous to obtain mixture B. Then add mixture B to a flask containing intermediate product 1 and react at 40°C for 2 hours. After the reaction is complete, raise the system temperature to 60°C to remove acetone, then raise the system temperature to 80°C, add mixture B, and reflux continuously for 8 hours. After the reaction is complete, cool to room temperature, filter, wash, and dry at 60°C for 12 hours to obtain the hydrophobic monomer with terminal double bonds. The ratio of the amount of cyanuric chloride in mixture B to that in step A1 is 20 mL: 0.01 mol, and the ratio of the amount of 3-buten-1-ol, sodium hydroxide, and deionized water in mixture B is 0.02 mol: 0.8 g: 20 mL.

[0036] Step A3: Methacrylic acid, methyl methacrylate, perfluorooctyl propyl acrylate, terminal double-bond hydrophobic monomers, and xylene are stirred and mixed thoroughly to obtain mixture C. Half of mixture C is added to one-third of sodium dodecyl sulfate solution and stirred until homogeneous to obtain a pre-emulsion. Then, the remaining half of mixture C and the bifunctionalized Ni-MOF are added to the remaining two-thirds of sodium dodecyl sulfate solution and stirred until homogeneous to obtain a seed emulsion. Next, the seed emulsion and one-half of the 2'2-azobisisobutyronitrile xylene solution are added to a reactor and reacted at 75°C under nitrogen atmosphere for 30 minutes. The temperature is then increased to 80°C, and the pre-emulsion and the remaining one-half of the 2'2-azobisisobutyronitrile xylene solution are added dropwise to the reactor. The addition time was 2 hours, followed by a 3-hour incubation period. After the reaction was complete, unreacted monomers and solvents were removed by rotary evaporation to obtain an acrylate emulsion. The ratio of methacrylic acid, methyl methacrylate, perfluorooctyl propyl acrylate, hydrophobic monomers with terminal double bonds, xylene, 2'2-azobisisobutyronitrile xylene solution, sodium dodecyl sulfate solution, and difunctionalized Ni-MOF was 8 g: 5 g: 1 g: 2 g: 10 g: 8 g: 10 mL: 0.1 g. The 2'2-azobisisobutyronitrile xylene solution was prepared by mixing 2'2-azobisisobutyronitrile and xylene in a ratio of 0.1 g: 8 g, and the sodium dodecyl sulfate solution was prepared by mixing sodium dodecyl sulfate and deionized water in a ratio of 0.5 g: 10 mL.

[0037] 2) The bifunctionalized Ni-MOF is prepared by the following steps:

[0038] Step B1: Add nickel nitrate hexahydrate to a beaker containing a mixture of N,N-dimethylformamide, ethanol, and deionized water, and stir at room temperature for 30 min. Then add 2-amino-5-sulfobenzoic acid and continue stirring for 30 min. Next, add carbon quantum dots and stir until homogeneous. Finally, transfer the mixture in the beaker to a hydrothermal reactor and react at 100°C for 24 h. After the reaction is complete, filter, wash, and vacuum dry at 50°C for 24 h to obtain MOF-74. The ratio of nickel nitrate hexahydrate, N,N-dimethylformamide, ethanol, deionized water, 2-amino-5-sulfobenzoic acid, and carbon quantum dots is 0.5 g: 75 mL: 5 mL: 5 mL: 0.1 g: 2 mL.

[0039] Step B2: Disperse MOF-74 ultrasonically in dichloromethane, then add methacrylic anhydride to the resulting solution, and stir at 300 rpm for 24 h. After the reaction is complete, filter, wash three times, and dry in a vacuum drying oven at 45℃ for 24 h to obtain bifunctionalized Ni-MOF. The ratio of MOF-74, dichloromethane, and methacrylic anhydride is 0.2 g: 40 mL: 2 mL.

[0040] Example 2

[0041] 1) The modified acrylate emulsion is prepared by the following steps:

[0042] Step A1: Add cyanuric chloride and acetone to a flask and stir until homogeneous. Add 2-decyltetradecyl-1-amine and sodium hydroxide to a beaker containing deionized water and stir until homogeneous to obtain mixture A. Then transfer mixture A to a flask and react at 0℃ for 2.5h. After the reaction is complete, intermediate product 1 is obtained. The ratio of cyanuric chloride, acetone and mixture A is 0.015mol:40mL:20mL. The ratio of 2-decyltetradecyl-1-amine, sodium hydroxide and deionized water in mixture A is 0.015mol:0.6g:20mL.

[0043] Step A2: Add 3-buten-1-ol and sodium hydroxide to a beaker containing deionized water and stir until homogeneous to obtain mixture B. Then add mixture B to a flask containing intermediate product 1 and react at 45°C for 2.5 h. After the reaction is complete, raise the system temperature to 60°C to remove acetone, then raise the system temperature to 85°C, add mixture B, and reflux continuously for 9 h. After the reaction is complete, cool to room temperature, filter, wash, and dry at 60°C for 12 h to obtain the hydrophobic monomer with terminal double bonds. The ratio of the amount of cyanuric chloride used in mixture B to that in step A1 is 30 mL: 0.015 mol, and the ratio of the amount of 3-buten-1-ol, sodium hydroxide, and deionized water used in mixture B is 0.03 mol: 0.12 g: 30 mL.

[0044] Step A3: Methacrylic acid, methyl methacrylate, perfluorooctyl propyl acrylate, terminal double-bond hydrophobic monomers, and xylene are stirred and mixed thoroughly to obtain mixture C. Half of mixture C is added to one-third of sodium dodecyl sulfate solution and stirred until homogeneous to obtain a pre-emulsion. Then, the remaining half of mixture C and the bifunctionalized Ni-MOF are added to the remaining two-thirds of sodium dodecyl sulfate solution and stirred until homogeneous to obtain a seed emulsion. Next, the seed emulsion and one-half of the 2'2-azobisisobutyronitrile xylene solution are added to a reactor and reacted at 75°C under nitrogen atmosphere for 30 minutes. The temperature is then increased to 85°C, and the pre-emulsion and the remaining one-half of the 2'2-azobisisobutyronitrile xylene solution are added dropwise to the reactor. The addition time was 2 hours, followed by a 4-hour incubation period. After the reaction was complete, unreacted monomers and solvents were removed by rotary evaporation to obtain an acrylate emulsion. The ratio of methacrylic acid, methyl methacrylate, perfluorooctyl propyl acrylate, hydrophobic monomers with terminal double bonds, xylene, 2'2-azobisisobutyronitrile xylene solution, sodium dodecyl sulfate solution, and difunctionalized Ni-MOF was 10 g: 7 g: 2 g: 3 g: 12 g: 9 g: 10 mL: 0.2 g. The 2'2-azobisisobutyronitrile xylene solution was prepared by mixing 2'2-azobisisobutyronitrile and xylene at a ratio of 0.1 g: 9 g, and the sodium dodecyl sulfate solution was prepared by mixing sodium dodecyl sulfate and deionized water at a ratio of 7 g: 10 mL.

[0045] 2) The bifunctionalized Ni-MOF is prepared by the following steps:

[0046] Step B1: Add nickel nitrate hexahydrate to a beaker containing a mixture of N,N-dimethylformamide, ethanol, and deionized water, and stir at room temperature for 30 min. Then add 2-amino-5-sulfobenzoic acid and continue stirring for 30 min. Next, add carbon quantum dots and stir until homogeneous. Finally, transfer the mixture in the beaker to a hydrothermal reactor and react at 100°C for 24 h. After the reaction is complete, filter, wash, and vacuum dry at 50°C for 24 h to obtain MOF-74. The ratio of nickel nitrate hexahydrate, N,N-dimethylformamide, ethanol, deionized water, 2-amino-5-sulfobenzoic acid, and carbon quantum dots is 0.75 g: 75 mL: 5 mL: 5 mL: 0.15 g: 3.5 mL.

[0047] Step B2: Disperse MOF-74 ultrasonically in dichloromethane, then add methacrylic anhydride to the resulting solution, and stir at 300 rpm for 36 h. After the reaction is complete, filter, wash three times, and dry in a vacuum drying oven at 45℃ for 24 h to obtain bifunctionalized Ni-MOF. The ratio of MOF-74, dichloromethane, and methacrylic anhydride is 0.35 g: 70 mL: 3.5 mL.

[0048] Example 3

[0049] 1) The modified acrylate emulsion is prepared by the following steps:

[0050] Step A1: Add cyanuric chloride and acetone to a flask and stir until homogeneous. Add 2-decyltetradecyl-1-amine and sodium hydroxide to a beaker containing deionized water and stir until homogeneous to obtain mixture A. Then transfer mixture A to a flask and react at 5°C for 3 hours. After the reaction is complete, intermediate product 1 is obtained. The ratio of cyanuric chloride, acetone and mixture A is 0.02 mol: 40 mL: 20 mL. The ratio of 2-decyltetradecyl-1-amine, sodium hydroxide and deionized water in mixture A is 0.02 mol: 0.8 g: 20 mL.

[0051] Step A2: Add 3-buten-1-ol and sodium hydroxide to a beaker containing deionized water and stir until homogeneous to obtain mixture B. Then add mixture B to a flask containing intermediate product 1 and react at 50°C for 3 hours. After the reaction is complete, raise the system temperature to 60°C to remove acetone, then raise the system temperature to 90°C, add mixture B, and reflux continuously for 10 hours. After the reaction is complete, cool to room temperature, filter, wash, and dry at 60°C for 12 hours to obtain the hydrophobic monomer with terminal double bonds. The ratio of the amount of cyanuric chloride used in mixture B to that in step A1 is 40 mL: 0.02 mol, and the ratio of the amount of 3-buten-1-ol, sodium hydroxide, and deionized water used in mixture B is 0.04 mol: 0.16 g: 40 mL.

[0052] Step A3: Mix methacrylic acid, methyl methacrylate, perfluorooctyl propyl acrylate, hydrophobic monomers with terminal double bonds, and xylene to obtain mixture C. Add half of mixture C to one-third of sodium dodecyl sulfate solution and mix thoroughly to obtain a pre-emulsion. Then, add the remaining half of mixture C and the bifunctionalized Ni-MOF to the remaining two-thirds of sodium dodecyl sulfate solution and mix thoroughly to obtain a seed emulsion. Next, add the seed emulsion and one-half of 2'2-azobisisobutyronitrile xylene solution to the reactor and react at 75°C under nitrogen for 30 minutes. Raise the temperature to 90°C, and then add the pre-emulsion and the remaining half of the 2'2-azobisisobutyronitrile xylene solution dropwise to the reactor. The reaction time was 2 hours, followed by a 5-hour incubation period. After the reaction was complete, unreacted monomers and solvents were removed by rotary evaporation to obtain an acrylate emulsion. The ratio of methacrylic acid, methyl methacrylate, perfluorooctyl propyl acrylate, hydrophobic monomers with terminal double bonds, xylene, 2'2-azobisisobutyronitrile xylene solution, sodium dodecyl sulfate solution, and difunctionalized Ni-MOF was 12 g: 8 g: 3 g: 4 g: 15 g: 10 g: 10 mL: 0.3 g. The 2'2-azobisisobutyronitrile xylene solution was prepared by mixing 2'2-azobisisobutyronitrile and xylene in a ratio of 0.15 g: 10 g, and the sodium dodecyl sulfate solution was prepared by mixing sodium dodecyl sulfate and deionized water in a ratio of 0.8 g: 10 mL.

[0053] 2) The bifunctionalized Ni-MOF is prepared by the following steps:

[0054] Step B1: Add nickel nitrate hexahydrate to a beaker containing a mixture of N,N-dimethylformamide, ethanol, and deionized water, and stir at room temperature for 30 min. Then add 2-amino-5-sulfobenzoic acid and continue stirring for 30 min. Next, add carbon quantum dots and stir until homogeneous. Finally, transfer the mixture in the beaker to a hydrothermal reactor and react at 100 °C for 24 h. After the reaction is complete, filter, wash, and vacuum dry at 50 °C for 24 h to obtain MOF-74. The ratio of nickel nitrate hexahydrate, N,N-dimethylformamide, ethanol, deionized water, 2-amino-5-sulfobenzoic acid, and carbon quantum dots is 1.0 g: 75 mL: 5 mL: 5 mL: 0.2 g: 5 mL.

[0055] Step B2: Disperse MOF-74 ultrasonically in dichloromethane, then add methacrylic anhydride to the resulting solution, and stir at 300 rpm for 48 h. After the reaction is complete, filter, wash three times, and dry in a vacuum drying oven at 45℃ for 24 h to obtain bifunctionalized Ni-MOF. The ratio of MOF-74, dichloromethane, and methacrylic anhydride is 0.5 g: 100 mL: 5 mL.

[0056] Example 4

[0057] Salt-resistant superabsorbent polymers are prepared by the following steps:

[0058] 3g of acrylic acid, 10g of methacrylate, 5g of 2-methyl-2-acrylate-2-sulfoethyl ester and 0.1g of tert-butyl peroxide were added to a beaker containing 40mL of xylene and mixed thoroughly. The mixture was slowly added dropwise over 3 hours while stirring at a constant speed. After the addition was complete, the mixture was refluxed at 130℃ for 2 hours. Then, 0.1g of tert-butyl peroxide was added and the mixture was stirred for another 1 hour. After the reaction was completed, the salt-resistant superabsorbent polymer material was obtained.

[0059] Example 5

[0060] A method for preparing a seawater-resistant and corrosion-resistant semiconducting resistive water strip includes the following steps:

[0061] Step S1: Coat one side of the adhesive fabric with the modified acrylic emulsion prepared in Example 1 and the salt-resistant superabsorbent polymer prepared in Example 4 to form a composite layer A; coat one side of the nylon fabric with the modified acrylic emulsion prepared in Example 1 to form a composite layer B; combine the side of composite layer A coated with the salt-resistant superabsorbent polymer prepared in Example 4 with the side of composite layer B coated with the modified acrylic emulsion prepared in Example 1 to obtain the pretreated water-blocking tape;

[0062] Step S2: Dry the pretreated water-blocking tape at 120°C to obtain a seawater-resistant and corrosion-resistant semi-conductive water-blocking tape.

[0063] Example 6

[0064] A method for preparing a seawater-resistant and corrosion-resistant semiconducting resistive water strip includes the following steps:

[0065] Step S1: Coat one side of the adhesive fabric with the modified acrylic emulsion prepared in Example 2 and the salt-resistant superabsorbent polymer prepared in Example 4 to form a composite layer A; coat one side of the nylon fabric with the modified acrylic emulsion prepared in Example 2 to form a composite layer B; combine the side of composite layer A coated with the salt-resistant superabsorbent polymer prepared in Example 4 with the side of composite layer B coated with the modified acrylic emulsion prepared in Example 2 to obtain the pretreated water-blocking tape;

[0066] Step S2: Dry the pretreated water-blocking tape at 150°C to obtain a seawater-resistant and corrosion-resistant semi-conductive water-blocking tape.

[0067] Example 7

[0068] A method for preparing a seawater-resistant and corrosion-resistant semiconducting resistive water strip includes the following steps:

[0069] Step S1: Coat one side of the adhesive fabric with the modified acrylic emulsion prepared in Example 3 and the salt-resistant superabsorbent polymer prepared in Example 4 to form a composite layer A; coat one side of the nylon fabric with the modified acrylic emulsion prepared in Example 3 to form a composite layer B; combine the side of composite layer A coated with the salt-resistant superabsorbent polymer prepared in Example 4 with the side of composite layer B coated with the modified acrylic emulsion prepared in Example 3 to obtain the pretreated water-blocking tape;

[0070] Step S2: Dry the pretreated water-blocking tape at 180°C to obtain a seawater-resistant and corrosion-resistant semi-conductive water-blocking tape.

[0071] Comparative Example 1

[0072] This comparative example is a semiconducting resistive water tape. The difference between this example and Example 7 is that the modified acrylate emulsion prepared in Example 3 is coated with an equal amount of acrylate instead of perfluorooctylpropyl acrylate, and the Ni-MOF is synthesized with 2-aminobenzoic acid as the organic ligand. All other aspects are the same.

[0073] Comparative Example 2

[0074] This comparative example is a semiconducting resistive water tape. The difference between this example and Example 7 is that the modified acrylate emulsion prepared in Example 3 is coated with an equal amount of acrylate instead of the hydrophobic monomer with terminal double bonds, and the Ni-MOF is synthesized with 2-aminobenzoic acid as the organic ligand. All other aspects are the same.

[0075] Comparative Example 3

[0076] This comparative example is a semiconducting resistive water tape. The difference between this example and Example 7 is that the Ni-MOF in the modified acrylate emulsion prepared in Example 3 is synthesized using only 2-aminobenzoic acid as the organic ligand and nickel nitrate hexahydrate as the metal source (without any other modification treatment). All other aspects are the same.

[0077] The semiconducting resistance water tapes prepared in Examples 5-7 and Comparative Examples 1-3 were applied to the surface of copper conductors, and their performance was tested according to JB / T10259-2014. Samples were prepared by uniformly coating the modified acrylic emulsion used in Examples 5-7 and Comparative Examples 1-3 onto the surface of a 5cm × 5cm adhesive cloth for performance testing. Contact angle testing: The contact angle was measured using an OCA40Micro dynamic contact angle meter. Alkali resistance testing: The sample was immersed in a 5% NaOH solution and sealed for 48 hours. Afterward, the sample was removed and rinsed with distilled water, and the coating surface was observed for peeling. The test results are shown in Table 1.

[0078] Table 1

[0079]

[0080]

[0081] As can be seen from Table 1, the semiconducting resistive water tapes prepared in Examples 5-7 expand rapidly in seawater, have a significant water-blocking effect, good conductivity, and good alkali resistance.

[0082] The above description is merely an example and illustration of the concept of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the concept of the invention or exceed the scope defined in the claims, they should all fall within the protection scope of the present invention.

Claims

1. A seawater-resistant and corrosion-resistant semi-conductive resistive water hose, characterized in that, From top to bottom, the layers are: a substrate layer, an inner semi-conductive adhesive layer, a salt-resistant absorbent layer, an outer semi-conductive adhesive layer, and a cover layer. The salt-resistant absorbent layer is a salt-resistant polymer absorbent material. The inner and outer semi-conductive adhesive layers are both modified acrylic emulsions. The substrate layer is made of adhesive fabric. The cover layer is made of nylon. The modified acrylate emulsion is prepared by the following steps: Step A1: Add cyanuric chloride and acetone to a flask and stir until homogeneous. Add 2-decyltetradecyl-1-amine and sodium hydroxide to a beaker containing deionized water and stir until homogeneous to obtain mixture A. Then transfer mixture A to a flask and react at -5 to -5℃ for 2 to 3 hours. After the reaction is complete, intermediate product 1 can be obtained. Step A2: Add 3-buten-1-ol and sodium hydroxide to a beaker containing deionized water and stir until homogeneous to obtain mixture B. Then add mixture B to a flask containing intermediate product 1 and react at 40-50℃ for 2-3 hours. After the reaction is complete, raise the system temperature to 60℃ to remove acetone, then raise the system temperature to 80-90℃, add mixture B, and reflux continuously for 8-10 hours. After the reaction is complete, cool to room temperature, filter, wash, and dry at 60℃ for 12 hours to obtain the hydrophobic monomer with terminal double bonds. Step A3: Mix methacrylic acid, methyl methacrylate, perfluorooctyl propyl acrylate, hydrophobic monomers with terminal double bonds, and xylene to obtain mixture C. Add 1 / 2 of mixture C to 1 / 3 of sodium dodecyl sulfate solution and stir to obtain pre-emulsion. Then add the remaining 1 / 2 of mixture C and bifunctionalized Ni-MOF to the remaining 2 / 3 of sodium dodecyl sulfate solution and stir to obtain seed emulsion. Then add the seed emulsion and 1 / 2 of 2'2-azobisisobutyronitrile xylene solution to the reactor and react at 75°C under nitrogen for 30 minutes. Raise the temperature to 80-90°C, and then add the pre-emulsion and the remaining 1 / 2 of 2'2-azobisisobutyronitrile xylene solution dropwise to the reactor over 2 hours. Then keep the reaction at this temperature for 3-5 hours. After the reaction is complete, remove unreacted monomers and solvents by rotary evaporation to obtain acrylate emulsion. The bifunctionalized Ni-MOF is prepared by the following steps: Step B1: Add nickel nitrate hexahydrate to a beaker containing a mixture of N,N-dimethylformamide, ethanol and deionized water, and stir at room temperature for 30 min. Then add 2-amino-5-sulfobenzoic acid and continue stirring for 30 min. Next, add carbon quantum dots and stir until homogeneous. Finally, transfer the mixture in the beaker to a hydrothermal reactor and react at 100 °C for 24 h. After the reaction is complete, filter, wash, and vacuum dry at 50 °C for 24 h to obtain MOF-74. Step B2: Disperse MOF-74 in dichloromethane using ultrasound, then add methacrylic anhydride to the resulting solution and stir at 300 rpm for 24-48 h. After the reaction is complete, filter, wash three times, and dry in a vacuum drying oven at 45℃ for 24 h to obtain bifunctionalized Ni-MOF.

2. The seawater-resistant and corrosion-resistant semi-conductive resistive water hose according to claim 1, characterized in that, In step A1, the ratio of cyanuric chloride, acetone, and mixture A is 0.01-0.02 mol: 40 mL: 20 mL. In mixture A, the ratio of 2-decyltetradecyl-1-amine, sodium hydroxide, and deionized water is 0.01-0.02 mol: 0.4-0.8 g: 20 mL.

3. The seawater-resistant and corrosion-resistant semi-conductive resistive water hose according to claim 1, characterized in that, In step A2, the ratio of the amount of cyanuric chloride used in mixture B to that used in step A1 is 20-40 mL: 0.01-0.02 mol. The ratio of the amount of 3-buten-1-ol, sodium hydroxide, and deionized water used in mixture B is 0.02-0.04 mol: 0.8-0.16 g: 20-40 mL.

4. The seawater-resistant and corrosion-resistant semi-conductive resistive water hose according to claim 1, characterized in that, In step A3, the ratio of methacrylic acid, methyl methacrylate, perfluorooctyl propyl acrylate, hydrophobic monomer with terminal double bond, xylene, 2'2-azobisisobutyronitrile xylene solution, sodium dodecyl sulfate solution, and difunctionalized Ni-MOF is 8-12g:5-8g:1-3g:2-4g:10-15g:8-10g:10mL:0.1-0.3g. The 2'2-azobisisobutyronitrile xylene solution is prepared by mixing 2'2-azobisisobutyronitrile and xylene in a ratio of 0.1-0.15g:8-10g. The sodium dodecyl sulfate solution is prepared by mixing sodium dodecyl sulfate and deionized water in a ratio of 0.5-0.8g:10mL.

5. The seawater-resistant and corrosion-resistant semi-conductive resistive water hose according to claim 1, characterized in that, In step B1, the ratio of nickel nitrate hexahydrate, N,N-dimethylformamide, ethanol, deionized water, 2-amino-5-sulfobenzoic acid and carbon quantum dots is 0.5-1.0g:75mL:5mL:5mL:0.1-0.2g:2-5mL.

6. The seawater-resistant and corrosion-resistant semi-conductive resistive water hose according to claim 1, characterized in that, In step B2, the ratio of MOF-74, dichloromethane, and methacrylic anhydride is 0.2-0.5g: 40-100mL: 2-5mL.

7. The seawater-resistant and corrosion-resistant semi-conductive resistive water hose according to claim 1, characterized in that, The salt-resistant superabsorbent polymer is synthesized using butyl acrylate, acrylic acid, methacrylate and 2-methyl-2-acrylate-2-sulfoethyl ester as monomers, xylene as solvent and tert-butyl peroxide as initiator.

8. The method for preparing a seawater-resistant and corrosion-resistant semi-conductive resistive water strip according to claim 1, characterized in that, Includes the following steps: Step S1: A modified acrylic emulsion and a salt-resistant superabsorbent polymer are uniformly coated sequentially on one side of the substrate layer to form a composite layer A; a modified acrylic emulsion is uniformly coated on one side of the cover layer to form a composite layer B; the side of composite layer A coated with the salt-resistant superabsorbent polymer is combined with the side of composite layer B coated with the modified acrylic emulsion to obtain the pretreated water-blocking tape. Step S2: Dry the pretreated water-blocking tape at 120-180℃ to obtain a seawater-resistant and corrosion-resistant semi-conductive water-blocking tape.

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