Long-acting anti-corrosion polyvinyl chloride fluorine-containing minium coating as well as preparation method and application thereof

Abstract

The invention discloses a long-acting anti-corrosion polyvinyl chloride fluorine-containing minium coating as well as a preparation method and application thereof, and belongs to the technical field of coating preparation. The long-acting anti-corrosion polyvinyl chloride fluorine-containing minium coating is prepared from a main agent and a polyurethane curing agent according to the mass ratio of (10 to 12) to (0.9 to 1.3), the main agent is prepared from the following components in parts by weight: 9 to 20 parts of modified polyvinyl chloride resin, 5 to 10 parts of fluorine-containing resin, 5 to 12 parts of acrylic resin, 40 to 50 parts of mixed solvent (prepared from cyclohexanone, dimethylbenzene and butyl acetate in a dosage ratio of 1: 1: 1), 2 to 6 parts of minium, 10 to 20 parts of pigment and filler, 0.15 to 0.28 part of modified weather-resistant agent and 0.05 to 0.15 part of defoaming agent. The coating prepared by the method has excellent corrosion resistance and weather resistance.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of paint preparation, and particularly relates to a long-acting anticorrosive PVC fluorine-containing Danlan paint, a preparation method and application thereof. BACKGROUND

[0002] As a traditional industrial protective material, PVC paint has poor compactness due to the linear structure and lack of cross-linking density, and electrolyte can easily penetrate into the metal substrate interface through the micropores, causing electrochemical corrosion. At the same time, PVC has limited temperature resistance and is prone to thermal aging and oxidative decomposition in high-temperature or strong oxidizing media, resulting in frequent coating brittleness and peeling, which cannot meet the demand of harsh working conditions. The solid content of traditional solvent-based PVC paint is generally less than 20%, which means that the coating film needs to rely on a large amount of organic solvent evaporation to achieve drying and curing. This characteristic directly leads to two consequences: first, defects such as pinholes and sagging are easily formed during solvent evaporation, further weakening the shielding function of the coating; second, high VOC content not only aggravates environmental pollution and harms the health of operators, but also increases the comprehensive application cost due to the high cost of solvents, so traditional PVC paint has been withdrawn from the market.

[0003] Patent CN119432215A discloses a functionalized graphene modified polyurethane composite coating and a preparation method. Compared with the traditional labyrinth shielding structure of polyurethane coating, the polyurethane coating added with functionalized graphene can form a more compact film structure through the layer-by-layer stacking of the two-dimensional sheet structure of graphene, thereby increasing the corrosion resistance and mechanical properties of the polyurethane coating. The nanoscale size, high hydrophobicity and conductivity of graphene reduce the corrosion rate of the metal and increase the corrosion resistance and mechanical properties of the coating. Amino pyridine can improve the corrosion current and impedance value of the polyurethane coating film and improve its corrosion resistance. The preparation method of blending makes the polyurethane coating film compatible with the flexible segment of polyurethane, further increasing the mechanical properties of the polyurethane coating. However, there is still room for optimization in terms of corrosion resistance and weather resistance. Although the two-dimensional barrier effect of graphene can block the corrosion medium, the micropore defects of the coating may gradually expose due to uneven dispersion of graphene or insufficient interfacial adhesion in long-term high-salt fog, high-humidity and high-temperature or strong acid and alkali environments, leading to the penetration of corrosion factors. In addition, although amino pyridine improves the electrochemical impedance, its resistance to extreme weather factors such as ultraviolet light and ozone is limited, and the coating is prone to cracking or powdering due to light aging. SUMMARY

[0004] The present application aims to provide a long-acting anticorrosive PVC fluorine-containing Danlan paint, a preparation method and application thereof, which can solve the technical problem of poor weather resistance and corrosion resistance of the coating in the prior art.

[0005] To achieve the above object, the present application adopts the following technical solutions: The present application provides a long-acting anticorrosive polyvinyl chloride fluorine-containing lustrous paint, which is composed of a main agent and a polyurethane curing agent with a mass ratio of (10-12):(0.9-1.3). The main agent is composed of the following components in parts by weight: 9-20 parts of modified polyvinyl chloride resin, 5-10 parts of fluorine-containing resin, 5-12 parts of acrylic resin, 40-50 parts of mixed solvent (composed of cyclohexanone, dimethylbenzene and butyl acetate with a use ratio of 1:1:1), 2-6 parts of lustrous paint, 10-20 parts of color filler, 0.15-0.28 parts of modified weathering agent, and 0.05-0.15 parts of defoaming agent.

[0006] As a preferred, the preparation method of the fluorine-containing resin comprises the following steps: Q1: octamethylcyclotetrasiloxane, 1,1,3,3-tetramethyldisiloxane and Karstedt catalyst are added to a container containing toluene, after nitrogen is introduced, magnetic stirring, temperature rising reflux reaction, temperature is lowered to room temperature, filtration, calcium carbonate is added for room temperature stirring, then filtration, vacuum drying, to obtain organic matter 1; Q2: organic matter 1, 4-hydroxystyrene, toluene and Karstedt catalyst are added to a container, reflux reaction under nitrogen environment, filtration, vacuum drying, to obtain organic matter 2; Q3: organic matter 2, diphenylmethane diisocyanate and dibutyltin dilaurate are added to a container containing acetone, after heating reaction, tridecafluoro-1-octanol is added to the container, continue heating reaction, after the reaction is completed, drying, to obtain the fluorine-containing resin.

[0007] In the above process, the synthesis reaction formula of the fluorine-containing resin is as follows:

[0008] As a preferred, in Q1, the use ratio of octamethylcyclotetrasiloxane, 1,1,3,3-tetramethyldisiloxane, Karstedt catalyst and toluene is (5.82-6.04) g:(12.85-14.02) g:(0.52-0.66) g:(18-23) mL, the temperature rising reflux reaction temperature is 108-112℃, the reaction time is 8-12h, and the room temperature stirring time of adding calcium carbonate is 8-10h.

[0009] As a preferred, in Q2, the use ratio of organic matter 1, 4-hydroxystyrene, toluene and Karstedt catalyst is (7.02-7.51) g:(1.18-1.52) g:(35-45) mL:(0.03-0.07) g, and the reflux reaction time is 20-24h.

[0010] As preferred, the molar ratio of the organic matter 2, diphenylmethane diisocyanate and tridecafluoro-1-octanol in the Q3 is (0.8-1.2):(1.9-2.2):(1.8-2.2), the heating reaction temperature is 50-60℃, the reaction time is 2-3h, the continued heating reaction temperature is 55-60℃, and the reaction time is 6-8h.

[0011] As preferred, the preparation method of the modified weathering agent comprises the following steps: S1: 5-chloro-2-hydroxyacetophenone and N-tert-butoxycarbonyl-4-piperidone are added to a container containing methanol, then tetrahydro-pyrrole is added, and the reaction is heated to reflux, after the reaction is completed, vacuum distillation, extraction, purification are performed to obtain intermediate 1; intermediate 1 is added to a container containing ethyl acetate, concentrated hydrochloric acid is added at room temperature, and the reaction is performed, after the reaction is completed, extraction, vacuum distillation are performed to obtain intermediate 2; S2: intermediate 2 and anhydrous potassium carbonate are added to a container containing N,N-dimethylformamide, then epoxy bromopropane is added, and the reaction is stirred, extracted, washed, dried, vacuum distilled, and purified to obtain intermediate 3; S3: intermediate 3 and 1-(4-pyridyl)piperazine are added to a container containing isopropyl alcohol, then potassium carbonate is added, and the reaction is condensed to reflux, extracted, dried, vacuum distilled, and purified to obtain the modified weathering agent.

[0012] In the above process, the synthesis reaction formula of the modified weathering agent is as follows:

[0013] The mass spectrometry analysis result of intermediate 1 is: m / z: 351.12 (100.0%), 353.12 (32.0%), 352.13 (19.9%), 354.12 (6.3%), 353.13 (2.7%); the mass spectrometry analysis result of intermediate 2 is: m / z: 251.07 (100.0%), 253.07 (32.0%), 252.07 (14.4%), 254.07 (4.7%), 253.08 (1.4%); the mass spectrometry analysis result of intermediate 3 is: m / z: 307.10 (100.0%), 309.09 (32.0%), 308.10 (17.6%), 310.10 (5.6%), 309.10 (2.1%); and the mass spectrometry analysis result of the modified weathering agent is: m / z: 470.21 (100.0%), 472.21 (33.0%), 471.21 (29.0%), 473.21 (8.9%), 472.22 (3.6%), 474.21 (1.5%).

[0014] As preferred, in the S1, the amount ratio of 5-chloro-2-hydroxyacetophenone, N-tert-butoxycarbonyl-4-piperidone, methanol and tetrahydropyrrole is (5-7.5) g:(5.81-8.25) g:(100-120) mL:(2.08-2.26) g, the reflux reaction time is 8-10 h; the amount ratio of intermediate 1, ethyl acetate and concentrated hydrochloric acid is (4.2-5.6) g:(15-18) mL:(0.8-1.3) g, the reaction time is 2-3 h.

[0015] As preferred, in the S2, the amount ratio of intermediate 2, anhydrous potassium carbonate, N,N-dimethylformamide and epoxy bromopropane is (5-6.2) g:(3.21-3.87) g:(28-35) mL:(2.88-3.12) g, the stirring reaction time is 10-12 h; in the S3, the amount ratio of intermediate 3, 1-(4-pyridyl)piperazine, isopropyl alcohol and potassium carbonate is (0.26-0.48) g:(0.18-0.21) g:(4-6) mL:(0.158-0.165) g, the reflux reaction time is 8-10 h.

[0016] As preferred, the preparation method of the long-acting corrosion-resistant polyvinyl chloride fluorine-containing Dan paint comprises the following steps: Step one: adding modified polyvinyl chloride resin, fluorine-containing resin and acrylic resin into a mixed solvent (composed of cyclohexanone, dimethylbenzene and butyl acetate with an amount ratio of 1:1:1), stirring to obtain a mixed solution; Step two: adding Dan, pigment and defoaming agent into the mixed solution, mixing and stirring, grinding, then adding a modified weathering agent, mixing, filtering to obtain a main agent; Step three: adding a polyurethane curing agent into the main agent, mechanically stirring, then standing and curing to obtain the long-acting corrosion-resistant polyvinyl chloride fluorine-containing Dan paint.

[0017] As preferred, the application of the long-acting corrosion-resistant polyvinyl chloride fluorine-containing Dan paint is applied to the steel structure plant, concrete frame and roof truss in the high-pollution industrial area.

[0018] In summary, due to the adoption of the above technical solutions, the beneficial effects of the present application are: 1. The prepared fluorine-containing resin and modified weathering agent are added into the polyvinyl chloride fluorine-containing Dan paint, which can effectively improve the corrosion resistance and weather resistance of the paint.

[0019] 2. The prepared fluorine-containing resin is added to the polyvinyl chloride fluorine-containing fluorescent paint, which can effectively improve the corrosion resistance and weather resistance of the paint, the fluorine-containing segment in the fluorine-containing resin has low surface energy, can form a dense hydrophobic barrier, effectively block the penetration of water, oxygen and corrosive ions, the organic silicon segment reduces the internal stress of the coating, reduces the microcracks, cooperates with the fluorocarbon chain to form a dense barrier to inhibit the diffusion of corrosion factors, at the same time, the siloxane chain resists UV aging, and the fluorocarbon chain resists photooxidation, so that the paint can resist ultraviolet, ozone and chemical medium degradation, thereby improving the service life.

[0020] 3. The prepared modified weathering agent is added to the polyvinyl chloride fluorine-containing fluorescent paint, which can effectively improve the weather resistance of the paint, the acetophenone structure in the modified weathering agent can absorb ultraviolet rays, and the piperazine and pyridine groups can quench active oxygen free radicals to improve the weather resistance of the paint and inhibit the oxidation aging of the coating. DETAILED DESCRIPTION

[0021] The technical solutions in the embodiments of the present application will be described below in a clear and complete manner. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0022] Embodiment 1: The present embodiment discloses a preparation method of a fluorine-containing resin, comprising the following steps: Q1: 5.93g octamethylcyclotetrasiloxane, 13.17g 1,1,3,3-tetramethyldisiloxane and 0.58g Karstedt catalyst are added to a container containing 20.5mL toluene, after nitrogen is introduced, magnetic stirring, 110℃ warming reflux reaction for 12h, then cooling to room temperature, filtering, adding 0.048g calcium carbonate, stirring at room temperature for 10h, filtering, vacuum drying, obtaining organic matter 1; Q2: 7.26g organic matter 1, 1.35g 4-hydroxystyrene, 40mL toluene and 0.05g Karstedt catalyst are added to a container, refluxed for 24h under nitrogen environment, filtered, vacuum dried, obtaining organic matter 2; Q3: 0.88g organic matter 2, 0.52g diphenylmethane diisocyanate and 0.02g dibutyltin dilaurate are added to a container containing 10mL acetone, heated at 56℃ for 2h, then 0.73g tridecafluoro-1-octanol is added to the container, continue to heat at 60℃ for 8h, after the reaction is completed, dry to obtain a fluorine-containing resin.

[0023] The present embodiment discloses a preparation method of a modified weathering agent, comprising the following steps: S1: 6.25g 5-chloro-2-hydroxyacetophenone and 6.87g N-tert-butoxycarbonyl-4-piperidone were added to a container containing 110mL of methanol, followed by 2.17g of tetrahydropyrrole, heated to reflux for 10h, after the reaction was completed, distilled under reduced pressure, extracted, purified to obtain intermediate 1; 4.9g of intermediate 1 was added to a container containing 16.5mL of ethyl acetate, 0.95g of concentrated hydrochloric acid was added at room temperature, reacted for 2h, after the reaction was completed, extracted, distilled under reduced pressure to obtain intermediate 2; S2: 5.6g of intermediate 2 and 3.54g of anhydrous potassium carbonate were added to a container containing 32mL of N,N-dimethylformamide, followed by 3.01g of epoxy bromopropane, stirred for 12h, extracted, washed, dried, distilled under reduced pressure, purified to obtain intermediate 3; S3: 0.37g of intermediate 3 and 0.19g of 1-(4-pyridyl)piperazine were added to a container containing 5mL of isopropanol, then 0.162g of potassium carbonate was added, condensed to reflux for 10h, extracted, dried, distilled under reduced pressure, purified to obtain a modified weathering agent.

[0024] The present embodiment discloses a long-acting anticorrosive polyvinyl chloride fluorine-containing Danlan paint, which is composed of a main agent and a polyurethane curing agent in a mass ratio of 11:1.1, and the main agent is composed of the following components in parts by weight: 14.5 parts of modified polyvinyl chloride resin, 7.5 parts of fluorine-containing resin, 8.5 parts of acrylic resin, 45 parts of mixed solvent (composed of cyclohexanone, xylene and butyl acetate in a use amount ratio of 1:1:1), 4 parts of Danlan, 15 parts of color filler, 0.23 parts of modified weathering agent and 0.1 part of defoaming agent.

[0025] The present embodiment discloses a preparation method of a long-acting anticorrosive polyvinyl chloride fluorine-containing Danlan paint, which comprises the following steps: Step one: modified polyvinyl chloride resin (modified by ACR-401), fluorine-containing resin and acrylic resin are added to a mixed solvent (composed of cyclohexanone, xylene and butyl acetate in a use amount ratio of 1:1:1), stirred to obtain a mixed solution; Step two: Danlan, color filler and defoaming agent are added to the mixed solution, mixed and stirred, ground, then modified weathering agent is added, mixed, filtered to obtain a main agent; Step three: when used, the polyurethane curing agent is added to the main agent, mechanically stirred, then placed for curing to obtain the long-acting anticorrosive polyvinyl chloride fluorine-containing Danlan paint.

[0026] Embodiment 2: The present embodiment discloses a preparation method of a fluorine-containing resin, which comprises the following steps: Q1: 5.82 g octamethylcyclotetrasiloxane, 12.85 g 1,1,3,3-tetramethyldisiloxane and 0.52 g Karstedt catalyst were added into a container containing 23 mL of toluene, after nitrogen was introduced, magnetic stirring, 110°C temperature was raised to reflux for 12 h, then cooled to room temperature, filtered, 0.048 g calcium carbonate was added, stirred at room temperature for 10 h, then filtered, vacuum dried to obtain organic matter 1; Q2: 7.02 g of organic matter 1, 1.18 g of 4-hydroxystyrene, 35 mL of toluene and 0.07 g of Karstedt catalyst were added into a container, and refluxed for 24 h under nitrogen environment, filtered, vacuum dried to obtain organic matter 2; Q3: 0.7 g of organic matter 2, 0.48 g of diphenylmethane diisocyanate and 0.02 g of dibutyltin dilaurate were added into a container containing 10 mL of acetone, heated at 56°C for 2 h, then 0.66 g of tridecafluoro-1-octanol was added into the container, and heated at 60°C for 8 h, after the reaction was completed, dried to obtain a fluorine-containing resin.

[0027] The embodiment discloses a preparation method of a modified weathering agent, comprising the following steps: S1: 5 g of 5-chloro-2-hydroxyacetophenone and 5.81 g of N-tert-butoxycarbonyl-4-piperidone were added into a container containing 100 mL of methanol, then 2.08 g of tetrahydropyrrole was added, and heated to reflux for 10 h, after the reaction was completed, distilled under reduced pressure, extracted, purified to obtain intermediate 1; 4.2 g of intermediate 1 was added into a container containing 18 mL of ethyl acetate, 0.8 g of concentrated hydrochloric acid was added at room temperature, reacted for 2 h, after the reaction was completed, extracted, distilled under reduced pressure to obtain intermediate 2; S2: 5 g of intermediate 2 and 3.21 g of anhydrous potassium carbonate were added into a container containing 28 mL of N,N-dimethylformamide, then 2.88 g of epoxy bromopropane was added, stirred for 12 h, extracted, washed, dried, distilled under reduced pressure, purified to obtain intermediate 3; S3: 0.26 g of intermediate 3 and 0.21 g of 1-(4-pyridyl)piperazine were added into a container containing 4 mL of isopropyl alcohol, then 0.158 g of potassium carbonate was added, and refluxed for 10 h, extracted, dried, distilled under reduced pressure, purified to obtain a modified weathering agent.

[0028] The embodiment discloses a long-acting anticorrosive polyvinyl chloride fluorine photine paint which is composed of a main agent and a polyurethane curing agent in a mass ratio of 10:1.3, and the main agent is composed of the following components in parts by weight: 20 parts of modified polyvinyl chloride resin, 10 parts of fluorine-containing resin, 12 parts of acrylic resin, 40 parts of mixed solvent (composed of cyclohexanone, dimethylbenzene and butyl acetate in a usage ratio of 1:1:1), 2 parts of photine, 10 parts of color filler, 0.15 parts of modified weather-resistant agent and 0.05 parts of defoaming agent.

[0029] The embodiment discloses a preparation method of a long-acting anticorrosive polyvinyl chloride fluorine photine paint. Step one: the modified polyvinyl chloride resin (modified by ACR-401), the fluorine-containing resin and the acrylic resin are added into the mixed solvent (composed of cyclohexanone, dimethylbenzene and butyl acetate in a usage ratio of 1:1:1) and stirred to obtain a mixed solution; Step two: the photine, the color filler and the defoaming agent are added into the mixed solution and mixed and stirred, then are ground, and then the modified weather-resistant agent is added and mixed and filtered to obtain the main agent; Step three: when in use, the polyurethane curing agent is added into the main agent, and after mechanical stirring, the long-acting anticorrosive polyvinyl chloride fluorine photine paint is obtained after standing and curing.

[0030] The embodiment discloses a preparation method of a fluorine-containing resin, and comprises the following steps. Q1: 6.04g octamethylcyclotetrasiloxane, 14.02g 1,1,3,3-tetramethyldisiloxane and 0.66g Karstedt catalyst are added into a container provided with 18mL toluene, after nitrogen is introduced, magnetic stirring is conducted, after temperature is raised to 110°C and reflux reaction is conducted for 12h, temperature is reduced to room temperature, filtration is conducted, 0.048g calcium carbonate is added and stirring is conducted at room temperature for 10h, then filtration is conducted, and vacuum drying is conducted to obtain organic matter 1; Q2: 7.51g organic matter 1, 1.52g 4-hydroxystyrene, 45mL toluene and 0.03g Karstedt catalyst are added into a container, reflux reaction is conducted for 24h in a nitrogen environment, filtration is conducted, and vacuum drying is conducted to obtain organic matter 2; Q3: 1.05g organic matter 2, 0.55g diphenylmethane diisocyanate and 0.02g dibutyltin dilaurate are added into a container provided with 10mL acetone, heating reaction is conducted at 56°C for 2h, then 0.81g tridecafluoro-1-octanol is added into the container, heating reaction is continuously conducted at 60°C for 8h, after the reaction is completed, drying is conducted to obtain the fluorine-containing resin.

[0031] The embodiment discloses a preparation method of a modified weather-resistant agent, and comprises the following steps. S1: 7.5 g of 5-chloro-2-hydroxyacetophenone and 8.25 g of N-tert-butoxycarbonyl-4-piperidone were added to a container containing 120 mL of methanol, followed by 2.26 g of tetrahydropyrrole, heated to reflux for 10 h, after the reaction was completed, distilled under reduced pressure, extracted, purified to obtain intermediate 1; 5.6 g of intermediate 1 was added to a container containing 15 mL of ethyl acetate, 1.3 g of concentrated hydrochloric acid was added at room temperature, reacted for 2 h, after the reaction was completed, extracted, distilled under reduced pressure to obtain intermediate 2; S2: 6.2 g of intermediate 2 and 3.87 g of anhydrous potassium carbonate were added to a container containing 35 mL of N,N-dimethylformamide, followed by 3.12 g of epoxy bromopropane, stirred for 12 h, extracted, washed, dried, distilled under reduced pressure, purified to obtain intermediate 3; S3: 0.48 g of intermediate 3 and 0.18 g of 1-(4-pyridyl)piperazine were added to a container containing 6 mL of isopropanol, followed by 0.165 g of potassium carbonate, condensed to reflux for 10 h, extracted, dried, distilled under reduced pressure, purified to obtain a modified weathering agent.

[0032] The embodiment discloses a long-acting anticorrosive polyvinyl chloride fluorine-containing danlan paint, which is composed of a main agent and a polyurethane curing agent in a mass ratio of 12:0.9, and the main agent is composed of 9 parts of modified polyvinyl chloride resin, 5 parts of fluorine-containing resin, 5 parts of acrylic resin, 50 parts of mixed solvent (composed of cyclohexanone, dimethylbenzene and butyl acetate in a usage ratio of 1:1:1), 6 parts of danlan, 20 parts of color filler, 0.28 parts of modified weathering agent and 0.15 parts of defoaming agent.

[0033] The embodiment discloses a preparation method of a long-acting anticorrosive polyvinyl chloride fluorine-containing danlan paint. Step one: modified polyvinyl chloride resin (modified by ACR-401), fluorine-containing resin and acrylic resin are added to a mixed solvent (composed of cyclohexanone, dimethylbenzene and butyl acetate in a usage ratio of 1:1:1) to obtain a mixed solution by stirring; Step two: danlan, color filler and defoaming agent are added to the mixed solution, mixed and stirred, and then ground, and then the modified weathering agent is added, mixed, filtered to obtain the main agent; Step three: when used, the polyurethane curing agent is added to the main agent, and after mechanical stirring, the long-acting anticorrosive polyvinyl chloride fluorine-containing danlan paint is obtained after standing and curing.

[0034] The embodiment discloses a preparation method of a fluorine-containing resin, which comprises the following steps: Q1: 5.87 g octamethylcyclotetrasiloxane, 13.01 g 1,1,3,3-tetramethyldisiloxane and 0.55 g Karstedt catalyst were added into a container containing 19 mL of toluene, after nitrogen was introduced, magnetic stirring, 110℃ was warmed to reflux for 12 h, then cooled to room temperature, filtered, 0.048 g of calcium carbonate was added and stirred at room temperature for 10 h, then filtered, vacuum dried to obtain organic matter 1; Q2: 7.18 g of organic matter 1, 1.21 g of 4-hydroxystyrene, 38 mL of toluene and 0.04 g of Karstedt catalyst were added into a container, and refluxed for 24 h under nitrogen environment, filtered, vacuum dried to obtain organic matter 2; Q3: 0.78 g of organic matter 2, 0.49 g of diphenylmethane diisocyanate and 0.02 g of dibutyltin dilaurate were added into a container containing 10 mL of acetone, heated at 56℃ for 2 h, then 0.68 g of tridecafluoro-1-octanol was added into the container, and heated at 60℃ for 8 h, after the reaction was completed, dried to obtain a fluorine-containing resin.

[0035] The embodiment discloses a preparation method of a modified weathering agent, comprising the following steps: S1: 5.5 g of 5-chloro-2-hydroxyacetophenone and 6.21 g of N-tert-butoxycarbonyl-4-piperidone were added into a container containing 105 mL of methanol, then 2.12 g of tetrahydropyrrole was added, heated to reflux for 10 h, after the reaction was completed, distilled under reduced pressure, extracted, purified to obtain intermediate 1; 4.5 g of intermediate 1 was added into a container containing 16 mL of ethyl acetate, 0.9 g of concentrated hydrochloric acid was added at room temperature, reacted for 2 h, after the reaction was completed, extracted, distilled under reduced pressure to obtain intermediate 2; S2: 5.2 g of intermediate 2 and 3.41 g of anhydrous potassium carbonate were added into a container containing 29 mL of N,N-dimethylformamide, then 2.91 g of epoxy bromopropane was added, stirred for 12 h, extracted, washed, dried, distilled under reduced pressure, purified to obtain intermediate 3; S3: 0.31 g of intermediate 3 and 0.2 g of 1-(4-pyridyl)piperazine were added into a container containing 4.5 mL of isopropanol, then 0.159 g of potassium carbonate was added, condensed to reflux for 10 h, extracted, dried, distilled under reduced pressure, purified to obtain a modified weathering agent.

[0036] The embodiment discloses a long-acting anticorrosive polyvinyl chloride fluorine photine paint which is composed of a main agent and a polyurethane curing agent in a mass ratio of 10.5:1, and the main agent is composed of the following components in parts by weight: 12 parts of modified polyvinyl chloride resin, 8 parts of fluorine-containing resin, 8 parts of acrylic resin, 42 parts of mixed solvent (composed of cyclohexanone, dimethylbenzene and butyl acetate in a usage ratio of 1:1:1), 4 parts of photine, 12 parts of color filler, 0.18 parts of modified weather-resistant agent and 0.08 parts of defoaming agent.

[0037] The embodiment discloses a preparation method of a long-acting anticorrosive polyvinyl chloride fluorine photine paint. Step one: the modified polyvinyl chloride resin (modified by ACR-401), the fluorine-containing resin and the acrylic resin are added into the mixed solvent (composed of cyclohexanone, dimethylbenzene and butyl acetate in a usage ratio of 1:1:1) and stirred to obtain a mixed solution; Step two: the photine, the color filler and the defoaming agent are added into the mixed solution and mixed and stirred, then grinded, and then the modified weather-resistant agent is added and mixed and filtered to obtain the main agent; Step three: when in use, the polyurethane curing agent is added into the main agent, mechanically stirred, then placed and aged to obtain the long-acting anticorrosive polyvinyl chloride fluorine photine paint.

[0038] The embodiment discloses a preparation method of a fluorine-containing resin, which comprises the following steps. Q1: 5.99g of octamethylcyclotetrasiloxane, 12.97g of 1,1,3,3-tetramethyldisiloxane and 0.61g of Karstedt catalyst are added into a container provided with 21mL of toluene, after nitrogen is introduced, magnetic stirring is conducted, after temperature is raised to 110 DEG C and reflux reaction is conducted for 12h, temperature is reduced to room temperature, filtration is conducted, 0.048g of calcium carbonate is added and stirring is conducted at room temperature for 10h, then filtration is conducted and vacuum drying is conducted to obtain organic matter 1; Q2: 7.43g of organic matter 1, 1.47g of 4-hydroxystyrene, 42mL of toluene and 0.06g of Karstedt catalyst are added into a container, reflux reaction is conducted for 24h under a nitrogen environment, filtration is conducted and vacuum drying is conducted to obtain organic matter 2; Q3: 0.93g of organic matter 2, 0.54g of diphenylmethane diisocyanate and 0.02g of dibutyltin dilaurate are added into a container provided with 10mL of acetone, heating reaction is conducted at 56 DEG C for 2h, then 0.78g of tridecafluoro-1-octanol is added into the container, heating reaction is continuously conducted at 60 DEG C for 8h, after reaction is completed, drying is conducted to obtain the fluorine-containing resin.

[0039] The embodiment discloses a preparation method of a modified weather-resistant agent, which comprises the following steps. S1: 6.5g 5-chloro-2-hydroxyacetophenone and 7.93g N-tert-butoxycarbonyl-4-piperidone were added to a container containing 115mL of methanol, followed by 2.21g of tetrahydro-pyrrole, heated to reflux for 10h, after the reaction was completed, distilled under reduced pressure, extracted, purified to obtain intermediate 1; 5.2g of intermediate 1 was added to a container containing 17mL of ethyl acetate, 1.2g of concentrated hydrochloric acid was added at room temperature, reacted for 2h, after the reaction was completed, extracted, distilled under reduced pressure to obtain intermediate 2; S2: 6.1g of intermediate 2 and 3.68g of anhydrous potassium carbonate were added to a container containing 34mL of N,N-dimethylformamide, followed by 3.08g of epoxy bromopropane, stirred for 12h, extracted, washed, dried, distilled under reduced pressure, purified to obtain intermediate 3; S3: 0.47g of intermediate 3 and 0.18g of 1-(4-pyridyl)piperazine were added to a container containing 5.5mL of isopropanol, then 0.163g of potassium carbonate was added, condensed to reflux for 10h, extracted, dried, distilled under reduced pressure, purified to obtain a modified weathering agent.

[0040] The present embodiment discloses a long-acting anticorrosive polyvinyl chloride fluorine Dan coating, which is composed of a main agent and a polyurethane curing agent in a mass ratio of 11.5:1.2, and the main agent is composed of the following components in parts by weight: 18 parts of modified polyvinyl chloride resin, 9 parts of fluorine-containing resin, 10 parts of acrylic resin, 48 parts of mixed solvent (composed of cyclohexanone, xylene and butyl acetate in a use amount ratio of 1:1:1), 5 parts of Dan, 17 parts of pigment and filler, 0.27 parts of modified weathering agent and 0.12 parts of defoaming agent.

[0041] The present embodiment discloses a preparation method of a long-acting anticorrosive polyvinyl chloride fluorine Dan coating, which comprises the following steps: Step one: the modified polyvinyl chloride resin (modified by ACR-401), fluorine-containing resin and acrylic resin are added to the mixed solvent (composed of cyclohexanone, xylene and butyl acetate in a use amount ratio of 1:1:1), stirred to obtain a mixed solution; Step two: Dan, pigment and filler and defoaming agent are added to the mixed solution, mixed and stirred, ground, then the modified weathering agent is added, mixed, filtered to obtain a main agent; Step three: when used, the polyurethane curing agent is added to the main agent, mechanically stirred, then placed for curing to obtain the long-acting anticorrosive polyvinyl chloride fluorine Dan coating.

[0042] Comparative example 1: compared with example 1, no fluorine-containing resin is added in the preparation process of the long-acting anticorrosive polyvinyl chloride fluorine Dan coating, and other conditions are unchanged.

[0043] Comparative Example 2: Comparative Example 2 is compared with Example 1, and Comparative Example 2 does not add a modified weathering agent in the process of preparing long-acting anticorrosive polyvinyl chloride fluorine-containing Danlan paint, and other conditions are unchanged.

[0044] Performance test The long-acting anticorrosive polyvinyl chloride fluorine-containing Danlan paint prepared according to Examples 1-5 and Comparative Examples 1-2 was subjected to performance testing, the corrosion resistance of the sample was tested according to GB / T 10125-2021, the weather resistance of the sample was tested according to GB / T 1865-2009, and the content of volatile organic compounds (VOC) and xylene of the sample was tested according to GB / T 18582-2020. The test results are shown in Table 1: Table 1

[0045] As can be seen from the test results in Table 1, by using the method of Examples 1-5, a paint with excellent weather resistance and corrosion resistance can be prepared. As can be seen from the comparison of Comparative Example 1 and Examples 1-5, the addition of fluorine-containing resin can effectively improve the weather resistance and corrosion resistance of the paint; as can be seen from the comparison of Comparative Example 2 and Examples 1-5, the addition of a modified weathering agent can effectively improve the weather resistance of the paint.

[0046] The above is only a preferred specific embodiment of the present application, but the protection scope of the present application is not limited thereto. Any person skilled in the art can make equivalent replacements or changes to the technical solution and inventive concept of the present application within the technical scope disclosed by the present application, which should be covered within the protection scope of the present application.

[0047] The preferred embodiments of the application disclosed above are only used to help explain the application. The preferred embodiments do not describe all the details, nor limit the application to the specific embodiments. Obviously, many modifications and changes can be made according to the content of the present application. The present application selects and describes these embodiments in order to better explain the principles and practical applications of the present application, so that those skilled in the art can well understand and utilize the present application. The present application is limited only by the claims and their entire scope and equivalents.

Claims

1. A long-lasting anti-corrosion polyvinyl chloride fluorinated fluorite coating, characterized in that, It consists of a main agent and a polyurethane curing agent in a mass ratio of (10-12):(0.9-1.3). The main agent is composed of the following components by weight: 9-20 parts modified polyvinyl chloride resin, 5-10 parts fluorinated resin, 5-12 parts acrylic resin, 40-50 parts mixed solvent (composed of cyclohexanone, xylene and butyl acetate in a ratio of 1:1:1), 2-6 parts red lead, 10-20 parts pigments and fillers, 0.15-0.28 parts modified weathering agent, and 0.05-0.15 parts defoamer.

2. The long-lasting anti-corrosion polyvinyl chloride fluorinated red lead coating according to claim 1, characterized in that, The method for preparing the fluorinated resin includes the following steps: Q1: Octamethylcyclotetrasiloxane, 1,1,3,3-tetramethyldisiloxane and Karstedt catalyst were added to a container containing toluene. After nitrogen was introduced, the mixture was magnetically stirred, heated to reflux, cooled to room temperature, filtered, calcium carbonate was added, stirred at room temperature, filtered, and dried under vacuum to obtain organic compound 1. Q2: Organic compound 1, 4-hydroxystyrene, toluene and Karstedt catalyst were added to a container, refluxed under nitrogen atmosphere, filtered, and dried under vacuum to obtain organic compound 2; Q3: Add organic compound 2, diphenylmethane diisocyanate and dibutyltin dilaurate to a container containing acetone, heat and react, then add tridecafluoro-1-octanol to the container, continue heating and reacting, and after the reaction is complete, dry to obtain a fluorinated resin.

3. The long-lasting anti-corrosion polyvinyl chloride fluorinated fluorite coating according to claim 2, characterized in that, In Q1, the ratio of octamethylcyclotetrasiloxane, 1,1,3,3-tetramethyldisiloxane, Karstedt catalyst and toluene is (5.82-6.04) g : (12.85-14.02) g : (0.52-0.66) g : (18-23) mL.

4. The long-lasting anti-corrosion polyvinyl chloride fluorinated fluorite coating according to claim 2, characterized in that, In Q2, the ratio of organic compound 1,4-hydroxystyrene, toluene and Karstedt catalyst is (7.02-7.51) g : (1.18-1.52) g : (35-45) mL : (0.03-0.07) g.

5. The long-lasting anti-corrosion polyvinyl chloride fluorinated fluorite coating according to claim 2, characterized in that, In Q3, the molar ratio of organic compound 2, diphenylmethane diisocyanate and tridecafluoro-1-octanol is (0.8-1.2):(1.9-2.2):(1.8-2.2).

6. The long-lasting anti-corrosion polyvinyl chloride fluorinated red lead coating according to claim 1, characterized in that, The preparation method of the modified weather-resistant agent includes the following steps: S1: 5-Chloro-2-hydroxyacetophenone and N-tert-butoxycarbonyl-4-piperidinone were added to a container containing methanol, followed by the addition of tetrahydropyrrole. The mixture was heated under reflux. After the reaction was completed, the mixture was extracted and purified by vacuum distillation to obtain intermediate 1. Intermediate 1 was added to a container containing ethyl acetate. Concentrated hydrochloric acid was added at room temperature. The mixture was reacted. After the reaction was completed, the mixture was extracted and distilled under vacuum to obtain intermediate 2. S2: Add intermediate 2 and anhydrous potassium carbonate to a container containing N,N-dimethylformamide, then add epichlorohydrin, stir the reaction, extract, wash, dry, distill under reduced pressure, and purify to obtain intermediate 3. S3: Add intermediate 3 and 1-(4-pyridyl)piperazine to a container containing isopropanol, then add potassium carbonate, reflux the mixture under condensation, extract, dry, distill under reduced pressure, and purify to obtain the modified weathering agent.

7. The long-lasting anti-corrosion polyvinyl chloride fluorinated fluorite coating according to claim 6, characterized in that, In S1, the ratio of 5-chloro-2-hydroxyacetophenone, N-tert-butoxycarbonyl-4-piperidinone, methanol and tetrahydropyrrole is (5-7.5) g : (5.81-8.25) g : (100-120) mL : (2.08-2.26) g; the ratio of intermediate 1, ethyl acetate and concentrated hydrochloric acid is (4.2-5.6) g : (15-18) mL : (0.8-1.3) g.

8. The long-lasting anti-corrosion polyvinyl chloride fluorinated red lead coating according to claim 6, characterized in that, In S2, the ratio of intermediate 2, anhydrous potassium carbonate, N,N-dimethylformamide, and epichlorohydrin is (5-6.2) g: (3.21-3.87) g: (28-35) mL: (2.88-3.12) g; in S3, the ratio of intermediate 3, 1-(4-pyridyl)piperazine, isopropanol, and potassium carbonate is (0.26-0.48) g: (0.18-0.21) g: (4-6) mL: (0.158-0.165) g.

9. A method for preparing a long-lasting anti-corrosion polyvinyl chloride fluorinated fluorite coating as described in any one of claims 1-8, characterized in that, Includes the following steps: Step 1: Add the modified polyvinyl chloride resin, fluorinated resin and acrylic resin to a mixed solvent (composed of cyclohexanone, xylene and butyl acetate in a ratio of 1:1:1), stir to obtain a mixture; Step 2: Add the fluorite, pigments, fillers, and defoamer to the mixture, stir and grind, then add the modified weather-resistant agent, mix, filter, and obtain the main agent; Step 3: When using, add the polyurethane curing agent to the main agent, stir mechanically, and let it stand to mature to obtain a long-lasting anti-corrosion polyvinyl chloride fluorinated red lead coating.

10. The application of a long-lasting anti-corrosion polyvinyl chloride coating containing fluorite, characterized in that, The long-lasting anti-corrosion polyvinyl chloride coating containing fluorite as described in claim 1 is applied to steel structure workshops, concrete frames, and roof trusses in highly polluted industrial areas.

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