A phase transition protective coating modified with petroleum aromatic resin and its preparation method

Abstract

This invention relates to the field of high-temperature resistant protective coatings, and more particularly to a phase transition protective coating modified with petroleum aromatic resin and its preparation method. The petroleum aromatic resin modified phase transition protective coating of this invention comprises the following components in parts by weight: component A 60.5–114.5 parts, component B 29–43 parts, and curing agent 4–10 parts; component A includes: methylphenyl silicone resin, propylene glycol methyl ether acetate, oleophilic nano-silica, barium sulfate, mica powder, mixed low-melting-point glass powder, α-phase alumina, aluminum fluoride, cerium oxide, ceramic microspheres, boric acid, basalt fiber, thixotropic agent, and leveling agent; component B includes: petroleum aromatic resin, xylene, and maleic anhydride. Through the synergistic effect of the modified petroleum aromatic resin and various high-temperature resistant fillers, this coating can significantly improve its thermal stability under high-temperature conditions, increasing its high-temperature service temperature from 500℃ to over 1000℃.

Description

Technical Field

[0001] This invention relates to the field of high-temperature resistant protective coatings, and in particular to a phase transition protective coating modified with petroleum aromatic resin and its preparation method. Background Technology

[0002] The rapid development of modern energy technologies has significantly improved the heat exchange efficiency of equipment such as waste incinerators, power plant heat exchangers, and steam pipelines, but it has also led to a continuous increase in operating temperatures. However, current mainstream thermal protection coating systems (such as ceramic or glass phase coatings) show significant shortcomings in addressing this challenge: their thermal protection capabilities are insufficient to meet actual engineering requirements, leading to an increased frequency of thermal protection failures, which in turn can cause equipment malfunctions and even safety accidents. These traditional coatings also suffer from inherent defects such as complex preparation processes, stringent high-temperature curing requirements, poor thermal shock resistance, and high costs. In high-temperature applications such as steam pipelines, radiators, boilers in thermal power plants, and waste incinerators, high-temperature resistant coatings not only provide critical protection for equipment but also effectively reduce heat loss and energy consumption, thereby reducing maintenance frequency and greenhouse gas emissions. However, existing coating technologies still face severe challenges: while organic coatings possess excellent mechanical properties and corrosion resistance, they are prone to oxidation and decomposition at high temperatures; while inorganic coatings, although heat-resistant, generally suffer from insufficient flexibility and adhesion. This performance contradiction makes the development of new composite systems that combine the advantages of both organic and inorganic coatings an urgent industry need. Summary of the Invention

[0003] The purpose of this invention is to provide an organic-inorganic composite petroleum aromatic resin modified phase transition protective coating and its preparation method, which has a wide temperature range, high wear resistance, high adhesion, and excellent high temperature resistance and corrosion resistance.

[0004] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0005] This invention provides a phase transition protective coating modified with petroleum aromatic resin, comprising the following components in parts by weight: 60.5-114.5 parts of component A, 29-43 parts of component B, and 4-10 parts of curing agent;

[0006] Component A comprises the following components in parts by weight: 20-30 parts methyl phenyl silicone resin, 10-20 parts propylene glycol methyl ether acetate, 2-5 parts oleophilic nano silica, 4-8 parts barium sulfate, 3-7 parts mica powder, 6-12 parts mixed low-melting-point glass powder, 7.5-12.5 parts α-phase alumina, 0-1 part aluminum fluoride, 1-3 parts cerium oxide, 3-5 parts ceramic microspheres, 0-1 part boric acid, 3-5 parts basalt fiber, 0.5-2.5 parts thixotropic agent, and 0.5-2.5 parts leveling agent;

[0007] Component B comprises the following components in parts by weight: 14-20 parts of petroleum aromatic resin, 14-20 parts of xylene, and 1-3 parts of maleic anhydride.

[0008] Optionally, the curing agent comprises the following components in parts by weight: 2-5 parts of γ-aminopropyltriethoxysilane and 2-5 parts of tetraethoxysilane.

[0009] Optionally, the phenyl content of the methylphenyl organosilicon resin is 15% to 60%; and the particle size of the oleophilic nano-silica is 5 to 25 nm.

[0010] Optionally, the softening temperature of the mixed low-melting-point glass powder is 300–600°C.

[0011] Optionally, the diameter of the α-phase alumina is 2–50 nm; the particle size of the ceramic microspheres is 10–100 μm; and the length of the basalt fiber is 30–100 μm.

[0012] Optionally, the petroleum aromatic resin includes one or more of DCPD cycloaliphatic resin, hydrogenated petroleum resin, C5 aliphatic petroleum resin, C9 aromatic petroleum resin, and condensed polynuclear aromatic resin.

[0013] Optionally, the thixotropic agent includes one or more of organobentonite, sodium-based bentonite, lithium-based bentonite, and fumed silica;

[0014] The leveling agent includes one or more of polydimethylsiloxane, alkyl-modified organosiloxane, polyether polyester-modified organosiloxane, and acrylate.

[0015] This invention also provides a method for preparing the above-mentioned petroleum aromatic resin modified phase transition protective coating, comprising the following steps:

[0016] Barium sulfate, mica powder, mixed low-melting-point glass powder, α-phase alumina, and aluminum fluoride are mixed and ground to obtain a mixed grinding powder. The mixed grinding powder, oleophilic nano-silica, cerium oxide, ceramic microspheres, boric acid, thixotropic agent, and leveling agent are added to a mixed solution of methyl phenyl silicone resin and propylene glycol methyl ether acetate to obtain a filler suspension. Basalt fiber is mixed with the filler suspension to obtain component A.

[0017] Petroleum aromatic resin is mixed with xylene and stirred at 50-80°C for 15-30 minutes to obtain a dissolved petroleum aromatic resin solution. Then maleic anhydride is added and stirred at 90-100°C for 1 hour to obtain component B.

[0018] Component A, component B and curing agent are stirred continuously at 50-80℃ and 100-300 r / min for 15-30 minutes to obtain a phase transition protective coating modified with petroleum aromatic resin.

[0019] The phase transition protective coating modified with petroleum aromatic resin was applied to the surface of the sample, cured, and then calcined to obtain the phase transition protective coating modified with petroleum aromatic resin.

[0020] Optionally, the curing temperature is 15–30°C and the curing time is 4–6 hours.

[0021] Optionally, the calcination temperature is 120–200°C, and the calcination time is 0.5–1 hour; the thickness of the petroleum aromatic resin modified phase transition protective coating is 80–500 μm.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] This invention provides a phase transition protective coating modified with petroleum aromatic resin. Through the synergistic effect of the modified petroleum aromatic resin and various high-temperature resistant fillers, this coating significantly improves its thermal stability under high-temperature conditions, increasing its high-temperature service temperature from 500℃ to over 1000℃. The coating has a simple preparation process, low application requirements, and the high-temperature phase transition occurs naturally during service without prior curing. It also exhibits a wide high-temperature service temperature range and excellent performance.

[0024] The specific advantages of this coating are: (1) After being applied at room temperature, the composite coating has good adhesion to the interface of different materials such as metal, ceramic, and glass, and can ensure good adhesion and integrity of the coating in a wide temperature range from room temperature to 1100℃; (2) The coating combines methyl phenyl silicone resin, petroleum aromatic resin and low melting point glass powder, so that the coating can be cured into a film by silicone resin at room temperature, and the adhesion and integrity of the paint film are maintained by the successive phase transformation of glass phase, ceramic phase and glass carbon phase during the temperature rise. The phase transformation continues during the application process, and no separate high temperature curing process is required; (3) The coating is mixed with low melting point glass powder under high temperature conditions. Before the phase transition, modified petroleum aromatic resin has a certain fluidity, which can automatically fill and repair micropores and microcracks. It can eliminate the internal stress caused by the difference in thermal expansion coefficient between the coating components and the substrate to a certain extent, so that the coating exhibits excellent mechanical properties; (4) Mixed low melting point glass powder and petroleum aromatic resin form glass phase, ceramic phase and glass carbon phase during the heating process, which can significantly reduce the friction coefficient of the coating surface and improve the wear resistance of the coating system; (5) Alumina, aluminum fluoride and nano silica generate mullite fiber and composite basalt fiber under high temperature conditions, which can maintain the integrity, mechanical properties and thermal shock resistance of the coating during the high temperature phase transition process. Attached Figure Description

[0025] Figure 1 This is a schematic diagram of the phase transformation of a high-temperature resistant protective coating modified with petroleum aromatic resin. Detailed Implementation

[0026] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0027] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0028] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0029] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be obvious to those skilled in the art. This application specification and embodiments are merely exemplary.

[0030] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0031] All raw materials used in this invention can be obtained commercially or prepared using existing technologies.

[0032] The room temperature mentioned in the embodiments of the present invention is 25±2℃.

[0033] This invention provides a phase transition protective coating modified with petroleum aromatic resin, comprising the following components in parts by weight: 60.5-114.5 parts of component A, 29-43 parts of component B, and 4-10 parts of curing agent;

[0034] Component A comprises the following components in parts by weight: 20-30 parts methyl phenyl silicone resin, 10-20 parts propylene glycol methyl ether acetate, 2-5 parts oleophilic nano silica, 4-8 parts barium sulfate, 3-7 parts mica powder, 6-12 parts mixed low-melting-point glass powder, 7.5-12.5 parts α-phase alumina, 0-1 part aluminum fluoride, 1-3 parts cerium oxide, 3-5 parts ceramic microspheres, 0-1 part boric acid, 3-5 parts basalt fiber, 0.5-2.5 parts thixotropic agent, and 0.5-2.5 parts leveling agent;

[0035] Component B comprises the following components in parts by weight: 14-20 parts of petroleum aromatic resin, 14-20 parts of xylene, and 1-3 parts of maleic anhydride.

[0036] In this invention, the phase transition protective coating modified with petroleum aromatic resin includes 60.5 to 114.5 parts of component A, for example, 60.5 parts, 78 parts, 80 parts, 83 parts, 88 parts, 100 parts, 110 parts, or 114.5 parts.

[0037] In this invention, the phase transition protective coating modified with petroleum aromatic resin includes 29 to 43 parts of component B, for example, 29 parts, 30 parts, 35 parts, 36 parts, 38 parts, 40 parts, 42 parts, or 44 parts, etc.

[0038] In this invention, the phase transition protective coating modified with petroleum aromatic resin includes 4 to 10 parts of curing agent, for example, 4, 5, 6, 7, 8, 9 or 10 parts.

[0039] In this invention, component A includes 20 to 30 parts of methylphenyl silicone resin, for example, 20 parts, 22 parts, 25 parts, 27 parts or 30 parts; the phenyl content of the methylphenyl silicone resin is 15% to 60%, for example, 15%, 20%, 25%, 30%, 40%, 45%, 50% or 55%.

[0040] In an embodiment of the present invention, the methylphenyl silicone resin is SH-9601 purchased from Hubei Longsheng Sihai New Materials Co., Ltd.

[0041] In this invention, component A includes 10 to 20 parts of propylene glycol methyl ether acetate, for example, 10 parts, 12 parts, 15 parts, 17 parts or 20 parts.

[0042] In this invention, component A includes 2 to 5 parts of oleophilic nano-silica, for example, 2, 3, 4 or 5 parts; the particle size of the oleophilic nano-silica is 5 to 25 nm, preferably 10 to 20 nm, and more preferably 15 to 18 nm.

[0043] In this invention, component A includes 4 to 8 parts of barium sulfate, for example, 4, 5, 6, 7 or 8 parts, etc.

[0044] In this invention, component A includes 3 to 7 parts of mica powder, for example, 3, 4, 5, 6 or 7 parts, etc.

[0045] In this invention, component A comprises 6 to 12 parts of mixed low-melting-point glass powder, for example, 6, 7, 8, 9, 10, 11, or 12 parts; the mixed low-melting-point glass powder is specifically obtained by mixing low-melting-point glass powders with different softening points in the range of 350 to 550°C, and the softening point temperature of the mixed low-melting-point glass powder is 300 to 600°C, for example, 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, or 600°C.

[0046] In this invention, component A comprises 7.5 to 12.5 parts of α-phase alumina, for example, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, 11 parts, 12 parts, or 12.5 parts; the α-phase alumina is spherical powder; the diameter of the α-phase alumina is 2 to 50 nm, preferably 3 to 40 nm, more preferably 5 to 25 nm, and even more preferably 10 to 20 nm.

[0047] In this invention, component A comprises 0 to 1 part of aluminum fluoride, preferably 0.5 to 1 part.

[0048] In this invention, component A includes 1 to 3 parts of cerium oxide, for example, 1 part, 1.5 parts, 2 parts, 2.5 parts, or 3 parts.

[0049] In this invention, component A comprises 3 to 5 parts of ceramic microspheres, for example, 3 parts, 3.5 parts, 4 parts, 4.5 parts, or 5 parts; the ceramic microspheres are aluminosilicate ceramics; the ceramic microspheres may contain one or more of zirconium oxide, silicon carbide, silicon nitride, etc.; the particle size of the ceramic microspheres is 10 to 100 μm, preferably 11 to 90 μm, more preferably 12 to 80 μm, even more preferably 13 to 50 μm, and even more preferably 15 to 40 μm.

[0050] In this invention, component A includes 0 to 1 part of boric acid, preferably 0.5 to 1 part.

[0051] In this invention, component A includes 3 to 5 parts of basalt fiber, for example, 3 parts, 3.5 parts, 4 parts, 4.5 parts, or 5 parts; the length of the basalt fiber is 30 to 100 μm, preferably 35 to 95 μm, more preferably 40 to 90 μm, and even more preferably 50 to 80 μm.

[0052] In this invention, component A includes 0.5 to 2.5 parts of a thixotropic agent, for example, 0.5 parts, 1 part, 1.5 parts, 2 parts, or 2.5 parts; the thixotropic agent includes one or more of organobentonite, sodium-based bentonite, lithium-based bentonite, and fumed silica, preferably organobentonite or sodium-based bentonite.

[0053] In this invention, component A includes 0.5 to 2.5 parts of a leveling agent, for example, 0.5 parts, 1 part, 1.5 parts, 2 parts, or 2.5 parts; the leveling agent includes one or more of polydimethylsiloxane, alkyl-modified organosiloxane, polyether polyester-modified organosiloxane, and acrylate, preferably polydimethylsiloxane or alkyl-modified organosiloxane.

[0054] In this invention, component B comprises 14 to 20 parts of petroleum aromatic resin, for example, 14, 15, 16, 17, 18, 19, or 20 parts; the petroleum aromatic resin comprises one or more of DCPD cycloaliphatic resin, hydrogenated petroleum resin, C5 aliphatic petroleum resin, C9 aromatic petroleum resin, and condensed polynuclear aromatic resin, preferably C9 aromatic petroleum resin.

[0055] The C9 aromatic petroleum resin was purchased from Zibo Ningsong Chemical Co., Ltd.

[0056] Understandably, petroleum aromatic resins, as byproducts of petroleum cracking, offer significant cost reductions for coating raw materials due to their low cost. More importantly, through specific modification treatments, this resin can transform into a glassy carbon phase at high temperatures. This in-situ phase transformation enhances the high-temperature resistance of the coating while maintaining the mechanical integrity of the substrate material. This innovative material system provides a breakthrough direction for developing novel coatings that offer wide-temperature-range protection, long-lasting corrosion resistance, and controllable costs.

[0057] In this invention, component B includes 14 to 20 parts of xylene, for example, 14, 15, 16, 17, 18, 19 or 20 parts.

[0058] In this invention, component B includes 1 to 3 parts of maleic anhydride, for example, 1 part, 1.5 parts, 2 parts, 2.5 parts, or 3 parts.

[0059] In this invention, the curing agent comprises the following components in parts by weight: 2-5 parts of γ-aminopropyltriethoxysilane and 2-5 parts of tetraethoxysilane.

[0060] In this invention, the curing agent includes 2 to 5 parts of γ-aminopropyltriethoxysilane (KH550), for example, 2 parts, 3 parts, 4 parts or 5 parts, etc.

[0061] In this invention, the curing agent includes 2 to 5 parts of tetraethoxysilane, for example, 2 parts, 3 parts, 4 parts or 5 parts, etc.

[0062] In this invention, the coating prepared by combining methylphenyl silicone resin with modified petroleum aromatic resin and high-temperature resistant filler can significantly improve the coating's high-temperature resistance range and the upper limit of its high-temperature service temperature.

[0063] This invention also provides a method for preparing the above-mentioned petroleum aromatic resin modified phase transition protective coating, comprising the following steps:

[0064] Barium sulfate, mica powder, mixed low-melting-point glass powder, α-phase alumina, and aluminum fluoride are mixed and ground to obtain a mixed grinding powder. The mixed grinding powder, oleophilic nano-silica, cerium oxide, ceramic microspheres, boric acid, thixotropic agent, and leveling agent are added to a mixed solution of methyl phenyl silicone resin and propylene glycol methyl ether acetate to obtain a filler suspension. Basalt fiber is mixed with the filler suspension to obtain component A.

[0065] Petroleum aromatic resin is mixed with xylene and stirred at 50-80°C for 15-30 minutes to obtain a dissolved petroleum aromatic resin solution. Then maleic anhydride is added and stirred at 90-100°C for 1 hour to obtain component B.

[0066] Component A, component B and curing agent are stirred continuously at 50-80℃ and 100-300 r / min for 15-30 minutes to obtain a phase transition protective coating modified with petroleum aromatic resin.

[0067] The phase transition protective coating modified with petroleum aromatic resin was applied to the surface of the sample, cured, and then calcined to obtain the phase transition protective coating modified with petroleum aromatic resin.

[0068] In an embodiment of the present invention, the barium sulfate, mica powder, mixed low-melting-point glass powder, α-phase alumina and aluminum fluoride are continuously stirred and mixed evenly at a speed of 100-200 r / min. The mixed powder is then added to a grinder and ground evenly to obtain a mixed ground powder for later use.

[0069] In an embodiment of the present invention, the grinding is carried out in a grinding mill, which can be a wet grinding mill or a dry grinding mill. When using a wet grinding mill, water is mainly used as a solvent, and dispersants such as sodium carboxymethyl cellulose can be added. After grinding, the powder is dehydrated and dried using conventional methods to obtain a dry mixed grinding powder.

[0070] In an embodiment of the present invention, the mixed solution of methylphenyl silicone resin and propylene glycol methyl ether acetate is obtained by adding methylphenyl silicone resin and propylene glycol methyl ether acetate into a container and stirring continuously at a speed of 300-600 r / min for 15-30 minutes at room temperature.

[0071] In an embodiment of the present invention, the mixed solution of the above-mentioned methylphenyl silicone resin and propylene glycol methyl ether acetate is continuously stirred at a speed of 300-600 r / min at room temperature. Then, oleophilic nano-silica, mixed grinding powder, cerium oxide, ceramic microspheres, boric acid, thixotropic agent and leveling agent are slowly added to the mixed solution of methylphenyl silicone resin and propylene glycol methyl ether acetate in sequence, and stirred continuously at a speed of 300-600 r / min at room temperature for 0.5-1 hour to obtain a uniformly mixed filler suspension.

[0072] In an embodiment of the present invention, the stirring speed of the filler suspension is adjusted to 100-200 r / min, basalt fiber is slowly added and stirred continuously at room temperature for 15-30 minutes to obtain component A of the coating solution.

[0073] In an embodiment of the present invention, petroleum aromatic resin is mixed with xylene and heated and stirred at a constant temperature of 50-80°C for 15-30 minutes to obtain a dissolved petroleum aromatic resin solution. Then, maleic anhydride is added and heated and stirred at a constant temperature of 90-100°C for 1 hour. The mixture is then naturally cooled to room temperature to obtain component B (modified aromatic resin solution).

[0074] In an embodiment of the present invention, component A, component B and curing agent are added to a container and stirred continuously at a speed of 100-300 r / min for 15-30 minutes under a constant temperature of 50-80°C to obtain a phase transition protective coating modified with petroleum aromatic resin.

[0075] In an embodiment of the present invention, the petroleum aromatic resin modified phase transition protective coating is applied to the surface of the sample, cured to obtain a high-temperature resistant coating, and then calcined to obtain the petroleum aromatic resin modified phase transition protective coating.

[0076] In this invention, the coating method includes brushing, roller coating, spraying, or dip coating, etc.; the coating thickness is affected by factors such as the coating method and paint viscosity, and multiple coatings can be applied to ensure a film thickness greater than 80 μm; in the embodiments of this invention, the thickness of a single coating is 80–150 μm, and after three coatings, the total film thickness can reach 250–500 μm.

[0077] In this invention, the curing temperature is 15-30°C, for example, 15°C, 20°C, 25°C or 30°C; the curing time is 4-6 hours, for example, 4 hours, 5 hours or 6 hours.

[0078] In this invention, the calcination heating rate is 5–15 °C / min, for example, 5 °C / min, 10 °C / min, or 15 °C / min; the calcination temperature is 120–200 °C, for example, 120 °C, 130 °C, 140 °C, 150 °C, 160 °C, 180 °C, or 200 °C; the calcination time is 0.5–1 hour, for example, 0.5 hours, 0.6 hours, 0.7 hours, 0.8 hours, 0.9 hours, or 1 hour; the thickness of the petroleum aromatic resin modified phase transition protective coating is 80–500 μm, for example, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 150 μm, 200 μm, 300 μm, 400 μm, or 500 μm.

[0079] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0080] In the embodiments of the present invention, the phenyl content of the methylphenyl organosilicon resin is 15% to 25%; the particle size of the oleophilic nano-silica is 20 nm; the particle size of the ceramic microspheres is 10 to 30 μm; the length of the basalt fiber is 200 to 500 μm; and the diameter of the α-phase alumina powder is 5 to 10 nm.

[0081] Example 1

[0082] The formulation of a phase transition protective coating modified with petroleum aromatic resin is as follows:

[0083] The formulation of component A of the high-temperature resistant composite coating is as follows: 25 kg of methyl phenyl silicone resin, 15 kg of propylene glycol methyl ether acetate, 3.5 kg of oleophilic nano silica, 6 kg of barium sulfate, 5 kg of mica powder, 9 kg of mixed low-melting-point glass powder, 10 kg of α-phase alumina, 0.5 kg of aluminum fluoride, 1.5 kg of cerium oxide, 4 kg of ceramic microspheres, 0.5 kg of boric acid, 4 kg of basalt fiber, 1.5 kg of organobentonite, and 1.5 kg of polydimethylsiloxane.

[0084] The formulation of component B of the high-temperature resistant composite coating is as follows: 17 kg of C9 aromatic petroleum resin, 17 kg of xylene, and 2 kg of maleic anhydride.

[0085] Silane coupling agent formulation: 3.5 kg of γ-aminopropyltriethylsilane and 2.5 kg of tetraethoxysilane.

[0086] The preparation method of petroleum aromatic resin modified phase transition protective coating is as follows:

[0087] Install a shearing head on the mixer, and circulate water through the double-layer mixing tank to maintain a constant tank wall temperature of 80±5℃. Add C9 aromatic petroleum resin and xylene to the double-layer mixing tank, and continuously stir the resin solution at 360 r / min for 30 minutes to obtain an aromatic resin solution. Add maleic anhydride to the mixing tank, adjust the temperature of the circulating water in the mixing tank to 90±5℃, and continue stirring the solution at 360 r / min for 1 hour to obtain a modified aromatic resin solution (component B) for later use.

[0088] Take 6 kg of barium sulfate, 5 kg of mica powder, 3 kg of low-melting-point glass powder (melting temperature 350℃), 3 kg of low-melting-point glass powder (melting temperature 450℃), 3 kg of low-melting-point glass powder (melting temperature 550℃), 10 kg of α-phase alumina, and 0.5 kg of aluminum fluoride, and grind them in a grinder for 5 minutes to obtain a mixed powder for later use. Add 25 kg of methylphenyl silicone resin and 15 kg of propylene glycol methyl ether acetate to a double-layer mixing tank. Install a shearing head on the mixer, circulate water through the mixing tank to cool it down, and keep the tank wall temperature below 50℃. Stir the resin continuously at 360 r / min for 15 minutes to obtain a silicone resin solution. Under continuous stirring, slowly add 3.5 kg of oleophilic nano-silica, 30.5 kg of mixed grinding powder, 1.5 kg of cerium oxide, 4 kg of ceramic microspheres, 0.5 kg of boric acid, 1.5 kg of organobentonite, and 1.5 kg of polydimethylsiloxane to the mixing tank in sequence. Keep the tank wall temperature below 50±5℃ and continuously stir the resin at 360 r / min for 45 minutes. Adjust the mixer speed to 180 r / min, add 4 kg of basalt fiber to the mixing tank, and continue stirring for 15 minutes to obtain component A of the coating solution for later use.

[0089] Add 83 kg of component A of the above coating solution to a double-layer mixing tank, then add 36 kg of component B of the above coating solution, 3.5 kg of γ-aminopropyltriethylsilane, and 2.5 kg of tetraethoxysilane to the mixing tank. While maintaining the tank wall temperature at 60±5℃, stir continuously at 300 r / min for 30 minutes to obtain a phase transition protective coating modified with petroleum aromatic resin.

[0090] Preparation method of phase transition protective coating modified with petroleum aromatic resin:

[0091] The above-mentioned high-temperature resistant coating solution was brushed onto the surface of the specimen, and then the specimen was placed in a room temperature ventilated environment to dry and cure for 4 hours. Then the specimen was placed in a muffle furnace and heated from room temperature to 200°C at a heating rate of 5°C / min, maintained at 200±10°C for 1 hour, and then cooled to room temperature to obtain a petroleum aromatic resin modified phase transition protective coating.

[0092] Example 2

[0093] The formulation of a phase transition protective coating modified with petroleum aromatic resin is as follows:

[0094] The formulation of component A of the high-temperature resistant composite coating is as follows: 20 kg of methyl phenyl silicone resin, 15 kg of propylene glycol methyl ether acetate, 3 kg of oleophilic nano silica, 5.5 kg of barium sulfate, 5 kg of mica powder, 9 kg of mixed low-melting-point glass powder, 9 kg of α-phase alumina, 0.5 kg of aluminum fluoride, 1.5 kg of cerium oxide, 4 kg of ceramic microspheres, 0.5 kg of boric acid, 4 kg of basalt fiber, 1.5 kg of organobentonite, and 1.5 kg of polydimethylsiloxane.

[0095] Formula for component B of high-temperature resistant composite coating: 20kg of C9 aromatic petroleum resin, 18kg of xylene, and 2kg of maleic anhydride.

[0096] Silane coupling agent formulation: 2.5 kg of γ-aminopropyltriethylsilane and 2.5 kg of tetraethoxysilane.

[0097] The preparation method of petroleum aromatic resin modified phase transition protective coating is as follows:

[0098] Install a shearing head on the mixer, and circulate water through the double-layer mixing tank to maintain a constant tank wall temperature of 80±5℃. Add 20kg of C9 aromatic petroleum resin and 18kg of xylene to the double-layer mixing tank, and continuously stir the resin solution at 360r / min for 30 minutes to obtain an aromatic resin solution. Add 2kg of maleic anhydride to the mixing tank, adjust the temperature of the circulating water in the mixing tank to 90±5℃, and continue stirring the solution at 360r / min for 1 hour to obtain a modified aromatic resin solution (component B) for later use.

[0099] Take 5.5 kg of barium sulfate, 5 kg of mica powder, 3 kg of low-melting-point glass powder (melting temperature 350℃), 3 kg of low-melting-point glass powder (melting temperature 450℃), 3 kg of low-melting-point glass powder (melting temperature 550℃), 9 kg of α-phase alumina, and 0.5 kg of aluminum fluoride, and grind them dry in a grinder for 5 minutes to obtain a mixed powder for later use. Add 20 kg of methylphenyl silicone resin and 15 kg of propylene glycol methyl ether acetate to a double-layer mixing tank. Install a shearing head on the mixer, circulate water through the mixing tank to cool it down, and keep the tank wall temperature below 50℃. Stir the resin continuously at 360 r / min for 15 minutes to obtain a silicone resin solution. Under continuous stirring, slowly add 3 kg of oleophilic nano-silica, 29 kg of mixed grinding powder, 1.5 kg of cerium oxide, 4 kg of ceramic microspheres, 0.5 kg of boric acid, 1.5 kg of organobentonite, and 1.5 kg of polydimethylsiloxane to the mixing tank in sequence. Keep the tank wall temperature below 50±5℃ and continuously stir the resin at 360 r / min for 45 minutes. Adjust the mixer speed to 180 r / min, add 4 kg of basalt fiber to the mixing tank, and continue stirring for 15 minutes to obtain component A of the coating solution for later use.

[0100] Add 80 kg of component A of the above coating solution to a double-layer mixing tank, then add 40 kg of component B of the above coating solution, 2.5 kg of γ-aminopropyltriethylsilane, and 2.5 kg of tetraethoxysilane to the mixing tank. While maintaining the tank wall temperature at 60±5℃, stir continuously at a speed of 300 r / min for 30 minutes to obtain a phase transition protective coating modified with petroleum aromatic resin.

[0101] Preparation method of phase transition protective coating modified with petroleum aromatic resin:

[0102] The above coating solution was brushed onto the surface of the specimen, and then the specimen was placed in a ventilated environment at room temperature to dry and cure for 4 hours. The specimen was then placed in a muffle furnace and heated from room temperature to 200°C at a rate of 5°C / min, maintained at 200±10°C for 1 hour, and then cooled to room temperature to obtain a phase transition protective coating modified with petroleum aromatic resin.

[0103] Example 3

[0104] The formulation of a phase transition protective coating modified with petroleum aromatic resin is as follows:

[0105] The formulation of component A of the high-temperature resistant composite coating is as follows: 20 kg of methyl phenyl silicone resin, 15 kg of propylene glycol methyl ether acetate, 3.5 kg of oleophilic nano silica, 6 kg of barium sulfate, 5 kg of mica powder, 9 kg of mixed low-melting-point glass powder, 10 kg of α-phase alumina, 0.5 kg of aluminum fluoride, 1.5 kg of cerium oxide, 4 kg of ceramic microspheres, 0.5 kg of boric acid, 4 kg of basalt fiber, 1.5 kg of organobentonite, and 1.5 kg of polydimethylsiloxane.

[0106] Formula for component B of high-temperature resistant composite coating: 17 kg of C5 aromatic petroleum resin, 17 kg of xylene, and 2 kg of maleic anhydride.

[0107] Silane coupling agent formulation: 3.5 kg of γ-aminopropyltriethylsilane and 2.5 kg of tetraethoxysilane.

[0108] The preparation method of petroleum aromatic resin modified phase transition protective coating is as follows:

[0109] Install a shearing head on the mixer, and circulate water through the double-layer mixing tank to maintain a constant tank wall temperature of 80±5℃. Add 17kg of C5 aromatic petroleum resin and 17kg of xylene to the double-layer mixing tank, and continuously stir the resin solution at 360r / min for 30 minutes to obtain an aromatic resin solution. Add 2kg of maleic anhydride to the mixing tank, adjust the temperature of the circulating water in the mixing tank to 90±5℃, and continue stirring the solution at 360r / min for 1 hour to obtain a modified aromatic resin solution (component B) for later use.

[0110] Take 6 kg of barium sulfate, 5 kg of mica powder, 3 kg of low-melting-point glass powder (melting temperature 350℃), 3 kg of low-melting-point glass powder (melting temperature 450℃), 3 kg of low-melting-point glass powder (melting temperature 550℃), 10 kg of α-phase alumina, and 0.5 kg of aluminum fluoride, and grind them in a grinder for 5 minutes to obtain a mixed powder for later use. Add 25 kg of methylphenyl silicone resin and 15 kg of propylene glycol methyl ether acetate to a double-layer mixing tank. Install a shearing head on the mixer, circulate water through the mixing tank to cool it down, and keep the tank wall temperature below 50℃. Stir the resin continuously at 360 r / min for 15 minutes to obtain a silicone resin solution. Under continuous stirring, slowly add 3.5 kg of oleophilic nano-silica, 30.5 kg of mixed grinding powder, 1.5 kg of cerium oxide, 4 kg of ceramic microspheres, 0.5 kg of boric acid, 1.5 kg of organobentonite, and 1.5 kg of polydimethylsiloxane to the mixing tank in sequence. Keep the tank wall temperature below 50±5℃ and continuously stir the resin at 360 r / min for 45 minutes. Adjust the mixer speed to 180 r / min, add 4 kg of basalt fiber to the mixing tank, and continue stirring for 15 minutes to obtain component A of the coating solution for later use.

[0111] 78 kg of component A of the above coating solution was added to a double-layered mixing tank. 36 kg of component B of the above coating solution, 3.5 kg of γ-aminopropyltriethylsilane, and 2.5 kg of tetraethoxysilane were added to the mixing tank. Under the condition of maintaining the tank wall temperature at 60±5℃, the mixture was continuously stirred at a speed of 300 r / min for 30 minutes to obtain a phase transition protective coating solution modified with petroleum aromatic resin.

[0112] The preparation method of petroleum aromatic resin modified phase transition protective coating is as follows:

[0113] The above-mentioned petroleum aromatic resin modified phase transition protective coating solution was brushed onto the surface of the specimen, and then the specimen was placed in a room temperature ventilated environment to dry and cure for 4 hours. Then the specimen was placed in a muffle furnace and heated from room temperature to 200℃ at a heating rate of 5℃ / min, maintained at 200±10℃ for 1 hour, and then cooled to room temperature to obtain the petroleum aromatic resin modified phase transition protective coating.

[0114] Example 4

[0115] The formulation of a phase transition protective coating modified with petroleum aromatic resin is as follows:

[0116] The formulation of component A of the high-temperature resistant composite coating is as follows: 30 kg of methyl phenyl silicone resin, 15 kg of propylene glycol methyl ether acetate, 3.5 kg of oleophilic nano silica, 6 kg of barium sulfate, 5 kg of mica powder, 9 kg of mixed low-melting-point glass powder, 10 kg of α-phase alumina, 0.5 kg of aluminum fluoride, 1.5 kg of cerium oxide, 4 kg of ceramic microspheres, 0.5 kg of boric acid, 4 kg of basalt fiber, 1.5 kg of organobentonite, and 1.5 kg of polydimethylsiloxane.

[0117] Formula for component B of high-temperature resistant composite coating: 15kg of C9 aromatic petroleum resin, 18kg of xylene, and 2kg of maleic anhydride.

[0118] Silane coupling agent formulation: 3.5 kg of γ-aminopropyltriethylsilane and 2.5 kg of tetraethoxysilane.

[0119] Preparation method of phase transition protective coating modified with petroleum aromatic resin:

[0120] Install a shearing head on the mixer, and circulate water through the double-layer mixing tank to maintain a constant tank wall temperature of 80±5℃. Add 17kg of C9 aromatic petroleum resin and 17kg of xylene to the double-layer mixing tank, and continuously stir the resin solution at 360r / min for 30 minutes to obtain an aromatic resin solution. Add 2kg of maleic anhydride to the mixing tank, adjust the temperature of the circulating water in the mixing tank to 90±5℃, and continue stirring the solution at 360r / min for 1 hour to obtain a modified aromatic resin solution (component B) for later use.

[0121] Take 6 kg of barium sulfate, 5 kg of mica powder, 3 kg of low-melting-point glass powder (melting temperature 350℃), 3 kg of low-melting-point glass powder (melting temperature 450℃), 3 kg of low-melting-point glass powder (melting temperature 550℃), 10 kg of α-phase alumina, and 0.5 kg of aluminum fluoride, and grind them in a grinder for 5 minutes to obtain a mixed powder for later use. Add 25 kg of methylphenyl silicone resin and 15 kg of propylene glycol methyl ether acetate to a double-layer mixing tank. Install a shearing head on the mixer, circulate water through the mixing tank to cool it down, and keep the tank wall temperature below 50℃. Stir the resin continuously at 360 r / min for 15 minutes to obtain a silicone resin solution. Under continuous stirring, slowly add 3.5 kg of oleophilic nano-silica, 30.5 kg of mixed grinding powder, 1.5 kg of cerium oxide, 4 kg of ceramic microspheres, 0.5 kg of boric acid, 1.5 kg of organobentonite, and 1.5 kg of polydimethylsiloxane to the mixing tank in sequence. Keep the tank wall temperature below 50±5℃ and continuously stir the resin at 360 r / min for 45 minutes. Adjust the mixer speed to 180 r / min, add 4 kg of basalt fiber to the mixing tank, and continue stirring for 15 minutes to obtain component A of the coating solution for later use.

[0122] Add 88 kg of component A of the above coating solution to a double-layer mixing tank. Add 35 kg of component B of the above coating solution, 3.5 kg of γ-aminopropyltriethylsilane, and 2.5 kg of tetraethoxysilane to the mixing tank. While maintaining the tank wall temperature at 60±5℃, stir continuously at 300 r / min for 30 minutes to obtain a phase transition protective coating solution modified with petroleum aromatic resin.

[0123] Preparation method of phase transition protective coating modified with petroleum aromatic resin:

[0124] The above-mentioned petroleum aromatic resin modified phase transition protective coating solution was brushed onto the surface of the specimen, and then the specimen was placed in a room temperature ventilated environment to dry and cure for 4 hours. Then the specimen was placed in a muffle furnace and heated from room temperature to 200℃ at a heating rate of 5℃ / min, maintained at 200±10℃ for 1 hour, and then cooled to room temperature to obtain the petroleum aromatic resin modified phase transition protective coating.

[0125] Comparative Example 1

[0126] The only difference from Example 1 is that the petroleum aromatic resin modified phase transition protective coating formulation does not contain C9 aromatic petroleum resin, while the rest of the formulation and preparation method remain unchanged.

[0127] Comparative Example 2

[0128] The only difference from Example 1 is that the petroleum aromatic resin modified phase transition protective coating formulation does not contain maleic anhydride; the rest of the formulation and preparation method remain unchanged.

[0129] The performance test results of the phase transition protective coatings modified with petroleum aromatic resins prepared in Examples 1-4 and Comparative Examples 1-2 are shown in Table 1.

[0130] Table 1. Performance test results of petroleum aromatic resin modified phase transformation protective coating

[0131]

[0132]

[0133] Table 1, comparing the examples and comparative examples, shows that maleic anhydride improves the compatibility of petroleum aromatic resin and methylphenyl silicone resin, enabling the two resins to mix uniformly. Modified petroleum aromatic resin not only enhances the self-healing properties of the coating and reduces cracking defects under high-temperature conditions, but also further transforms the coating material from a glassy and ceramic phase to a glassy carbon phase at high temperatures. This maintains the structural integrity of the coating at around 1000℃, providing excellent high-temperature protection for the substrate. Experiments revealed that without the addition of modified petroleum aromatic resin, the coating provides some high-temperature protection to the substrate up to 500℃, but at higher temperatures, the coating experiences cracking, desorption, and other failures, losing its protective effect on the substrate.

[0134] Figure 1 This diagram illustrates the phase transformation process of the coating as the temperature increases. It shows that different components of the coating play different roles and form different phase transformations within different temperature ranges. Below 200℃, methylphenyl silicone resin mainly serves as the film-forming material. Between 200 and 450℃, the silicone resin undergoes oxidative fracture and re-crosslinking, transforming into a glassy phase along with low-melting-point glass powder as the film-forming material. Between 450 and 750℃, ceramic microspheres react with the molten glassy phase, generating mullite fibers in situ, which further form chemical bonds with basalt fibers and borosilicate glass. During the formation of the complex ceramic phase, bonding and fracture ensure the structural integrity of the coating. Between 750 and 1100℃, cerium oxide catalyzes the graphitization of residual carbon in the resin, and the glassy phase melts and self-heals, forming a glassy carbon phase with the residual carbon graphite. Although the process of different phase transformations of the coating as the temperature rises is unidirectional and irreversible, regardless of whether the coating transforms into a glass phase, ceramic phase, or glassy carbon phase, it has excellent adhesion to the substrate, wear resistance, and shielding effect against corrosive agents. Therefore, the coating exhibits good protective performance in a wide temperature range from room temperature to 1100℃.

[0135] In summary, the petroleum aromatic resin-modified phase transition protective coating proposed in this invention exhibits excellent high-temperature corrosion resistance, superior adhesion, and wide-range high-temperature protection. This coating comprises methylphenyl silicone resin, modified petroleum aromatic resin, and various high-temperature resistant phase transition fillers, with a coating thickness of approximately 100–200 μm. This coating undergoes multiple phase transitions as the temperature increases, providing long-lasting high-temperature protection to the substrate over a wide temperature range from room temperature to 1100°C. The coating demonstrates excellent high-temperature resistance, corrosion resistance, and abrasion resistance in high-temperature environments.

[0136] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A phase transition protective coating modified with petroleum aromatic resin, characterized in that, It includes the following components in parts by weight: 60.5 to 114.5 parts of component A, 29 to 43 parts of component B, and 4 to 10 parts of curing agent; Component A comprises the following components in parts by weight: 20-30 parts methyl phenyl silicone resin, 10-20 parts propylene glycol methyl ether acetate, 2-5 parts oleophilic nano silica, 4-8 parts barium sulfate, 3-7 parts mica powder, 6-12 parts mixed low-melting-point glass powder, 7.5-12.5 parts α-phase alumina, 0-1 part aluminum fluoride, 1-3 parts cerium oxide, 3-5 parts ceramic microspheres, 0-1 part boric acid, 3-5 parts basalt fiber, 0.5-2.5 parts thixotropic agent, and 0.5-2.5 parts leveling agent; Component B comprises the following components in parts by weight: 14-20 parts of petroleum aromatic resin, 14-20 parts of xylene, and 1-3 parts of maleic anhydride; The preparation method of component B is as follows: petroleum aromatic resin is mixed with xylene and mixed at 50~80℃ for 15~30 minutes to obtain a dissolved petroleum aromatic resin solution. Then maleic anhydride is added and stirred at 90~100℃ for 1 hour to obtain component B. The mixed low-melting-point glass powder is composed of low-melting-point glass powder with a melting temperature of 350°C, low-melting-point glass powder with a melting temperature of 450°C, and low-melting-point glass powder with a melting temperature of 550°C.

2. The phase transition protective coating modified with petroleum aromatic resin according to claim 1, characterized in that, The curing agent comprises the following components in parts by weight: 2-5 parts of γ-aminopropyltriethoxysilane and 2-5 parts of tetraethoxysilane.

3. The phase transition protective coating modified with petroleum aromatic resin according to claim 1, characterized in that, The phenyl content of the methylphenyl organosilicon resin is 15%~60%; the particle size of the oleophilic nano-silica is 5~25 nm.

4. The phase transition protective coating modified with petroleum aromatic resin according to claim 1, characterized in that, The diameter of the α-phase alumina is 2~50 nm; the particle size of the ceramic microspheres is 10~100 μm; and the length of the basalt fiber is 30~100 μm.

5. The phase transition protective coating modified with petroleum aromatic resin according to claim 1, characterized in that, The petroleum aromatic resins include one or more of the following: DCPD cycloaliphatic resins, hydrogenated petroleum resins, C5 aliphatic petroleum resins, C9 aromatic petroleum resins, and condensed polynuclear aromatic resins.

6. The phase transition protective coating modified with petroleum aromatic resin according to claim 1, characterized in that, The thixotropic agent includes one or more of organobentonite, sodium-based bentonite, lithium-based bentonite, and fumed silica. The leveling agent includes one or more of polydimethylsiloxane, alkyl-modified organosiloxane, polyether polyester-modified organosiloxane, and acrylate.

7. The method for preparing the petroleum aromatic resin modified phase transition protective coating according to any one of claims 1 to 6, characterized in that, Includes the following steps: Barium sulfate, mica powder, mixed low-melting-point glass powder, α-phase alumina, and aluminum fluoride are mixed and ground to obtain a mixed grinding powder. The mixed grinding powder, oleophilic nano-silica, cerium oxide, ceramic microspheres, boric acid, thixotropic agent, and leveling agent are added to a mixed solution of methyl phenyl silicone resin and propylene glycol methyl ether acetate to obtain a filler suspension. Basalt fiber is mixed with the filler suspension to obtain component A. Petroleum aromatic resin is mixed with xylene and stirred at 50-80°C for 15-30 minutes to obtain a dissolved petroleum aromatic resin solution. Then maleic anhydride is added and stirred at 90-100°C for 1 hour to obtain component B. Component A, component B and curing agent are stirred continuously at 100-300 r / min at 50-80℃ for 15-30 minutes to obtain a phase transition protective coating modified with petroleum aromatic resin. The phase transition protective coating modified with petroleum aromatic resin was applied to the surface of the sample, cured, and then calcined to obtain the phase transition protective coating modified with petroleum aromatic resin.

8. The preparation method according to claim 7, characterized in that, The curing temperature is 15~30℃ and the time is 4~6h.

9. The preparation method according to claim 8, characterized in that, The calcination temperature is 120~200℃, and the calcination time is 0.5~1 hour; the thickness of the petroleum aromatic resin modified phase transformation protective coating is 80~500 μm.

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