A high temperature resistant and anticorrosive polyarylether coating containing phenyl-s-triazine rings and a preparation method thereof

Abstract

The present invention belongs to the technical field of anti-corrosion coatings, and provides a method for preparing a high-temperature resistant anti-corrosion phenyl-s-triazine ring-containing polyarylether coating, using phenyl-s-triazine ring-containing difluoromonomer, dichlorobenzonitrile and biphenyl diphenol as raw materials, and preparing a series of main chain phenyl-s-triazine ring-containing polyarylethers and high-temperature resistant anti-corrosion coatings by solution nucleophilic substitution polycondensation method, replacing silicone coatings, silicone phenolic coatings and glass fiber reinforced plastic coatings, and improving the heat resistance and corrosion resistance of the coating. The high-temperature resistant anti-corrosion coating prepared by the present invention has good heat resistance and high glass transition temperature while maintaining high toughness, high adhesion and high hardness, and is suitable for high-temperature application scenarios above 500°C.

Description

Technical Field

[0001] The invention belongs to the technical field of anti-corrosion coatings, and relates to a high-temperature resistant and anti-corrosion phenyl-s-triazine ring-containing polyarylether coating and a preparation method thereof. Background Art

[0002] With the development of modern industry, a large number of metal materials are used in industry, civil infrastructure, daily life and even national defense construction. However, these metal materials are prone to corrosion and aging in harsh environments such as atmospheric corrosion, seawater corrosion, acid and alkali corrosion, and high temperature corrosion, which affects their service life, reliability and stability. In order to prevent material corrosion or damage, coating protection on the material surface is a better solution.

[0003] As harsh environments place higher demands on the heat resistance and corrosion resistance of protective coatings, many metal materials need to operate for long periods of time in high-temperature environments. Long-term high temperatures will intensify the oxidation reaction between metals and elements such as oxygen, nitrogen, and phosphorus in the air to generate metal oxides that gradually fall off and eventually lead to metal corrosion. At present, the common high-temperature resistant and anti-corrosion coatings on the market are mainly silicone coatings, silicone phenolic coatings, and fiberglass coatings. However, the performance of these traditional coatings is limited in harsh environments such as high temperature, acid and alkali, and the durability needs to be improved, making it difficult to meet the demand for high-performance coatings in harsh environments.

[0004] Therefore, there is an urgent need to develop a new type of high-performance anti-corrosion coating that is resistant to high temperature, corrosion, has good adhesion and strong impact resistance. The development of a high-temperature resistant and high-strength polyarylether coating is a feasible solution. Summary of the invention

[0005] The purpose of the present invention is to overcome the above-mentioned deficiencies of the prior art and to provide a high temperature resistant anti-corrosion coating which can enable metal materials to achieve long-term stability of moisture and heat resistance and anti-corrosion performance in an environment with a temperature of 500°C or above.

[0006] The technical solution of the present invention:

[0007] A high temperature resistant and anticorrosive polyarylether coating containing phenyl-s-triazine rings, wherein the polyarylether resin containing phenyl-s-triazine rings is a polymer, and its structural formula is as follows:

[0008]

[0009] The number average molecular weight of the polyarylether resin containing phenyl-s-triazine rings is 25000-45000.

[0010] A method for preparing a high temperature resistant and anticorrosive phenyl s-triazine ring-containing polyarylether coating, comprising mixing a phenyl s-triazine ring-containing polyarylether resin with an organic solvent, filtering the mixture with a 100-300 mesh filter cloth, and preparing the coating on the surface of a substrate, wherein the mass ratio of the phenyl s-triazine ring-containing polyarylether to the organic solvent is 5-30:95-70;

[0011] In the high temperature resistant and anticorrosive polyarylether coating containing phenyl-s-triazine rings, the polyarylether resin containing phenyl-s-triazine rings is prepared by the following method:

[0012] Under nitrogen protection, 10-90 mole parts of BFPT, 90-10 mole parts of DCBN, 50-150 mole parts of BP, 100-200 mole parts of K2CO3, 200-400 parts of sulfolane and 300-700 parts of toluene are added to a reaction container with mechanical stirring, and the toluene is refluxed with water at 110-140°C for 2-4 hours, and then the temperature is raised to 160-180°C to remove the toluene, and then the reaction is continued at 190-200°C for 3-6 hours, and then diluted with 300-500 parts of sulfolane, precipitated in hot water, boiled in water for 12 hours, and then dried in an oven at 80°C for 24 hours, and then dissolved in an organic solvent, precipitated in anhydrous ethanol, boiled in water for 12 hours, and then dried in an oven at 80°C to obtain a polyarylether resin containing phenyl-s-triazine rings.

[0013] The organic solvent is one or a mixture of two or more of sulfolane, xylene, N-methylpyrrolidone, tetrachloroethane, and N,N-dimethylacetamide.

[0014] The preparation method of the high-temperature resistant and anti-corrosion phenyl s-triazine ring-containing polyarylether coating comprises the following steps: mixing the phenyl s-triazine ring-containing polyarylether resin with a solvent, applying the mixture on the surface of a metal substrate by spraying, brushing or roller coating, drying the mixture on a hot plate at 40-80°C for 2-4 hours, and then heating the mixture at 60-100°C / 30 minutes, 100-140°C / 15 minutes, 130-170°C / 15 minutes, 160-200°C / 20 minutes, 200-240°C / 60 minutes, 260-300°C / 10 minutes, and 280-320°C / 5 minutes to obtain the high-temperature resistant and anti-corrosion coating.

[0015] Beneficial effects of the present invention:

[0016] (1) The present invention synthesizes a novel polyarylether resin containing phenyl-s-triazine rings by introducing triphenyl-s-triazine and benzonitrile structures and prepares a high-temperature resistant anticorrosion coating to replace traditional silicone coatings, silicone phenolic coatings and glass fiber reinforced plastic coatings. The high rigidity of triphenyl-s-triazine gives the material excellent heat resistance, and the cyano group in benzonitrile further enhances the heat resistance and mechanical strength of the material through dipole-dipole action, so that it has good heat resistance while maintaining high toughness, high adhesion and high hardness, and the 5% thermal weight loss temperature is above 500°C, which greatly improves the heat resistance of the coating.

[0017] (2) Compared with traditional silicone coatings, silicone phenolic coatings and fiberglass coatings, the polyarylether coating containing phenyl triazine rings has excellent salt spray corrosion resistance. After 1200 hours of salt spray test, the surface is still intact without peeling or damage, and it can still provide efficient protection for the metal substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 It is the infrared spectrum of the polyarylether resin containing phenyl-s-triazine ring;

[0019] Figure 2 This is the thermal weight loss curve of the high temperature resistant anticorrosion coating containing phenyl-s-triazine ring polyarylether;

[0020] Figure 3 This is a real picture of the salt spray test of the high temperature resistant anticorrosion coating containing phenyl-s-triazine ring polyarylether. DETAILED DESCRIPTION

[0021] The following is combined with Figure 1 and technical solutions to further illustrate the specific implementation methods of the present invention.

[0022] Example 1

[0023] Preparation of polyarylether resin containing phenyl triazine ring: under nitrogen protection, 10 mol parts of BFPT, 90 mol parts of DCBN, 100 mol parts of BP, 120 mol parts of K2CO3, 330 parts of cyclopentane sulfone and 500 parts of toluene were added into a reaction vessel with mechanical stirring, toluene was refluxed with water at 135°C for 2 hours, then the temperature was raised to 160°C to remove toluene, and then the reaction was continued at 190°C for 3-6 hours, and then the mixture was diluted with 400 parts of cyclopentane sulfone, precipitated in hot water, boiled in water for 12 hours, and then dried in an oven at 80°C for 24 hours, and then dissolved in NMP as a solvent, precipitated in anhydrous ethanol, boiled in water for 12 hours, and then dried in an oven at 80°C to obtain polymer 1.

[0024] After mixing 10 parts by mass of polymer 1 with 90 parts by mass of N-methylpyrrolidone (NMP), the mixture was applied to the surface of the metal substrate by a spraying process, dried on a hot plate at 60°C for 3 h, and then heated at a program of 80°C / 30 min, 120°C / 15 min, 150°C / 15 min, 180°C / 20 min, 220°C / 60 min, 280°C / 10 min, and 300°C / 5 min.

[0025] Example 2

[0026] Preparation of polyarylether resin containing phenyl triazine rings: under nitrogen protection, 30 mol parts of BFPT, 70 mol parts of DCBN, 100 mol parts of BP, 120 mol parts of K2CO3, 330 parts of cyclopentane sulfone and 500 parts of toluene were added to a reaction vessel with mechanical stirring, toluene was refluxed with water at 135°C for 2 hours, then the temperature was raised to 160°C to remove toluene, and then the reaction was continued at 190°C for 3-6 hours, and then the mixture was diluted with 400 parts of cyclopentane sulfone, precipitated in hot water, boiled in water for 12 hours, and then dried in an oven at 80°C for 24 hours, and then dissolved in NMP as a solvent, precipitated in anhydrous ethanol, boiled in water for 12 hours, and then dried in an oven at 80°C to obtain polymer 2.

[0027] After mixing 10 parts by mass of polymer 2 with 90 parts by mass of N-methylpyrrolidone (NMP), the mixture was applied to the surface of the metal substrate by a spraying process, dried on a hot plate at 60°C for 3 hours, and then heated at a program of 80°C / 30min, 120°C / 15min, 150°C / 15min, 180°C / 20min, 220°C / 60min, 280°C / 10min, and 300°C / 5min.

[0028] Example 3

[0029] Preparation of polyarylether resin containing phenyl triazine rings: under nitrogen protection, 50 mol parts of BFPT, 50 mol parts of DCBN, 100 mol parts of BP, 120 mol parts of K2CO3, 330 parts of cyclopentane sulfone and 500 parts of toluene were added to a reaction vessel with mechanical stirring, toluene was refluxed with water at 135°C for 2 hours, then the temperature was raised to 160°C to remove the toluene, and then the reaction was continued at 190°C for 3-6 hours, and then the mixture was diluted with 400 parts of cyclopentane sulfone, precipitated in hot water, boiled in water for 12 hours, and then dried in an oven at 80°C for 24 hours, and then dissolved in NMP as a solvent, precipitated in anhydrous ethanol, boiled in water for 12 hours, and then dried in an oven at 80°C to obtain polymer 3.

[0030] After mixing 10 parts by mass of polymer 3 with 90 parts by mass of N-methylpyrrolidone (NMP), the mixture was applied to the surface of the metal substrate by a spraying process, dried on a hot plate at 60°C for 3 h, and then heated at a program of 80°C / 30 min, 120°C / 15 min, 150°C / 15 min, 180°C / 20 min, 220°C / 60 min, 280°C / 10 min, and 300°C / 5 min.

[0031] Example 4

[0032] Preparation of polyarylether resin containing phenyl triazine rings: under nitrogen protection, add 70 mol parts of BFPT, 30 mol parts of DCBN, 100 mol parts of BP, 120 mol parts of K2CO3, 330 parts of cyclopentane sulfone and 500 parts of toluene into a reaction vessel with mechanical stirring, reflux toluene with water at 135°C for 2 hours, then heat to 160°C to remove toluene, react at 190°C for 3-6 hours, dilute with 400 parts of cyclopentane sulfone, precipitate in hot water, boil in water for 12 hours, and dry in an oven at 80°C for 24 hours, then dissolve it with NMP as solvent, precipitate in anhydrous ethanol, boil in water for 12 hours, and dry in an oven at 80°C to obtain polymer 4.

[0033] After mixing 10 parts by mass of polymer 4 with 90 parts by mass of N-methylpyrrolidone (NMP), the mixture was applied to the surface of the metal substrate by a spraying process, dried on a hot plate at 60°C for 3 h, and then heated at a program of 80°C / 30 min, 120°C / 15 min, 150°C / 15 min, 180°C / 20 min, 220°C / 60 min, 280°C / 10 min, and 300°C / 5 min.

[0034] Example 5

[0035] Preparation of polyarylether resin containing phenyl triazine rings: under nitrogen protection, 90 mol parts of BFPT, 10 mol parts of DCBN, 100 mol parts of BP, 120 mol parts of K2CO3, 330 parts of cyclopentane sulfone and 500 parts of toluene were added into a reaction vessel with mechanical stirring, toluene was refluxed with water at 135°C for 2 hours, then the temperature was raised to 160°C to remove toluene, and then the reaction was continued at 190°C for 3-6 hours, and then the mixture was diluted with 400 parts of cyclopentane sulfone, precipitated in hot water, boiled in water for 12 hours, and then dried in an oven at 80°C for 24 hours, and then dissolved in NMP as a solvent, precipitated in anhydrous ethanol, boiled in water for 12 hours, and then dried in an oven at 80°C to obtain polymer 5.

[0036] After mixing 10 parts by mass of polymer 5 with 90 parts by mass of N-methylpyrrolidone (NMP), the mixture was applied to the surface of the metal substrate by a spraying process, dried on a hot plate at 60°C for 3 h, and then heated at a program of 80°C / 30 min, 120°C / 15 min, 150°C / 15 min, 180°C / 20 min, 220°C / 60 min, 280°C / 10 min, and 300°C / 5 min.

[0037] After the high temperature resistant and anticorrosive polyarylether coating containing phenyl-s-triazine rings in the above embodiment was prepared, its adhesion, impact resistance, hardness, bending performance, glass transition temperature (T g ), thermal weight loss temperature (T d5％ ) and solvent wiping resistance were tested, and the results are shown in Table 1:

[0038] Table 1 Summary of properties of high temperature resistant and anticorrosive polyarylether coatings containing phenyl triazine rings

[0039]

[0040] The above-described embodiments are only preferred embodiments for fully illustrating the present invention, and the protection scope of the present invention is not limited thereto. Equivalent substitutions or changes made by those skilled in the art based on the present invention are within the protection scope of the present invention. The protection scope of the present invention shall be subject to the claims.

Claims

1. A method for preparing a high temperature resistant and anticorrosive polyarylether coating containing phenyl-s-triazine rings, characterized in that: The phenyl-s-triazine ring-containing polyarylether resin in the high temperature resistant and anticorrosive phenyl-s-triazine ring-containing polyarylether coating is a polymer, and its structural formula is as follows: The phenyl-s-triazine ring-containing polyarylether resin is prepared by the following method: Under nitrogen protection, 10-90 mole parts of BFPT, 90-10 mole parts of DCBN, 50-150 mole parts of BP, 100-200 mole parts of K2CO3, 200-400 parts of sulfolane and 300-700 parts of toluene are added to a reaction container with mechanical stirring, and the toluene is refluxed with water at 110-140°C for 2-4 hours, and then the temperature is raised to 160-180°C to remove the toluene, and then the reaction is continued at 190-200°C for 3-6 hours, and then diluted with 300-500 parts of sulfolane, precipitated in hot water, boiled in water for 12 hours, and then dried in an oven at 80°C for 24 hours, and then dissolved in an organic solvent, precipitated in anhydrous ethanol, boiled in water for 12 hours, and then dried in an oven at 80°C to obtain a polyarylether resin containing phenyl-s-triazine rings.

2. The preparation method according to claim 1, characterized in that: The number average molecular weight of the polyarylether resin containing phenyl-s-triazine rings is 25000-45000.

3. The preparation method according to claim 1 or 2, characterized in that: The polyarylether resin containing phenyl s-triazine rings is mixed with an organic solvent and filtered with a filter cloth with a mesh size of 100-300 to prepare the polyarylether resin on the surface of a base material, wherein the mass ratio of the polyarylether containing phenyl s-triazine rings to the organic solvent is 5-30:95-70.

4. The preparation method according to claim 3, characterized in that: The preparation method of the high-temperature resistant and anti-corrosion phenyl-s-triazine ring-containing polyarylether coating comprises the following steps: mixing the phenyl-s-triazine ring-containing polyarylether resin with an organic solvent, applying the mixture on the surface of a metal substrate by spraying, brushing or roller coating, drying the mixture on a hot plate at 40-80°C for 2-4 hours, and then heating the mixture at 60-100°C / 30 minutes, 100-140°C / 15 minutes, 130-170°C / 15 minutes, 160-200°C / 20 minutes, 200-240°C / 60 minutes, 260-300°C / 10 minutes and 280-320°C / 5 minutes to obtain the high-temperature resistant and anti-corrosion phenyl-s-triazine ring-containing polyarylether coating.

5. The preparation method according to claim 3, characterized in that: The organic solvent is one or a mixture of two or more of sulfolane, xylene, N-methylpyrrolidone, tetrachloroethane, and N,N-dimethylacetamide.

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