High chlorinated polyethylene anticorrosive paint and preparation method thereof

Abstract

The invention discloses a high chlorinated polyethylene anticorrosive coating and a preparation method thereof. The coating is prepared by mixing high chlorinated polyethylene resin, a plasticizer, a coupling agent, an organic pigment, a polyethylene grafted nano material, polyvinyl chloride microspheres, a dispersing agent, an anti-settling anti-sagging agent, toluene and the like. Wherein the polyethylene grafted nano material is obtained by grafting a yttrium oxide-zirconium oxide-nitrogen doped graphene composite nano material with polyethylene. The paint has excellent corrosion resistance and heat resistance, and has a good application prospect.

Description

Technical Field

[0001] The invention belongs to the technical field of coating preparation, and particularly relates to a highly chlorinated polyethylene anti-corrosion coating and a preparation method thereof. Background Art

[0002] Highly chlorinated polyethylene (HCPE) is a polyethylene product produced by chlorinating polyethylene (PE) to replace some of the hydrogen atoms in its molecular chain with chlorine atoms. The chlorine content is high, and the chlorine atoms are randomly distributed. HCP exhibits excellent weathering, ozone, and aging resistance, as well as good corrosion resistance, and has broad application prospects in the chemical and metallurgical industries.

[0003] Highly chlorinated polyethylene (CPE) coatings offer excellent corrosion protection for surfaces such as metal, wood, and concrete. They offer excellent adhesion, low cost, and low-temperature curing, making them widely used in the coatings industry. However, their heat resistance is limited, typically not exceeding 60°C, limiting their application.

[0004] Patent application CN107629564A discloses a highly chlorinated polyethylene anticorrosive coating. The coating is prepared by mixing highly chlorinated polyethylene, propylene glycol diacetate, titanium dioxide, an anti-rust pigment, a solvent, talc, and additives, stirring under high pressure, grinding, and packaging. This patent application primarily relies on the anticorrosive properties of highly chlorinated polyethylene. The resulting coating's anticorrosive properties still require significant improvement, and its heat resistance is average.

[0005] Patent application CN114213911A discloses a high-efficiency carbon nanotube anticorrosive coating composed of highly chlorinated polyethylene resin, organic bentonite, carbon nanotubes, an organic solvent, an organosilica sol, a defoamer, a dispersant, a curing agent, a film-forming aid, a diluent, silver powder, a plasticizer, and deionized water. This patent application primarily utilizes carbon nanotubes to improve the coating's heat resistance. However, the carbon nanotubes have poor compatibility within the system and are prone to release and precipitation during long-term storage or use, resulting in reduced or even complete loss of heat resistance.

[0006] How to further improve the anti-corrosion performance of highly chlorinated polyethylene coatings and improve their heat resistance is the current research focus of highly chlorinated polyethylene coatings. Summary of the Invention

[0007] In view of the shortcomings of the prior art, the object of the present invention is to provide a highly chlorinated polyethylene anti-corrosion coating and a preparation method thereof, which has excellent corrosion resistance and heat resistance.

[0008] In order to achieve the above object, the present invention adopts the following technical solutions: A highly chlorinated polyethylene anti-corrosion coating is prepared from the following components, measured in parts by weight: 30-35 parts of highly chlorinated polyethylene resin, 10-15 parts of a plasticizer, 2-3 parts of a coupling agent, 2-15 parts of an organic pigment, 10-15 parts of a polyethylene grafted nanomaterial, 4-5 parts of polyvinyl chloride microspheres, 1-2 parts of a dispersant, 1.5-2 parts of an anti-settling and anti-sagging agent, and 20-30 parts of toluene; wherein the polyethylene grafted nanomaterial is obtained by grafting yttria-zirconium oxide-nitrogen-doped graphene composite nanomaterial onto polyethylene.

[0009] Preferably, the chlorine content of the highly chlorinated polyethylene resin is 65% to 69%, the brand is HE-CT 20, purchased from Weifang Shandao Chemical; the plasticizer is dioctyl phthalate or dibutyl phthalate, the coupling agent is maleic anhydride grafted high-density polyethylene (brand 1040, Exxon), the dispersant is BYK-P 104S, and the anti-settling and anti-sagging agent is polyamide wax 6650.

[0010] Preferably, the polyvinyl chloride microspheres are prepared by the following method: (A) First, vinyl chloride monomer, n-octadecane, alkylphenol polyoxyethylene ether, and azobisisobutyronitrile are stirred and mixed in a mass ratio of 10:1.5-2:0.8-1:0.15-0.2 to obtain a premixed solution A; (B) mixing a sodium chloride aqueous solution having a mass concentration of 1.8% to 2.2% with the oil phase at a volume ratio of 3.5 to 4.5:1 to obtain a premixed solution B; (C) Add 1.5 to 2 times the volume of deionized water to the premixed solution, let it stand for 40 to 50 minutes, heat and stir to react, centrifuge to obtain the precipitate, wash with water, and dry to obtain the product.

[0011] More preferably, in step (A), the stirring condition is: stirring at 400-500 r / min for 20-30 minutes.

[0012] More preferably, in step (B), the stirring condition is: stirring at 3000-4000 r / min for 3-4 minutes.

[0013] More preferably, in step (C), the heating and stirring reaction conditions are: 100-200 r / min and 85-95° C. for 4-5 hours.

[0014] Preferably, the polyethylene grafted nanomaterial is prepared by the following method: (a) First, nitrogen-doped graphene is prepared using graphene oxide and urea solution as raw materials; (b) ultrasonically dispersing the nitrogen-doped graphene in an aqueous solution of yttrium nitrate and zirconium nitrate, subjecting the mixture to a hydrothermal reaction, collecting the precipitate by centrifugation, washing the precipitate with water, and drying the precipitate to obtain a yttrium oxide-zirconium oxide-nitrogen-doped graphene composite nanomaterial; (c) ultrasonically dispersing the yttria-zirconia-nitrogen-doped graphene composite nanomaterial in a 1-1.5% polyvinyl alcohol aqueous solution with a mass concentration of 5-7 times the weight of the yttria-zirconia-nitrogen-doped graphene composite nanomaterial to obtain a nanomaterial dispersion. The nanomaterial dispersion, azobisisobutyronitrile, vinyl chloride, and deionized water are then added to a polymerization reactor for polymerization reaction and post-treatment to obtain the polyethylene grafted nanomaterial.

[0015] Preferably, the specific method of step (a) is: ultrasonically dispersing graphene oxide in water to obtain a graphene oxide dispersion with a concentration of 0.5 to 1 mg / mL, then stirring the graphene oxide dispersion with a 30% to 40% urea solution in a volume ratio of 8 to 10:1, hydrothermally reacting at 160 to 170° C. for 8 to 10 hours, centrifuging the precipitate, washing with water, and drying to obtain nitrogen-doped graphene.

[0016] Preferably, in step (b), the molar ratio of nitrogen-doped graphene to yttrium nitrate and zirconium nitrate contained in the yttrium nitrate and zirconium nitrate aqueous solution is 1:0.3-0.5:0.8-1, and the total concentration of yttrium nitrate and zirconium nitrate contained in the yttrium nitrate and zirconium nitrate aqueous solution is 0.2-0.3 mol / L.

[0017] Preferably, in step (c), the mass ratio of yttria-zirconium oxide-nitrogen-doped graphene composite nanomaterial, azobisisobutyronitrile, vinyl chloride, and deionized water is 0.8-1:0.008-0.01:10:15-20.

[0018] Preferably, in step (c), the polymerization reaction conditions are: stirring the polymerization reaction at 50-60°C until the system pressure is less than 1.5 kg / cm 2 , ending the polymerization reaction.

[0019] Preferably, in step (c), the post-treatment includes: removing unreacted vinyl chloride, discharging, filtering, and drying.

[0020] The preparation method of the aforementioned highly chlorinated polyethylene anti-corrosion coating comprises the following specific steps: (1) First, stir and disperse the formulated amount of high-chlorinated polyethylene resin in 1 / 3 to 1 / 2 of the formulated amount of toluene to obtain a resin material; (2) Stir and disperse the formulated amount of dispersant in the remaining formulated amount of toluene, then add the formulated amount of plasticizer, coupling agent, organic pigment, polyethylene grafted nanomaterial, anti-settling and anti-sagging agent, stir and disperse evenly to obtain a dispersion; (3) Then, the resin material and the formulated amount of polyvinyl chloride microspheres are added to the dispersion material, stirred and mixed to obtain a mixed liquid, pulsed laser treated, dispersed at high speed, and ground to a fineness of ≤30 μm to obtain the anti-corrosion coating.

[0021] Preferably, in steps (1), (2) and (3), the stirring rate is 300 to 500 r / min.

[0022] Preferably, in step (3), the pulse laser treatment conditions are: the laser focus is concentrated on the surface of the mixed liquid, and the laser power density in the action area is 10 5 W / cm 2 , the laser action time is 30s, the wavelength of the pulse laser beam is 1.06μm, the pulse width is 1.0ms, and the pulse frequency is 10Hz.

[0023] Preferably, in step (3), the high-speed dispersion condition is: 20,000 to 25,000 r / min for 20 to 30 minutes.

[0024] Compared with the prior art, the present invention has the following beneficial effects: The present invention provides a highly chlorinated polyethylene anti-corrosion coating and its preparation method. The coating is prepared by mixing highly chlorinated polyethylene resin, a plasticizer, a coupling agent, an organic pigment, a polyethylene-grafted nanomaterial, polyvinyl chloride microspheres, a dispersant, an anti-settling and anti-sagging agent, and toluene. The polyethylene-grafted nanomaterial is obtained by grafting polyethylene onto an yttria-zirconia-nitrogen-doped graphene composite nanomaterial. The resulting coating has excellent corrosion resistance and heat resistance and has promising application prospects.

[0025] During preparation, the formulated amount of highly chlorinated polyethylene resin is first stirred and dispersed in 1 / 3 to 1 / 2 of the formulated amount of toluene to obtain a resin material. The formulated amount of dispersant is then stirred and dispersed in the remaining formulated amount of toluene. The formulated amount of plasticizer, coupling agent, organic pigment, polyethylene grafted nanomaterial, and anti-settling and anti-sagging agent are then added and stirred and dispersed uniformly to obtain a dispersion material. The resin material and the formulated amount of polyvinyl chloride microspheres are then added to the dispersion material and stirred and mixed to obtain a mixed solution. The mixture is then pulsed laser treated, dispersed at high speed, and ground to a fineness of ≤30μm. The polyethylene grafted nanomaterial exhibits good compatibility in the system, ensuring the product's corrosion resistance and heat resistance.

[0026] Pulse laser treatment is beneficial to the full dispersion of various components, improves uniformity, and ensures the corrosion resistance and heat resistance of the product.

[0027] PVC microspheres have a rich pore structure, which helps to improve the heat resistance of the product. The introduction of a small amount of microscopic pore structure helps to evenly mix the system, making the macroscopic coating more dense and improving the corrosion resistance of the product. DETAILED DESCRIPTION

[0028] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0029] In the examples and comparative examples, the chlorine content of the highly chlorinated polyethylene resin is 65% to 69%, with the brand name HE-CT 20, purchased from Weifang Sando Chemical; the plasticizer is dioctyl phthalate; the coupling agent is maleic anhydride grafted high-density polyethylene (brand name 1040, Exxon); the organic pigment is Permanent Orange GP, purchased from Shenzhen Daxing Chemical Co., Ltd.; the dispersant is BYK-P104S; the anti-settling and anti-sagging agent is polyamide wax 6650; and polyvinyl alcohol is brand name 2099.

[0030] Example 1 A highly chlorinated polyethylene anti-corrosion coating is prepared from the following components: 3 kg of highly chlorinated polyethylene resin, 1 kg of plasticizer, 0.2 kg of coupling agent, 0.2 kg of organic pigment, 1 kg of polyethylene grafted nanomaterial, 0.4 kg of polyvinyl chloride microspheres, 0.1 kg of dispersant, 0.15 kg of anti-settling and anti-sagging agent, and 2 kg of toluene; wherein the polyethylene grafted nanomaterial is obtained by grafting yttria-zirconium oxide-nitrogen-doped graphene composite nanomaterial onto polyethylene.

[0031] Wherein, the polyvinyl chloride microspheres are prepared by the following method: (A) First, vinyl chloride monomer, n-octadecane, alkylphenol polyoxyethylene ether, and azobisisobutyronitrile are stirred and mixed in a mass ratio of 10:1.5:0.8:0.15 to obtain a premixed solution A; (B) mixing a 1.8% sodium chloride aqueous solution and the oil phase at a volume ratio of 3.5:1 to obtain a premixed solution B; (C) Add 1.5 times the volume of deionized water to the premixed solution, let it stand for 40 minutes, heat and stir to react, centrifuge to obtain the precipitate, wash with water, and dry to obtain the product.

[0032] In step (A), the stirring condition is: stirring at 400 r / min for 20 minutes.

[0033] In step (B), the stirring condition is: 3000 r / min for 3 minutes.

[0034] In step (C), the heating and stirring reaction conditions are: 100 r / min and 85° C. for 4 hours.

[0035] The polyethylene grafted nanomaterial is prepared by the following method: (a) First, nitrogen-doped graphene is prepared using graphene oxide and urea solution as raw materials; (b) ultrasonically dispersing the nitrogen-doped graphene in an aqueous solution of yttrium nitrate and zirconium nitrate, subjecting the mixture to a hydrothermal reaction, collecting the precipitate by centrifugation, washing the precipitate with water, and drying the precipitate to obtain a yttrium oxide-zirconium oxide-nitrogen-doped graphene composite nanomaterial; (c) The yttria-zirconia-nitrogen-doped graphene composite nanomaterial is ultrasonically dispersed in a 1% polyvinyl alcohol aqueous solution with a mass concentration of 5 times its weight to obtain a nanomaterial dispersion. The nanomaterial dispersion, azobisisobutyronitrile, vinyl chloride, and deionized water are then added to a polymerization kettle for polymerization reaction and post-treatment to obtain the polyethylene grafted nanomaterial.

[0036] The specific method of step (a) is as follows: ultrasonically dispersing graphene oxide in water to obtain a graphene oxide dispersion with a concentration of 0.5 mg / mL, then stirring the graphene oxide dispersion with a 30% urea solution in a volume ratio of 8:1, hydrothermally reacting at 160° C. for 8 hours, centrifuging the precipitate, washing with water, and drying to obtain nitrogen-doped graphene.

[0037] In step (b), the molar ratio of nitrogen-doped graphene to yttrium nitrate and zirconium nitrate contained in the yttrium nitrate and zirconium nitrate aqueous solution is 1:0.3:0.8, and the total concentration of yttrium nitrate and zirconium nitrate contained in the yttrium nitrate and zirconium nitrate aqueous solution is 0.2 mol / L.

[0038] In step (c), the mass ratio of yttria-zirconium oxide-nitrogen-doped graphene composite nanomaterial, azobisisobutyronitrile, vinyl chloride, and deionized water is 0.8:0.008:10:15.

[0039] The polymerization reaction conditions are: stirring the polymerization reaction at 50℃ until the system pressure is less than 1.5kg / cm 2 , ending the polymerization reaction.

[0040] Post-processing includes: removing unreacted vinyl chloride, discharging, filtering and drying.

[0041] The preparation method of the aforementioned highly chlorinated polyethylene anti-corrosion coating comprises the following specific steps: (1) First, stir and disperse the formulated amount of high-chlorinated polyethylene resin in 1 / 3 of the formulated amount of toluene to obtain a resin material; (2) Stir and disperse the formulated amount of dispersant in the remaining formulated amount of toluene, then add the formulated amount of plasticizer, coupling agent, organic pigment, polyethylene grafted nanomaterial, anti-settling and anti-sagging agent, stir and disperse evenly to obtain a dispersion; (3) Then, the resin material and the formulated amount of polyvinyl chloride microspheres are added to the dispersion material, stirred and mixed to obtain a mixed liquid, pulsed laser treated, dispersed at high speed, and ground to a fineness of ≤30 μm to obtain the anti-corrosion coating.

[0042] In steps (1), (2) and (3), the stirring rate is 300 r / min.

[0043] In step (3), the pulse laser treatment conditions are: the laser focus is concentrated on the surface of the mixed liquid, and the laser power density in the action area is 10 5 W / cm 2 , the laser action time is 30s, the wavelength of the pulse laser beam is 1.06μm, the pulse width is 1.0ms, and the pulse frequency is 10Hz.

[0044] In step (3), the high-speed dispersion condition is: 20000r / min high-speed dispersion for 20 minutes.

[0045] Example 2 A highly chlorinated polyethylene anti-corrosion coating is prepared from the following components: 3.5 kg of highly chlorinated polyethylene resin, 1.5 kg of plasticizer, 0.3 kg of coupling agent, 1.5 kg of organic pigment, 1.5 kg of polyethylene grafted nanomaterial, 0.5 kg of polyvinyl chloride microspheres, 0.2 kg of dispersant, 0.2 kg of anti-settling and anti-sagging agent, and 3 kg of toluene; wherein the polyethylene grafted nanomaterial is obtained by grafting yttria-zirconium oxide-nitrogen-doped graphene composite nanomaterial onto polyethylene.

[0046] Wherein, the polyvinyl chloride microspheres are prepared by the following method: (A) Vinyl chloride monomer, n-octadecane, alkylphenol polyoxyethylene ether, and azobisisobutyronitrile are mixed in a mass ratio of 10:2:1:0.2 to obtain a premixed solution A; (B) A 2.2% sodium chloride aqueous solution and the oil phase were mixed and stirred at a volume ratio of 4.5:1 to obtain a premixed solution B; (C) Add 2 times the volume of deionized water to the premixed solution, let it stand for 50 minutes, heat and stir to react, centrifuge to obtain the precipitate, wash with water, and dry to obtain the product.

[0047] In step (A), the stirring condition is: 500 r / min for 30 minutes.

[0048] In step (B), the stirring condition is: 4000 r / min for 4 minutes.

[0049] In step (C), the heating and stirring reaction conditions are: 200 r / min and 95° C. for 5 hours.

[0050] The polyethylene grafted nanomaterial is prepared by the following method: (a) First, nitrogen-doped graphene is prepared using graphene oxide and urea solution as raw materials; (b) ultrasonically dispersing the nitrogen-doped graphene in an aqueous solution of yttrium nitrate and zirconium nitrate, subjecting the mixture to a hydrothermal reaction, collecting the precipitate by centrifugation, washing the precipitate with water, and drying the precipitate to obtain a yttrium oxide-zirconium oxide-nitrogen-doped graphene composite nanomaterial; (c) The yttria-zirconia-nitrogen-doped graphene composite nanomaterial is ultrasonically dispersed in a 1.5% polyvinyl alcohol aqueous solution with a mass concentration of 7 times its weight to obtain a nanomaterial dispersion. The nanomaterial dispersion, azobisisobutyronitrile, vinyl chloride, and deionized water are then added to a polymerization kettle for polymerization reaction and post-treatment to obtain the polyethylene grafted nanomaterial.

[0051] The specific method of step (a) is as follows: ultrasonically dispersing graphene oxide in water to obtain a graphene oxide dispersion with a concentration of 1 mg / mL, then stirring the graphene oxide dispersion and a 40% urea solution in a volume ratio of 10:1, hydrothermally reacting at 170° C. for 10 hours, centrifuging the precipitate, washing with water, and drying to obtain nitrogen-doped graphene.

[0052] In step (b), the molar ratio of nitrogen-doped graphene to yttrium nitrate and zirconium nitrate contained in the yttrium nitrate and zirconium nitrate aqueous solution is 1:0.5:1, and the total concentration of yttrium nitrate and zirconium nitrate contained in the yttrium nitrate and zirconium nitrate aqueous solution is 0.3 mol / L.

[0053] In step (c), the mass ratio of yttria-zirconium oxide-nitrogen-doped graphene composite nanomaterial, azobisisobutyronitrile, vinyl chloride, and deionized water is 1:0.01:10:20.

[0054] The polymerization reaction conditions are: stirring the polymerization reaction at 60℃ until the system pressure is less than 1.5kg / cm 2 , ending the polymerization reaction.

[0055] Post-processing includes: removing unreacted vinyl chloride, discharging, filtering and drying.

[0056] The preparation method of the aforementioned highly chlorinated polyethylene anti-corrosion coating comprises the following specific steps: (1) First, stir and disperse the formulated amount of high-chlorinated polyethylene resin in 1 / 2 formulated amount of toluene to obtain a resin material; (2) Stir and disperse the formulated amount of dispersant in the remaining formulated amount of toluene, then add the formulated amount of plasticizer, coupling agent, organic pigment, polyethylene grafted nanomaterial, anti-settling and anti-sagging agent, stir and disperse evenly to obtain a dispersion; (3) Then, the resin material and the formulated amount of polyvinyl chloride microspheres are added to the dispersion material, stirred and mixed to obtain a mixed liquid, pulsed laser treated, dispersed at high speed, and ground to a fineness of ≤30 μm to obtain the anti-corrosion coating.

[0057] In steps (1), (2) and (3), the stirring rate is 500 r / min.

[0058] In step (3), the pulse laser treatment conditions are: the laser focus is concentrated on the surface of the mixed liquid, and the laser power density in the action area is 10 5 W / cm 2 , the laser action time is 30s, the wavelength of the pulse laser beam is 1.06μm, the pulse width is 1.0ms, and the pulse frequency is 10Hz.

[0059] In step (3), the high-speed dispersion condition is: 25000r / min high-speed dispersion for 30 minutes.

[0060] Example 3 A highly chlorinated polyethylene anti-corrosion coating is prepared from the following components: 3.3 kg of highly chlorinated polyethylene resin, 1.2 kg of plasticizer, 0.25 kg of coupling agent, 1 kg of organic pigment, 1.2 kg of polyethylene grafted nanomaterial, 0.45 kg of polyvinyl chloride microspheres, 0.15 kg of dispersant, 0.18 kg of anti-settling and anti-sagging agent, and 2.5 kg of toluene; wherein the polyethylene grafted nanomaterial is obtained by grafting yttria-zirconium oxide-nitrogen-doped graphene composite nanomaterial onto polyethylene.

[0061] Wherein, the polyvinyl chloride microspheres are prepared by the following method: (A) First, vinyl chloride monomer, n-octadecane, alkylphenol polyoxyethylene ether, and azobisisobutyronitrile are stirred and mixed in a mass ratio of 10:1.8:0.9:0.18 to obtain a premixed solution A; (B) Mixing a 2% sodium chloride aqueous solution and the oil phase in a volume ratio of 4:1 to obtain a premixed solution B; (C) Add 1.8 times the volume of deionized water to the premixed solution, let it stand for 45 minutes, heat and stir to react, centrifuge to obtain the precipitate, wash with water, and dry to obtain the product.

[0062] In step (A), the stirring condition is: 500 r / min for 25 minutes.

[0063] In step (B), the stirring condition is: 3500 r / min for 3 minutes.

[0064] In step (C), the heating and stirring reaction conditions are: 200 r / min and 90° C. for 4.5 hours.

[0065] The polyethylene grafted nanomaterial is prepared by the following method: (a) First, nitrogen-doped graphene is prepared using graphene oxide and urea solution as raw materials; (b) ultrasonically dispersing the nitrogen-doped graphene in an aqueous solution of yttrium nitrate and zirconium nitrate, subjecting the mixture to a hydrothermal reaction, collecting the precipitate by centrifugation, washing the precipitate with water, and drying the precipitate to obtain a yttrium oxide-zirconium oxide-nitrogen-doped graphene composite nanomaterial; (c) The yttria-zirconia-nitrogen-doped graphene composite nanomaterial is ultrasonically dispersed in a 1.2% polyvinyl alcohol aqueous solution with a mass concentration of 6 times its weight to obtain a nanomaterial dispersion. The nanomaterial dispersion, azobisisobutyronitrile, vinyl chloride, and deionized water are then added to a polymerization kettle for polymerization reaction and post-treatment to obtain the polyethylene grafted nanomaterial.

[0066] The specific method of step (a) is as follows: ultrasonically dispersing graphene oxide in water to obtain a graphene oxide dispersion with a concentration of 0.8 mg / mL, then stirring the graphene oxide dispersion with a 35% urea solution in a volume ratio of 9:1, hydrothermally reacting at 165° C. for 9 hours, centrifuging the precipitate, washing with water, and drying to obtain nitrogen-doped graphene.

[0067] In step (b), the molar ratio of nitrogen-doped graphene to yttrium nitrate and zirconium nitrate contained in the yttrium nitrate and zirconium nitrate aqueous solution is 1:0.4:0.9, and the total concentration of yttrium nitrate and zirconium nitrate contained in the yttrium nitrate and zirconium nitrate aqueous solution is 0.2 mol / L.

[0068] In step (c), the mass ratio of yttria-zirconium oxide-nitrogen-doped graphene composite nanomaterial, azobisisobutyronitrile, vinyl chloride, and deionized water is 0.9:0.009:10:18.

[0069] The polymerization reaction conditions are: stirring the polymerization reaction at 55℃ until the system pressure is less than 1.5kg / cm 2 , ending the polymerization reaction.

[0070] Post-processing includes: removing unreacted vinyl chloride, discharging, filtering and drying.

[0071] The preparation method of the aforementioned highly chlorinated polyethylene anti-corrosion coating comprises the following specific steps: (1) First, stir and disperse the formulated amount of high-chlorinated polyethylene resin in 1 / 3 of the formulated amount of toluene to obtain a resin material; (2) Stir and disperse the formulated amount of dispersant in the remaining formulated amount of toluene, then add the formulated amount of plasticizer, coupling agent, organic pigment, polyethylene grafted nanomaterial, anti-settling and anti-sagging agent, stir and disperse evenly to obtain a dispersion; (3) Then, the resin material and the formulated amount of polyvinyl chloride microspheres are added to the dispersion material, stirred and mixed to obtain a mixed liquid, pulsed laser treated, dispersed at high speed, and ground to a fineness of ≤30 μm to obtain the anti-corrosion coating.

[0072] In steps (1), (2) and (3), the stirring rate is 400 r / min.

[0073] In step (3), the pulse laser treatment conditions are: the laser focus is concentrated on the surface of the mixed liquid, and the laser power density in the action area is 10 5 W / cm 2 , the laser action time is 30s, the wavelength of the pulse laser beam is 1.06μm, the pulse width is 1.0ms, and the pulse frequency is 10Hz.

[0074] In step (3), the high-speed dispersion condition is: 22000r / min high-speed dispersion for 25 minutes.

[0075] Comparative Example 1 A highly chlorinated polyethylene anti-corrosion coating is prepared from the following components: 3 kg of highly chlorinated polyethylene resin, 1 kg of plasticizer, 0.2 kg of coupling agent, 0.2 kg of organic pigment, 1 kg of polyethylene grafted nanomaterial, 0.1 kg of dispersant, 0.15 kg of anti-settling and anti-sagging agent, and 2 kg of toluene; wherein the polyethylene grafted nanomaterial is obtained by grafting yttria-zirconium oxide-nitrogen-doped graphene composite nanomaterial onto polyethylene.

[0076] Wherein, the polyethylene grafted nanomaterial is prepared by the following method: (a) First, nitrogen-doped graphene is prepared using graphene oxide and urea solution as raw materials; (b) ultrasonically dispersing the nitrogen-doped graphene in an aqueous solution of yttrium nitrate and zirconium nitrate, subjecting the mixture to a hydrothermal reaction, collecting the precipitate by centrifugation, washing the precipitate with water, and drying the precipitate to obtain a yttrium oxide-zirconium oxide-nitrogen-doped graphene composite nanomaterial; (c) The yttria-zirconia-nitrogen-doped graphene composite nanomaterial is ultrasonically dispersed in a 1% polyvinyl alcohol aqueous solution with a mass concentration of 5 times its weight to obtain a nanomaterial dispersion. The nanomaterial dispersion, azobisisobutyronitrile, vinyl chloride, and deionized water are then added to a polymerization kettle for polymerization reaction and post-treatment to obtain the polyethylene grafted nanomaterial.

[0077] The specific method of step (a) is as follows: ultrasonically dispersing graphene oxide in water to obtain a graphene oxide dispersion with a concentration of 0.5 mg / mL, then stirring the graphene oxide dispersion with a 30% urea solution in a volume ratio of 8:1, hydrothermally reacting at 160° C. for 8 hours, centrifuging the precipitate, washing with water, and drying to obtain nitrogen-doped graphene.

[0078] In step (b), the molar ratio of nitrogen-doped graphene to yttrium nitrate and zirconium nitrate contained in the yttrium nitrate and zirconium nitrate aqueous solution is 1:0.3:0.8, and the total concentration of yttrium nitrate and zirconium nitrate contained in the yttrium nitrate and zirconium nitrate aqueous solution is 0.2 mol / L.

[0079] In step (c), the mass ratio of yttria-zirconium oxide-nitrogen-doped graphene composite nanomaterial, azobisisobutyronitrile, vinyl chloride, and deionized water is 0.8:0.008:10:15.

[0080] The polymerization reaction conditions are: stirring the polymerization reaction at 50℃ until the system pressure is less than 1.5kg / cm 2 , ending the polymerization reaction.

[0081] Post-processing includes: removing unreacted vinyl chloride, discharging, filtering and drying.

[0082] The preparation method of the aforementioned highly chlorinated polyethylene anti-corrosion coating comprises the following specific steps: (1) First, stir and disperse the formulated amount of high-chlorinated polyethylene resin in 1 / 3 of the formulated amount of toluene to obtain a resin material; (2) Stir and disperse the formulated amount of dispersant in the remaining formulated amount of toluene, then add the formulated amount of plasticizer, coupling agent, organic pigment, polyethylene grafted nanomaterial, anti-settling and anti-sagging agent, stir and disperse evenly to obtain a dispersion; (3) Then, the resin material is added to the dispersion material, stirred and mixed to obtain a mixed solution, pulsed laser treated, dispersed at high speed, and ground to a fineness of ≤30 μm to obtain the anti-corrosion coating.

[0083] In steps (1), (2) and (3), the stirring rate is 300 r / min.

[0084] In step (3), the pulse laser treatment conditions are: the laser focus is concentrated on the surface of the mixed liquid, and the laser power density in the action area is 10 5 W / cm 2 , the laser action time is 30s, the wavelength of the pulse laser beam is 1.06μm, the pulse width is 1.0ms, and the pulse frequency is 10Hz.

[0085] In step (3), the high-speed dispersion condition is: 20000r / min high-speed dispersion for 20 minutes.

[0086] Comparative Example 2 A highly chlorinated polyethylene anti-corrosion coating is prepared from the following components: 3 kg of highly chlorinated polyethylene resin, 1 kg of plasticizer, 0.2 kg of coupling agent, 0.2 kg of organic pigment, 0.4 kg of polyvinyl chloride microspheres, 0.1 kg of dispersant, 0.15 kg of anti-settling and anti-sagging agent, and 2 kg of toluene; wherein the polyethylene-grafted nanomaterial is obtained by grafting yttria-zirconia-nitrogen-doped graphene composite nanomaterial onto polyethylene.

[0087] Wherein, the polyvinyl chloride microspheres are prepared by the following method: (A) First, vinyl chloride monomer, n-octadecane, alkylphenol polyoxyethylene ether, and azobisisobutyronitrile are stirred and mixed in a mass ratio of 10:1.5:0.8:0.15 to obtain a premixed solution A; (B) mixing a 1.8% sodium chloride aqueous solution and the oil phase at a volume ratio of 3.5:1 to obtain a premixed solution B; (C) Add 1.5 times the volume of deionized water to the premixed solution, let it stand for 40 minutes, heat and stir to react, centrifuge to obtain the precipitate, wash with water, and dry to obtain the product.

[0088] In step (A), the stirring condition is: 400 r / min for 20 minutes.

[0089] In step (B), the stirring condition is: 3000 r / min for 3 minutes.

[0090] In step (C), the heating and stirring reaction conditions are: 100 r / min and 85° C. for 4 hours.

[0091] The preparation method of the aforementioned highly chlorinated polyethylene anti-corrosion coating comprises the following specific steps: (1) First, stir and disperse the formulated amount of high-chlorinated polyethylene resin in 1 / 3 of the formulated amount of toluene to obtain a resin material; (2) Stir and disperse the formulated amount of dispersant in the remaining formulated amount of toluene, then add the formulated amount of plasticizer, coupling agent, organic pigment, anti-settling and anti-sagging agent, stir and disperse evenly to obtain a dispersion; (3) Then, the resin material and the formulated amount of polyvinyl chloride microspheres are added to the dispersion material, stirred and mixed to obtain a mixed liquid, pulsed laser treated, dispersed at high speed, and ground to a fineness of ≤30 μm to obtain the anti-corrosion coating.

[0092] In steps (1), (2) and (3), the stirring rate is 300 r / min.

[0093] In step (3), the pulse laser treatment conditions are: the laser focus is concentrated on the surface of the mixed liquid, and the laser power density in the action area is 10 5 W / cm 2 , the laser action time is 30s, the wavelength of the pulse laser beam is 1.06μm, the pulse width is 1.0ms, and the pulse frequency is 10Hz.

[0094] In step (3), the high-speed dispersion condition is: 20000r / min high-speed dispersion for 20 minutes.

[0095] Comparative Example 3 A highly chlorinated polyethylene anti-corrosion coating is prepared from the following components: 3 kg of highly chlorinated polyethylene resin, 1 kg of plasticizer, 0.2 kg of coupling agent, 0.2 kg of organic pigment, 1 kg of polyethylene grafted nanomaterial, 0.4 kg of polyvinyl chloride microspheres, 0.1 kg of dispersant, 0.15 kg of anti-settling and anti-sagging agent, and 2 kg of toluene; wherein the polyethylene grafted nanomaterial is obtained by grafting yttria-zirconium oxide-nitrogen-doped graphene composite nanomaterial onto polyethylene.

[0096] Wherein, the polyvinyl chloride microspheres are prepared by the following method: (A) First, vinyl chloride monomer, n-octadecane, alkylphenol polyoxyethylene ether, and azobisisobutyronitrile are stirred and mixed in a mass ratio of 10:1.5:0.8:0.15 to obtain a premixed solution A; (B) mixing a 1.8% sodium chloride aqueous solution and the oil phase at a volume ratio of 3.5:1 to obtain a premixed solution B; (C) Add 1.5 times the volume of deionized water to the premixed solution, let it stand for 40 minutes, heat and stir to react, centrifuge to obtain the precipitate, wash with water, and dry to obtain the product.

[0097] In step (A), the stirring condition is: 400 r / min for 20 minutes.

[0098] In step (B), the stirring condition is: 3000 r / min for 3 minutes.

[0099] In step (C), the heating and stirring reaction conditions are: 100 r / min and 85° C. for 4 hours.

[0100] The polyethylene grafted nanomaterial is prepared by the following method: (a) First, nitrogen-doped graphene is prepared using graphene oxide and urea solution as raw materials; (b) ultrasonically dispersing the nitrogen-doped graphene in an aqueous solution of yttrium nitrate and zirconium nitrate, subjecting the mixture to a hydrothermal reaction, collecting the precipitate by centrifugation, washing the precipitate with water, and drying the precipitate to obtain a yttrium oxide-zirconium oxide-nitrogen-doped graphene composite nanomaterial; (c) The yttria-zirconia-nitrogen-doped graphene composite nanomaterial is ultrasonically dispersed in a 1% polyvinyl alcohol aqueous solution with a mass concentration of 5 times its weight to obtain a nanomaterial dispersion. The nanomaterial dispersion, azobisisobutyronitrile, vinyl chloride, and deionized water are then added to a polymerization kettle for polymerization reaction and post-treatment to obtain the polyethylene grafted nanomaterial.

[0101] The specific method of step (a) is as follows: ultrasonically dispersing graphene oxide in water to obtain a graphene oxide dispersion with a concentration of 0.5 mg / mL, then stirring the graphene oxide dispersion with a 30% urea solution in a volume ratio of 8:1, hydrothermally reacting at 160° C. for 8 hours, centrifuging the precipitate, washing with water, and drying to obtain nitrogen-doped graphene.

[0102] In step (b), the molar ratio of nitrogen-doped graphene to yttrium nitrate and zirconium nitrate contained in the yttrium nitrate and zirconium nitrate aqueous solution is 1:0.3:0.8, and the total concentration of yttrium nitrate and zirconium nitrate contained in the yttrium nitrate and zirconium nitrate aqueous solution is 0.2 mol / L.

[0103] In step (c), the mass ratio of yttria-zirconium oxide-nitrogen-doped graphene composite nanomaterial, azobisisobutyronitrile, vinyl chloride, and deionized water is 0.8:0.008:10:15.

[0104] The polymerization reaction conditions are: stirring the polymerization reaction at 50℃ until the system pressure is less than 1.5kg / cm 2 , ending the polymerization reaction.

[0105] Post-processing includes: removing unreacted vinyl chloride, discharging, filtering and drying.

[0106] The preparation method of the aforementioned highly chlorinated polyethylene anti-corrosion coating comprises the following specific steps: (1) First, stir and disperse the formulated amount of high-chlorinated polyethylene resin in 1 / 3 of the formulated amount of toluene to obtain a resin material; (2) Stir and disperse the formulated amount of dispersant in the remaining formulated amount of toluene, then add the formulated amount of plasticizer, coupling agent, organic pigment, polyethylene grafted nanomaterial, anti-settling and anti-sagging agent, stir and disperse evenly to obtain a dispersion; (3) Then, the resin material and the formulated amount of polyvinyl chloride microspheres are added to the dispersion material, stirred and mixed to obtain a mixed liquid, dispersed at high speed, and ground to a fineness of ≤30 μm to obtain the anti-corrosion coating.

[0107] In steps (1), (2) and (3), the stirring rate is 300 r / min.

[0108] In step (3), the high-speed dispersion condition is: 20000r / min high-speed dispersion for 20 minutes.

[0109] The performance tests of the anticorrosive coatings obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were respectively conducted (sprayed on the surface of steel plates, with a coating thickness of 120 μm after drying), including: 1. Impact resistance: Tested in accordance with GB / T 1732-2020 "Determination of impact resistance of paint films". The results are expressed as the maximum height (cm) at which no cracks, wrinkles or peeling are observed after three tests. 2. Corrosion resistance: Refer to GB / T 1771-2007 "Paints and varnishes - Determination of resistance to neutral salt spray" for testing, the test time is 1000h; 3. Heat resistance: Refer to GB / T 1735-2009 "Paints and varnishes - Determination of heat resistance" and place in an environment of 180°C for 72 hours.

[0110] The test results are shown in Table 1.

[0111] Table 1 Anticorrosion coating performance test

[0112] As can be seen from Table 1, the anti-corrosion coatings obtained in Examples 1 to 3 have excellent impact resistance, corrosion resistance and heat resistance.

[0113] In Comparative Example 1, polyvinyl chloride microspheres were omitted, in Comparative Example 2, polyethylene grafted nanomaterials were omitted, and in Comparative Example 3, pulsed laser treatment was omitted during preparation. All properties of the coatings deteriorated significantly, indicating that polyvinyl chloride microspheres, polyethylene grafted nanomaterials, etc. synergistically improved the coating performance, and appropriate pulsed laser treatment was conducive to further improvement of the coating performance.

[0114] While the present invention is illustrated by the aforementioned embodiments, the present invention is not limited to these embodiments, nor does it necessarily rely on these embodiments for implementation. Those skilled in the art will appreciate that any improvements to the present invention, equivalent replacements for individual raw materials in the present invention, additions of auxiliary ingredients, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

Claims

1. A highly chlorinated polyethylene anti-corrosion coating, characterized in that: The invention is prepared from the following components in parts by weight: 30-35 parts of highly chlorinated polyethylene resin, 10-15 parts of plasticizer, 2-3 parts of coupling agent, 2-15 parts of organic pigment, 10-15 parts of polyethylene grafted nanomaterial, 4-5 parts of polyvinyl chloride microspheres, 1-2 parts of dispersant, 1.5-2 parts of anti-settling and anti-sagging agent, and 20-30 parts of toluene; wherein the polyethylene grafted nanomaterial is obtained by grafting yttria-zirconia-nitrogen-doped graphene composite nanomaterial onto polyethylene.

2. A highly chlorinated polyethylene anticorrosive coating according to claim 1, characterized in that: The polyvinyl chloride microspheres are prepared by the following method: (A) First, vinyl chloride monomer, n-octadecane, alkylphenol polyoxyethylene ether, and azobisisobutyronitrile are stirred and mixed in a mass ratio of 10:1.5-2:0.8-1:0.15-0.2 to obtain a premixed solution A; (B) mixing a sodium chloride aqueous solution having a mass concentration of 1.8% to 2.2% with the oil phase at a volume ratio of 3.5 to 4.5:1 to obtain a premixed solution B; (C) Add 1.5 to 2 times the volume of deionized water to the premixed solution, let it stand for 40 to 50 minutes, heat and stir to react, centrifuge to obtain the precipitate, wash with water, and dry to obtain the product.

3. A highly chlorinated polyethylene anticorrosive coating according to claim 2, characterized in that: In step (A), the stirring condition is: 400-500 r / min for 20-30 minutes.

4. A highly chlorinated polyethylene anticorrosive coating according to claim 2, characterized in that: In step (B), the stirring condition is: 3000-4000 r / min for 3-4 minutes.

5. A highly chlorinated polyethylene anticorrosive coating according to claim 2, characterized in that: In step (C), the heating and stirring reaction conditions are: 100-200 r / min and 85-95° C. for 4-5 hours.

6. A highly chlorinated polyethylene anticorrosive coating according to claim 1, characterized in that: The polyethylene grafted nanomaterial is prepared by the following method: (a) First, nitrogen-doped graphene is prepared using graphene oxide and urea solution as raw materials; (b) ultrasonically dispersing the nitrogen-doped graphene in an aqueous solution of yttrium nitrate and zirconium nitrate, subjecting the mixture to a hydrothermal reaction, collecting the precipitate by centrifugation, washing the precipitate with water, and drying the precipitate to obtain a yttrium oxide-zirconium oxide-nitrogen-doped graphene composite nanomaterial; (c) ultrasonically dispersing the yttria-zirconia-nitrogen-doped graphene composite nanomaterial in a 1% to 1.5% polyvinyl alcohol aqueous solution having a mass concentration of 5 to 7 times the weight of the yttria-zirconia-nitrogen-doped graphene composite nanomaterial to obtain a nanomaterial dispersion, and then adding the nanomaterial dispersion, azobisisobutyronitrile, vinyl chloride, and deionized water into a polymerization kettle, carrying out polymerization reaction, and post-treatment to obtain the polyethylene grafted nanomaterial.

7. The method for preparing a highly chlorinated polyethylene anticorrosive coating according to any one of claims 1 to 6, characterized in that: The specific steps are as follows: (1) First, stir and disperse the formulated amount of high-chlorinated polyethylene resin in 1 / 3 to 1 / 2 of the formulated amount of toluene to obtain a resin material; (2) Stir and disperse the formulated amount of dispersant in the remaining formulated amount of toluene, then add the formulated amount of plasticizer, coupling agent, organic pigment, polyethylene grafted nanomaterial, anti-settling and anti-sagging agent, stir and disperse evenly to obtain a dispersion; (3) Then, the resin material and the formulated amount of polyvinyl chloride microspheres are added to the dispersion material, stirred and mixed to obtain a mixed liquid, pulsed laser treated, dispersed at high speed, and ground to a fineness of ≤30 μm to obtain the anti-corrosion coating.

8. The preparation method according to claim 7, characterized in that In steps (1), (2) and (3), the stirring rate is 300 to 500 r / min.

9. The preparation method according to claim 7, characterized in that In step (3), the pulse laser treatment conditions are: the laser focus is concentrated on the surface of the mixed liquid, and the laser power density in the action area is 10 5 W / cm 2 , the laser action time is 30s, the wavelength of the pulsed laser beam is 1.06μm, the pulse width is 1.0ms, and the pulse frequency is 10Hz.

10. The preparation method according to claim 7, characterized in that In step (3), the high-speed dispersion condition is: 20000-25000 r / min high-speed dispersion for 20-30 minutes.

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