CN115418166B - Polyborosilazane/epoxy composite high-temperature-resistant corrosion-resistant coating and preparation method thereof - Google Patents

Polyborosilazane/epoxy composite high-temperature-resistant corrosion-resistant coating and preparation method thereof Download PDF

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CN115418166B
CN115418166B CN202211244391.2A CN202211244391A CN115418166B CN 115418166 B CN115418166 B CN 115418166B CN 202211244391 A CN202211244391 A CN 202211244391A CN 115418166 B CN115418166 B CN 115418166B
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CN115418166A (en
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赵玮
甘明洋
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Hangzhou Wanguan Technology Co ltd
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    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
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Abstract

The invention relates to a polyborosilazane/epoxy composite high-temperature-resistant corrosion-resistant coating which comprises the following raw materials in parts by mass: 15-25 parts of polyborosilazane prepolymer, 10-20 parts of epoxy resin, 3-5 parts of epoxy resin slurry, 1-5 parts of silane coupling agent and 45-73 parts of solvent, wherein the epoxy resin slurry comprises the following raw materials in parts by mass: 20-40 parts of epoxy resin, 10-20 parts of high temperature resistant nano powder, 1-5 parts of dispersing agent and 35-65 parts of solvent; the polyborosilazane prepolymer is polymerized by the following monomers: dihydrocarbyldichlorosilane, alkenyl-containing dichlorosilane, silazane, and boron chloride. According to the invention, the temperature resistance of the epoxy resin system is improved by introducing the polyborosilazane, and the usage amount of polyborosilazane resin is reduced, so that the whole coating has the advantages of polyborosilazane resin, the cost is reduced, and the commercial value is very good.

Description

Polyborosilazane/epoxy composite high-temperature-resistant corrosion-resistant coating and preparation method thereof
Technical Field
The invention relates to the technical field of preparation of anti-corrosion coatings, in particular to a polyborosilazane/epoxy composite high-temperature-resistant anti-corrosion coating and a preparation method thereof.
Background
With the progress of human society technology, various industries have problems of corrosion of organic matters. Some conventional industry corrosions are: the ocean heavy corrosion protection, river and lake heavy corrosion protection, outdoor acid rain resistance and other corrosion resistance have excellent products. However, corrosion in the high temperature industry has some problems to be solved: the petroleum pipeline is resistant to heat and petroleum corrosion and permeation (200 ℃), the outer side of a chimney of a steelmaking furnace, a thermal power plant and the like is resistant to corrosion (200-300 ℃), the outer wall of an incinerator is resistant to corrosion (100-300 ℃), the inner wall and the outer wall of a heating waterway pipeline are resistant to corrosion (50-90 ℃), and the like, and the problems of blank products, single type, high production cost, difficult construction process and the like exist. Therefore, with the increasing demand of the high-temperature industry for high-temperature-resistant corrosion-resistant coatings, developing high-temperature-resistant corrosion-resistant coatings is also one of the research hotspots of the coating industry.
Epoxy resins, which are one of the most used resins in corrosion-resistant coatings, have very excellent mechanical properties, chemical resistance, water resistance, and workability. Meanwhile, the use of epoxy resins in the corrosion resistant field has been verified over time, and the excellent effect of the epoxy resins itself is widely accepted by society. However, the common epoxy resin and the curing agent have the problems of poor moisture and heat resistance, low high-temperature residual quantity and the like after being cured, and the application of the epoxy resin in the high-temperature corrosion-resistant field is limited.
The polysilazane resin is a resin composed of Si, N, O, C, H and other elements, and has excellent physical and chemical properties such as high hardness, high temperature resistance, water repellency, oleophobic property and the like. Some studies have been made in the prior art on polysilazane/epoxy coatings. Coating compositions such as those disclosed in CN113402974a, comprising a methylpolysiloxane resin, polysilazane, a modified silicone oil, a fluorosurfactant and a solvent; CN113444446a discloses a corrosion resistant coating comprising methylpolysiloxane resin, perhydro polysilazane, modified silicone oil, silane coupling agent, fluorosilane and solvent; the surface energy of the coating is reduced by adding the fluorine-containing reagent to finish the hydrophobic modification of the coating, but the salt fog resistance and the high temperature resistance are poor; CN111961412a discloses a polysilazane modified epoxy anticorrosive paint, which comprises polysilazane modified epoxy resin, a catalyst, a filler and a solvent, wherein the polysilazane modified epoxy resin is prepared by ring-opening reaction of Si-N bonding epoxy to prepare a prepolymer with a main chain containing Si-O-C, si-N-C, and the prepolymer contains double bonds, active hydrogen and other active groups, and the prepolymer reacts under heating conditions, so that the crosslinking density is increased, and the temperature resistance is improved. When water enters the coating, the water can be hydrolyzed with Si-N bond preferentially, so that the speed of penetration of corrosion grafting to the substrate is relieved, and the aim of corrosion prevention is fulfilled.
There are some problems: 1. polysilazane forms a ceramic or ceramic-like coating after curing, so that the thickness of the polysilazane coating is relatively thin, typically only 3-7 μm;2. the polysilazane resin has late starting in China, few mass-produced enterprises and the main body basically depends on import, so that the polysilazane resin has high price, the current import price is more than 2000 yuan/kg, and the price of some companies in China is 1500-3000 yuan/kg; 3. the polysilazane has low viscosity, and the viscosity of the common polysilazane resin in the market is basically similar to that of water, so that the polysilazane resin has weak capillary resistance, and has high cost in construction of wall surfaces, pipelines and the like, and the construction of brushing, roller coating and the like is difficult; 4. most practical use projects of polysilazane at present are abroad, and only a small part of enterprises except for high schools at home use and research polysilazane; 5. early polysilazane is used as a technical block, and although some types of polysilazane are in an open state at present, some types of polysilazane are in a blocked state, so that the development and the use of polysilazane in China and the like are limited to a certain extent.
With the recent years, more and more students, experts and engineers have paid attention to polysilazane resins, the properties of which have come closer to foreign products, polyborosilazane produced by my company is a derivative of silazane resins, has better high temperature resistance (1700 ℃ after ceramization), thick coating (film thickness 10-15 μm), high hardness (room temperature curing 7-8H, ceramization > 10H) and price than polysilazane resins, and also has great advantages. Therefore, how to use polyborosilazane and epoxy resin in combination to prepare a coating capable of resisting corrosion under high temperature conditions has become an urgent problem to be solved.
Disclosure of Invention
In order to solve some defects of the high-temperature corrosion-resistant coating in the prior art, the invention firstly grinds the high-temperature-resistant powder with the micro-nano structure and the epoxy resin into stable stored slurry through grinding equipment, and then forms a layer of high-temperature-resistant coating by crosslinking and curing the polyborosilazane, the epoxy resin, the silane coupling agent and the epoxy color paste containing the nano powder. The nano powder with high temperature resistance is added into the coating, so that the coating is more compact to a certain extent, and the penetration of corrosive substances to the coating can be effectively blocked when the coating faces various corrosions. Meanwhile, the high viscosity of epoxy resin in the coating enables the whole coating system to be well constructed on the base materials with serious capillary phenomena such as walls, corroded pipelines, cement and the like. In addition, the use of the epoxy resin also ensures the film thickness of the whole coating system, thereby avoiding the defects of weak capillary resistance, thin film thickness, poor powder bearing effect and the like of polysilazane. On the other hand, by introducing polyborosilazane, the temperature resistance of the epoxy resin system is greatly improved, and meanwhile, the polyborosilazane resin is compounded with the epoxy resin, so that the use amount of the polyborosilazane resin is reduced, the whole coating has various advantages of polyborosilazane resin, and the price is greatly reduced, thereby the coating system has good commercial value.
The polyborosilazane/epoxy composite high-temperature-resistant corrosion-resistant coating comprises the following raw materials in parts by mass: 15-25 parts of polyborosilazane prepolymer, 10-20 parts of epoxy resin, 3-5 parts of epoxy resin slurry, 1-5 parts of silane coupling agent and 45-73 parts of solvent, wherein the epoxy resin slurry comprises the following raw materials in parts by mass: 20-40 parts of epoxy resin, 10-20 parts of high temperature resistant nano powder, 1-5 parts of dispersing agent and 35-65 parts of solvent; the polyborosilazane prepolymer is polymerized by the following monomers: dihydrocarbyldichlorosilane, alkenyl-containing dichlorosilane, silazane, and boron chloride.
Further, the epoxy resin has an epoxy equivalent of 180-230g/eq, and the epoxy resin is selected from bisphenol type epoxy resins such as bisphenol A, bisphenol AF, bisphenol S, bisphenol F, etc., preferably bisphenol A type epoxy resins such as at least one of E-35, E38, E-44, E-51.
Further, the silane coupling agent is at least one selected from epoxy silane coupling agents, amino silane coupling agents and double bond silane coupling agents; the epoxy silane coupling agent is at least one selected from 3-glycidoxypropyl trimethoxysilane, 3- (2, 3-glycidoxypropyl) propyl triethoxysilane and 3- (2, 3-glycidoxypropyl) propyl methyl dimethoxy silane; the silane coupling agent with amino is at least one selected from gamma-aminopropyl trimethoxy silane, gamma-aminopropyl triethoxy silane, gamma-diethylenetriamine propyl methyl dimethoxy silane and N-2-aminoethyl-3-aminopropyl trimethoxy silane; the silane coupling agent with double bond is at least one selected from vinyl trimethoxy silane, vinyl triethoxy silane and vinyl tri (beta-methoxyethoxy) silane.
Preferably, the silane coupling agent is a mixed silane coupling agent with epoxy silane coupling agent, amino silane coupling agent and double bond, wherein the mass ratio of the silane coupling agent to the amino silane coupling agent is 4-6:1-2:1-2, and the dosage of the silane coupling agent is 2.5-3.5 parts. The inventor finds that the coating prepared by the coupling agent compounded according to the proportion has optimal comprehensive performance. Wherein, the epoxy group can react with the silicon nitrogen bond in the silazane, so that the adhesive force between the coating and the base material or the adhesiveness between the coating and the nano particles is increased while the crosslinking density is increased; the double bond can be further crosslinked with the double bond in the silazane at high temperature, so that the crosslinking density of the coating is increased, the strength of the coating is improved, and the adhesive force and the adhesiveness can be also increased; the amino group can accelerate the curing rate of polysilazane and increase the crosslinking density and mechanical property of the coating.
The grain diameter of the high temperature resistant nano powder is 10-400nm, preferably 50-200nm; specifically, the nano silicon nitride, nano boron carbide, nano aluminum oxide, nano aluminum nitride, nano boron nitride, nano silicon carbide, nano magnesium oxide, nano zinc oxide and nano titanium dioxide.
Further, the polyborosilazane prepolymer is obtained by polymerizing monomers comprising the following parts by mass: 10-15 parts of dialkyl dichlorosilane, 8-13 parts of dichlorosilane containing alkenyl, 30-40 parts of silazane and 10-15 parts of boron chloride.
Further, the dialkyl dichlorosilane is at least one selected from dimethyl dichlorosilane, diethyl dichlorosilane, dipropyl dichlorosilane, diphenyl dichlorosilane and methylethyl dichlorosilane; the dichloro silane containing alkenyl is selected from at least one of methyl vinyl dichloro silane, methyl propenyl dichloro silane and ethyl vinyl dichloro silane; the silazane is at least one selected from hexamethyldisilazane, tetramethyl divinyl disilazane, hexamethyl cyclotrisilazane and octamethyl cyclotetrasilazane.
The solvent and the dispersant are not particularly limited, and may be used in the art. For example, the solvent is at least one selected from propylene glycol methyl ether acetate, n-butyl acetate, amyl acetate, methyl isobutyl ketone and methyl amyl ketone; the dispersant is polyurethane oil dispersant, such as at least one of Silok7423, silok7007, silok7096 and Silok 7421.
The invention firstly grinds high temperature resistant powder with micro-nano structure and epoxy resin into stable storage slurry through grinding equipment, and then prepares the high temperature resistant anticorrosive paint by utilizing polyborosilazane prepolymer, epoxy resin, silane coupling agent and epoxy slurry containing nano powder. The high-temperature-resistant anticorrosive paint can be coated in various modes of spraying, roller coating, brushing and the like, and can be coated on various base materials such as metal, wood, concrete, glass, plastic, ceramic and the like. Curing for 10-30min at 80-130 ℃ after uniform coating, and curing for 3-5 days to obtain the high-quality high-temperature-resistant anti-corrosion coating. The coating obtained by the invention has excellent high temperature resistance, and can not generate bad phenomena such as rhagadia, falling off and the like at 350 ℃; has excellent corrosion resistance and salt fog resistance, can effectively resist neutral salt fog for 500-600 hours, and does not generate rust.
The reaction mechanism of the chemical structure obtained by the reaction of polysilazane is complex, various reactions occur, and no unified theorem exists at present. The reaction mechanism is reported in the prior art as follows:
Figure BDA0003885805750000051
also known in the art is a structure having a backbone- (B-N) 3 -a six-membered ring structure is present. The product structure is as follows:
Figure BDA0003885805750000052
but the applicant believes that it also includes the following structure:
Figure BDA0003885805750000053
wherein R is 1 And R is 2 Identical or different, R 1 And R is 2 At least one of them being a reactive group-CH=CH 2 The other is-H, C 1 -C 4 Alkyl, -ch=ch 2 、-C 6 H 5 or-NH 2 N is an integer of 3 to 3000. Wave line
Figure BDA0003885805750000054
Representing a structure similar to that drawn above, i.e. the bond between the nitrogen-containing moiety NH and the boron element B in the silaborazine. Since the stable valence of the boron element is generally +3, the boron element has 3 reactive sites and is easy to react with NH groups which are active in the system to form a crosslinked three-dimensional network structure.
The second object of the invention is to provide a preparation method of the polyborosilazane/epoxy composite high temperature resistant corrosion resistant paint, which comprises the following steps:
(S1) preparation of polyborosilazane prepolymer: adding a monomer dialkyl dichlorosilane, an alkenyl-containing dichlorosilane and a boron chloride n-hexane solution according to a proportion, cooling to 0-5 ℃, gradually adding silazane, recovering to room temperature, continuously stirring for 5-10h, heating to 200-240 ℃ after the reaction is finished, removing by-products trimethyl chlorosilane, an n-hexane solvent and a monomer which does not participate in the reaction, and carrying out vacuum drying to obtain a polyborosilazane prepolymer;
(S2) preparation of epoxy resin slurry: uniformly mixing epoxy resin, high-temperature-resistant nano powder, a dispersing agent and a solvent, and grinding until the fineness is less than 10 mu m to obtain epoxy resin slurry;
(S3) preparation of high-temperature-resistant and corrosion-resistant paint: and (3) uniformly stirring the polyborosilazane prepolymer obtained in the step (S1), the epoxy resin slurry obtained in the step (S2), the epoxy resin, the silane coupling agent and the solvent to obtain the high-temperature-resistant corrosion-resistant coating.
The high-temperature-resistant corrosion-resistant coating is simple in application mode, the high-temperature-resistant corrosion-resistant coating is uniformly coated on the surface of a clean substrate, the thickness of a wet coating is controlled to be 30-50 mu m, the wet coating is cured for 10-30min at the temperature of 80-130 ℃, and then the high-quality high-temperature-resistant corrosion-resistant coating can be obtained after curing for 3-5 days. The manner of uniform coating is not particularly limited as long as it is possible to achieve uniform coating of the coating material on the surface of the substrate with a prescribed thickness, including but not limited to spraying, rolling, brushing.
Compared with the prior art, the invention has the following beneficial effects:
1. the film forming material of the high temperature resistant anticorrosive paint adopts polyborosilazane resin and silane coupling agent to cure epoxy resin, and utilizes polar Si-N bond and epoxy group to produce ring-opening reaction, so that stable coating containing Si-O-C, si-N-C structure is formed. Meanwhile, the side chain of the polyborosilazane resin contains active vinyl groups and other groups, and the active groups can further undergo addition reaction under the action of heating or a catalyst, so that the crosslinking density of the coating is obviously increased, and high barrier shielding property is provided for the cured coating. Secondly, the introduction of N-B bond increases the temperature resistance of the coating, and when designing a room temperature or medium and low temperature cured anticorrosive coating formula, the selection of the type and molecular weight of the epoxy resin can not be limited by temperature, so that the selection is more flexible and changeable. Therefore, the coating based on the composite resin has the characteristics of excellent corrosion resistance, easy adjustment of film thickness, strong substrate applicability and the like, and provides a new material selection and thinking for the preparation of high-temperature corrosion-resistant coatings.
2. The invention can expand the application range of the epoxy resin anti-corrosion coating, in particular to the aspect of high temperature resistant anti-corrosion coating, the production and preparation process is simple, the invention is applicable to various different substrates and large-scale production, the thermal stability and the chemical stability are good, the weather resistance of the epoxy resin can be well improved, the temperature resistance of the coating is conducive to realizing the coating inside the substrate, thereby greatly prolonging the service life of the substrate. Meanwhile, the coating has simple construction process and controllable quality. No special chemical treatment, plasma treatment, flame or heat treatment, etc. are required for the substrate prior to coating. In addition, butyl acetate is used as a solvent, so that the coating is more energy-saving and environment-friendly, is suitable for commercial popularization, has wide coating thickness adjustment range, wide application range, good adhesive force and excellent corrosion resistance, can be used as dip coating liquid to completely replace hot galvanizing in the aspects of process, performance and the like, and has important potential application values in petroleum transportation pipelines, heating pipelines, inner walls of chimneys of steelmaking furnaces or high-temperature furnaces and the like in the future.
3. The high-temperature-resistant corrosion-resistant coating provided by the invention is prepared by utilizing the high viscosity of the epoxy resin to enhance the capillary resistance of the coating, and simultaneously utilizing the high mechanical property and the strong adhesion property of the epoxy resin, so that the prepared coating can be well applied to base materials with large oil absorption such as wall surfaces, cement surfaces, rough ceramic surfaces and the like; the addition of the silane coupling agent and the polyborosilazane resin can improve the hardness, wear resistance and high temperature resistance of the coating, and meanwhile, the silane coupling agent and the epoxy resin can be well crosslinked after being cured to enable the coating to be more compact, so that the coating has better corrosion resistance; the high-temperature-resistant color paste is added into the coating, so that the hardness and the temperature resistance of the whole coating can be improved, the integrity of the coating can be ensured when the coating faces high-temperature particulate matter impact and high-speed corrosive fluid, and meanwhile, the micro-nano powder can fill resin gaps in a microstructure, so that the corrosion resistance of the coating is further enhanced.
Drawings
FIG. 1 is a photograph of a conventional epoxy coating and the coating obtained in example 1 baked at 400℃for 10 hours;
FIG. 2 is a photograph showing a conventional epoxy coating and the coating obtained in example 1 after being baked at a high temperature of 260℃for 10 hours and subjected to a salt spray resistance test for 560 hours, respectively.
Detailed Description
The present application is further illustrated by the following examples.
The reagents used in the present invention are all commercially available from conventional sources.
The "parts" in the examples of the present invention are parts by mass unless otherwise specified, and the "%" is percent by mass unless otherwise specified.
Example 1
(S1) preparation of polyborosilazane prepolymer
Weighing 12.5 parts of methyldichlorosilane, 11.3 parts of methylvinyldichlorosilane and 11.7 parts of boron chloride (1M n-hexane solution), uniformly mixing, cooling to 0 ℃, dropwise adding 36.8 parts of hexamethyldisilazane into the solution under the stirring condition, returning the temperature to room temperature after the dropwise adding, continuously stirring for 6 hours, gradually heating to 200 ℃ to remove by-products of trimethylchlorosilane, n-hexane solvent and monomers which do not participate in the reaction, and finally drying in vacuum at 120 ℃ for 1 hour to obtain a polyborosilazane prepolymer;
(S2) preparation of epoxy paste
Weighing 30 parts of epoxy resin E44, 15 parts of silicon nitride nano powder (with the average particle size of 200 nm), placing 3 parts of dispersing agent Silok7423 and 62 parts of propylene glycol methyl ether acetate into a grinding tank, adding grinding zirconium beads, sealing the grinding tank, starting a high-speed grinding machine, grinding for 1h at a rotating speed of 2500rpm, and filtering the zirconium beads by a stainless steel filter screen when the fineness is less than 10 mu m to obtain epoxy slurry;
(S3) preparing high-temperature-resistant and corrosion-resistant paint
Weighing 20 parts of epoxy resin E44, 20 parts of polyborosilazane prepared in the step (S1), 3.5 parts of high-temperature-resistant epoxy paste prepared in the step (S2), and 2.5 parts of silane coupling agent (KH 560, KH-550 and A171 are mixed according to the mass ratio of 4:1:1), adding the mixture into 45 parts of propylene glycol methyl ether acetate, stirring the mixture for 30min by a high-speed stirrer, and obtaining the high-temperature-resistant corrosion-resistant coating after all the components are mixed.
Fig. 1 and 2 are pictures of a conventional epoxy coating and a coating obtained in the example, respectively, baked at a high temperature of 400 c for 10 hours and subjected to a salt spray resistance test after being baked at a high temperature of 260 c for 10 hours. It can be seen that the anti-corrosion coating of the invention has no obvious shedding and color change phenomenon after being baked at a high temperature of 400 ℃; after being baked for 10 hours at 260 ℃, the salt fog resistance can be kept very good.
Example 2
Other conditions and operations were the same as in example 1 except that in the preparation of the polyborosilazane prepolymer in step (S1), the monomer amount was changed to 10 parts of methyldichlorosilane, 13 parts of methylvinyldichlorosilane, 15 parts of boron chloride, and 30 parts of hexamethyldisilazane.
Example 3
Other conditions and operations were the same as in example 1 except that in the preparation of the polyborosilazane prepolymer in step (S1), the monomer amount was changed to 10 parts of methyldichlorosilane, 15 parts of methylvinyldichlorosilane, 10 parts of boron chloride, and 40 parts of hexamethyldisilazane.
Example 4
Other conditions and operations were the same as in example 1 except that in step (S3), the silane coupling agent was 3.5 parts of a compounded silane coupling agent of KH561, KH-540 and A151 in a mass ratio of 6:1:2.
Example 5
Other conditions and operations are the same as in example 1 except that in the step (S3), the silane coupling agent is a compound silane coupling agent of KH560 and KH-550 in a mass ratio of 4:1.
Example 6
Other conditions and operations are the same as in example 1 except that in the step (S3), the silane coupling agent is a compound silane coupling agent of KH560 and a171 in a mass ratio of 4:1.
Example 7
Other conditions and operations are the same as in example 1 except that in the step (S3), the silane coupling agent is a compound silane coupling agent of KH-550 and A171 in a mass ratio of 1:1.
Application example
Wiping a carbon steel plate (CR 4 grade cold rolled carbon steel conforming to ISO 3574) with butyl acetate, cleaning greasy dirt, dust, particulate matters and the like on the surface of the carbon steel plate, scrubbing the carbon steel plate with the diameter of 75mm and the diameter of 150mm, and placing the cleaned base material in a baking oven at 50-60 ℃ for baking and drying for later use; and (3) placing a proper amount of high-temperature-resistant and corrosion-resistant paint into a hopper of an air spray gun, taking out a steel plate substrate, placing the steel plate substrate at a proper position for spraying, controlling the thickness of a sprayed wet film to be about 30 mu m, placing the sprayed steel plate in a baking oven at 100 ℃ for baking for 10min after surface drying, taking out and curing for 3d, thus obtaining the high-temperature-resistant and corrosion-resistant coating, wherein the adhesive force of the test coating is 0 level (the test method GB/T9286 hundred lattice method).
The coatings of the above examples and comparative examples were subjected to the following performance tests after having obtained the coatings according to the above method:
1) Salt spray resistance test: and placing the sample plate with the surface coated by the polyborosilazane/epoxy composite coating and the sample plate with the substrate coated by the epoxy resin in a neutral salt spray test box for salt spray resistance test. Salt spray tests are carried out according to the related requirements in GB/T10125-2021, neutral salt spray is adopted in salt spray tests, and 5% NaCl solution is adopted in salt water, wherein the pH value is about 7. In the salt spray test, the corrosion condition of the sample plate is observed by adopting the frequency of one-time observation in 24 hours, and the test can be stopped when the foaming, pulverization or scratch corrosion exceeds 2mm, and the sample plate is taken out.
2) High temperature resistance experiment: placing the template with the surface coated by the polyborosilazane/epoxy composite coating and the template with the substrate coated by the epoxy resin in a muffle furnace, raising the temperature in the furnace to 400 ℃ at a heating rate of 5 ℃/min, continuously baking at 400 ℃ for 10 hours, and then taking out the template to observe the appearance change of the coating. The results are shown in Table 1 below.
TABLE 1 coating Performance test
Figure BDA0003885805750000101
As can be seen from the data in Table 1, the coating provided by the invention has excellent high temperature resistance and corrosion resistance. Under the condition of high temperature, the conventional coating has the defects of oxidation, falling off and the like, the corrosion resistance can be greatly reduced, and the application of the coating in certain fields is limited. According to the invention, the polyborosilazane prepolymer compounded epoxy resin is utilized, and under the interaction of the high-temperature-resistant nano powder and the silane coupling agent, the high-temperature-resistant anticorrosive paint with excellent comprehensive performance is prepared.
At present, the salt spray test and the product with longer salt spray resistance are basically aimed at the normal temperature environment. The corrosion resistance of the current product with corrosion resistance in the environment of 200-400 ℃ is greatly reduced. Products aimed at this temperature range mostly require high temperature curing at 100-200 ℃, which limits the use in certain fields. Therefore, the product can be baked at 400 ℃ for 10 hours without color change and salt fog resistance, has flexible and various curing modes, and has advantages in the field of high temperature resistance and corrosion resistance.

Claims (8)

1. The polyborosilazane/epoxy composite high-temperature-resistant corrosion-resistant coating is characterized by comprising the following raw materials in parts by mass: 15-25 parts of polyborosilazane prepolymer, 10-20 parts of epoxy resin, 3-5 parts of epoxy resin slurry, 2.5-3.5 parts of silane coupling agent and 45-73 parts of solvent, wherein the epoxy resin slurry comprises the following raw materials in parts by mass: 20-40 parts of epoxy resin, 10-20 parts of high temperature resistant nano powder, 1-5 parts of dispersing agent and 35-65 parts of solvent; the polyborosilazane prepolymer is polymerized by the following monomers: dihydrocarbyldichlorosilane, alkenyl-containing dichlorosilane, silazane, and boron chloride; the silane coupling agent is a mixed silane coupling agent with epoxy silane coupling agent, amino silane coupling agent and double bond according to the mass ratio of 4-6:1-2:1-2.
2. The polyborosilazane/epoxy composite high temperature resistant corrosion resistant coating according to claim 1, wherein the epoxy resin has an epoxy equivalent of 180-230g/eq and is selected from bisphenol type epoxy resins.
3. The polyborosilazane/epoxy composite high temperature resistant corrosion resistant coating according to claim 1, wherein the epoxy silane coupling agent is at least one selected from the group consisting of 3-glycidoxypropyl trimethoxysilane, 3- (2, 3-glycidoxypropyl) propyltriethoxysilane, 3- (2, 3-glycidoxypropyl) propylmethyldimethoxysilane; the silane coupling agent with amino is at least one selected from gamma-aminopropyl trimethoxy silane, gamma-aminopropyl triethoxy silane, gamma-diethylenetriamine propyl methyl dimethoxy silane and N-2-aminoethyl-3-aminopropyl trimethoxy silane; the silane coupling agent with double bond is at least one selected from vinyl trimethoxy silane, vinyl triethoxy silane and vinyl tri (beta-methoxyethoxy) silane.
4. The polyborosilazane/epoxy composite high temperature resistant and corrosion resistant coating according to claim 1, wherein the particle size of the high temperature resistant nano powder is 10-400nm; at least one selected from the group consisting of nano silicon nitride, nano boron carbide, nano aluminum oxide, nano aluminum nitride, nano boron nitride, nano silicon carbide, nano magnesium oxide, nano zinc oxide and nano titanium dioxide.
5. The polyborosilazane/epoxy composite high temperature resistant and corrosion resistant coating according to claim 1, wherein the particle size of the high temperature resistant nano powder is 50-200nm.
6. The polyborosilazane/epoxy composite high temperature resistant corrosion resistant coating according to claim 1, wherein the polyborosilazane prepolymer is obtained by polymerizing monomers comprising the following components in parts by mass: 10-15 parts of dialkyl dichlorosilane, 8-13 parts of dichlorosilane containing alkenyl, 30-40 parts of silazane and 10-15 parts of boron chloride.
7. The polyborosilazane/epoxy composite high temperature resistant corrosion resistant coating according to claim 6, wherein said dihydrocarbyl dichlorosilane is selected from at least one of dimethyldichlorosilane, diethyldichlorosilane, dipropyldichlorosilane, diphenyldichlorosilane, methylethyldichlorosilane; the dichloro silane containing alkenyl is selected from at least one of methyl vinyl dichloro silane, methyl propenyl dichloro silane and ethyl vinyl dichloro silane; the silazane is at least one selected from hexamethyldisilazane, tetramethyl divinyl disilazane, hexamethyl cyclotrisilazane and octamethyl cyclotetrasilazane.
8. The polyborosilazane/epoxy composite high temperature resistant corrosion resistant coating according to claim 1, wherein the solvent is at least one selected from propylene glycol methyl ether acetate, n-butyl acetate, amyl acetate, methyl isobutyl ketone, methyl amyl ketone; the dispersing agent is polyurethane oily dispersing agent.
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