Carborane-siloxane resin-based ablation-resistant heat-proof coating as well as preparation method and application of carborane-siloxane resin-based ablation-resistant heat-proof coating

Abstract

The invention discloses an ablation-resistant heat-proof coating based on carborane-siloxane resin as well as a preparation method and application of the ablation-resistant heat-proof coating. The ablation-resistant heat-proof coating is prepared from the following raw materials: a carborane-siloxane resin matrix, a catalyst, an antioxidant ablation-resistant powder filler and a ceramic powder filler, the carborane-siloxane resin matrix is selected from at least one of hydroxyl-terminated linear polycarborane siloxane, vinyl functionalized branched polycarborane siloxane and a poly (carborane-silica / silazane) polymer. The invention further discloses a preparation method of the polycarborane-siloxane resin matrix. The performance of the coating in all directions is uniform, the anti-ablation effect of the coating is guaranteed, the coating still has 90% or above of residual weight at 800 DEG C in the air atmosphere, and good anti-ablation performance is shown. And after being ablated at 1000 DEG C for 30 minutes, the steel sheet still has the residual weight of 85% or above, and has good adhesive force with a steel sheet matrix.

Description

Technical Field

[0001] The present invention relates to the preparation of an ablation-resistant heat-resistant coating, and in particular to a novel carborane-siloxane resin-based ablation-resistant heat-resistant coating, a preparation method thereof, and applications thereof. Background Art

[0002] When high-speed aircraft fly through the atmosphere at high speed, the air is subjected to intense compression and friction, converting most of the kinetic energy into heat. This causes the surrounding temperature to rise sharply, resulting in high temperatures, high pressures, and high heat fluxes. To prevent the aircraft from burning in such a harsh environment, effective thermal protection measures must be implemented to ensure structural integrity, protect the payload, and provide specific functions such as shape control, roll control, wave transmission, laser resistance, and stealth.

[0003] Thermal protection ablative coating sacrifices the quality of the material to protect the aircraft from burning out. It has the advantages of high thermal protection efficiency, simple construction and low cost, and has become an effective method to solve the heat protection of various types of aircraft. Summary of the Invention

[0004] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0005] A heat-resistant ablation-resistant coating, the raw materials of which include a carborane-siloxane resin matrix, a catalyst, an antioxidant and ablation-resistant powder filler, and a ceramic powder filler.

[0006] According to an embodiment of the present invention, the carborane-siloxane resin matrix is ​​selected from at least one of hydroxyl terminated linear polycarborane siloxane, vinyl functionalized branched polycarborane siloxane, and poly(carborane-siloxy / silazane) polymer.

[0007] According to an embodiment of the present invention, the hydroxyl-terminated linear polycarborane siloxane is selected from at least one of the substances having the structure shown in Formula 1;

[0008]

[0009] In formula 1, R a and R b Independently selected from C 1-6 Alkyl (for example, methyl), C 6-10 Aryl (e.g., phenyl);

[0010] n is selected from 1 to 4, for example, 2 or 3;

[0011] n is selected from 80 to 300, for example, 100 or 200.

[0012] According to an embodiment of the present invention, the vinyl-functionalized branched polycarborane siloxane is obtained by reacting a carborane monomer derivative and an organosilane monomer in the presence of a Pt catalyst (such as a karsdet-Pt catalyst or an isopropyl alcohol-Pt catalyst).

[0013] According to an exemplary embodiment of the present invention, the vinyl-functionalized branched polycarborane siloxane is selected from at least one of the following formulas (I-1) to (I-5):

[0014]

[0015]

[0016] In formula (I-1) to formula (I-5), n is selected from 1 to 10,000, for example, 10, 100, or 1,000; and m is selected from 0 to 1,000, for example, 1, 10, or 100.

[0017] According to an embodiment of the present invention, the poly(carborane-siloxane / silazane) polymer is selected from the poly(carborane-siloxane / silazane) polymer disclosed in patent document CN102167832A.

[0018] According to an embodiment of the present invention, the catalyst is selected from at least one of karsdet-Pt catalyst, isopropyl alcohol-Pt catalyst, tetraethyl orthosilicate, polysilazane, and KH-CL.

[0019] According to an embodiment of the present invention, the antioxidant and ablation-resistant powder filler is selected from inorganic metal and oxide powders and / or non-metal and oxide powders.

[0020] According to an embodiment of the present invention, the inorganic metal is, for example, at least one selected from aluminum, iron, calcium, and zirconium.

[0021] According to an embodiment of the present invention, the non-metal is selected from at least one of Si, B, and C, for example.

[0022] According to an exemplary embodiment of the present invention, the antioxidant and ablation-resistant powder filler is selected from one or more of aluminum powder, aluminum oxide, clay, calcium carbonate, talc, silica alumina carbon black, mica, wollastonite, kaolin, asbestos, zirconium oxide, magnesium oxide, sodium silicate, feldspar powder, dolomite, boron powder, boron oxide, iron oxide, ferroferric oxide, etc.

[0023] According to an embodiment of the present invention, the ceramic powder filler is selected from any one, two or more of silicon carbide, hafnium carbide, tantalum carbide, zirconium carbide and the like.

[0024] According to an embodiment of the present invention, the amount of the catalyst used is 0.01%-10% by mass of the carborane-siloxane resin matrix, preferably 0.05%-5%.

[0025] According to an embodiment of the present invention, in the antioxidant and ablation-resistant powder filler, the mass ratio of Al:B:Fe is 1:0.2-1.8:0.1-0.9.

[0026] According to an embodiment of the present invention, the mass fraction of the antioxidant and ablation-resistant powder filler in the carborane-siloxane resin matrix is ​​10% to 60%.

[0027] According to an embodiment of the present invention, the mass fraction of the ceramic powder filler in the carborane-siloxane resin matrix is ​​5% to 45%.

[0028] According to an embodiment of the present invention, the ablation-resistant heat-protective coating has a dense structure.

[0029] According to the embodiment of the present invention, the ablation-resistant heat-resistant coating has excellent ablation resistance.

[0030] According to an embodiment of the present invention, the ablation-resistant thermal protection coating has good resistance to neutron and gamma-ray radiation.

[0031] According to an embodiment of the present invention, the ablation-resistant heat-resistant coating still has more than 90% of its residual weight at 800° C. in an air atmosphere.

[0032] According to an embodiment of the present invention, the ablation-resistant heat-protective coating still has a residual weight of more than 85% after being ablated at 1000° C. for 30 minutes.

[0033] According to the embodiment of the present invention, the ablation-resistant and heat-resistant coating has good adhesion to the steel sheet substrate.

[0034] The present invention also provides a method for preparing the above-mentioned ablation-resistant heat-resistant coating, the method comprising: mixing the raw materials of the ablation-resistant heat-resistant coating, adding a curing agent and curing the mixture to obtain the resin matrix;

[0035] The raw materials of the ablation-resistant and heat-resistant coating have the meanings as described above, for example, including a carborane-siloxane resin matrix, a catalyst, an antioxidant and ablation-resistant powder filler, and a ceramic powder filler.

[0036] According to an embodiment of the present invention, the curing agent is selected from at least one of tetraethyl orthosilicate, methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, polysilazane, KH—Cl, and hydrogen-containing silicone oil.

[0037] According to an embodiment of the present invention, the curing conditions are: curing temperature is 30°C-120°C, for example, 100°C; curing time is 15min-24h, for example, 30min, 1h, 5h, 10h.

[0038] The present invention also provides applications of the above-mentioned ablation-resistant and heat-resistant coating, for example, in the fields of aviation, aerospace, shipbuilding, nuclear power, etc.

[0039] Compared with the prior art, the present invention has at least the following beneficial effects:

[0040] First, the resin matrix used in the present invention has excellent ablation resistance; second, the resin matrix is ​​combined with antioxidant, ablation-resistant powder and ceramic powder to give full play to the respective advantages of the three, so that the coating structure after final ablation is dense and has excellent adhesion performance with the bonded substrate, which has the function of maintaining structural integrity and maintaining shape.

[0041] The present invention provides a novel carborane-siloxane resin-based ablation-resistant and heat-resistant coating. The coating prepared by the present invention not only has excellent ablation resistance, but also has excellent tolerance to neutron and gamma-ray radiation, and can be used in aviation, aerospace, shipbuilding, nuclear power and other fields.

[0042] The present invention utilizes a carborane-siloxane resin matrix and various powders to form a uniformly composed ablation-resistant coating. The resulting coating exhibits uniform properties in all directions, ensuring excellent ablation resistance. The coating retains over 90% of its weight at 800°C in air, demonstrating excellent ablation resistance. Even after ablation at 1000°C for 30 minutes, it retains over 85% of its weight and exhibits excellent adhesion to the steel substrate.

[0043] Definitions and Explanations of Terms

[0044] Unless defined otherwise, all technical and scientific terms herein have the same meaning as commonly understood by one of ordinary skill in the art to which the claimed subject matter belongs.

[0045] The term "C 1-20 "Alkyl" is understood to mean a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 20 carbon atoms. For example, "C 1-6The term "alkyl" refers to straight-chain and branched alkyl groups having 1, 2, 3, 4, 5, or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, or 1,2-dimethylbutyl, or isomers thereof.

[0046] The term "C 3-20 "Cycloalkyl" is understood to mean a saturated monocyclic or bicyclic hydrocarbon ring having 3 to 20 carbon atoms, preferably "C 3-12 Cycloalkyl". The term "C 3-12 "Cycloalkyl" is understood to mean a saturated monovalent monocyclic or bicyclic hydrocarbon ring having 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms. 3-12 The cycloalkyl group may be a monocyclic hydrocarbon group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl, or a bicyclic hydrocarbon group such as a decalin ring.

[0047] The term "C 2-20 "Alkenyl" is understood to mean a linear or branched monovalent hydrocarbon radical containing one or more double bonds and having 2 to 20 carbon atoms, preferably "C 2-6 Alkenyl". "C 2-6 "Alkenyl" is understood to mean preferably a linear or branched monovalent hydrocarbon radical which contains one or more double bonds and has 2, 3, 4, 5 or 6 carbon atoms, in particular 2 or 3 carbon atoms ("C 2-3"alkenyl"), it being understood that where the alkenyl contains more than one double bond, the double bonds may be separated from one another or conjugated. The alkenyl is, for example, vinyl, allyl, (E)-2-methylvinyl, (Z)-2-methylvinyl, (E)-but-2-enyl, (Z)-but-2-enyl, (E)-but-1-enyl, (Z)-but-1-enyl, pent-4-enyl, (E)-pent-3-enyl, (Z)-pent-3-enyl. -enyl, (E)-pent-2-enyl, (Z)-pent-2-enyl, (E)-pent-1-enyl, (Z)-pent-1-enyl, hex-5-enyl, (E)-hex-4-enyl, (Z)-hex-4-enyl, (E)-hex-3-enyl, (Z)-hex-3-enyl, (E)-hex-2-enyl, (Z)-hex-2-enyl, (E)-hex-1-enyl, (Z)-hex-1-enyl, isopropenyl, 2-enyl -methylprop-2-enyl, 1-methylprop-2-enyl, 2-methylprop-1-enyl, (E)-1-methylprop-1-enyl, (Z)-1-methylprop-1-enyl, 3-methylbut-3-enyl, 2-methylbut-3-enyl, 1-methylbut-3-enyl, 3-methylbut-2-enyl, (E)-2-methylbut-2-enyl, (Z)-2-methylbut-2-enyl, (E)-1-methylbut-2-enyl 1-ethylprop-1-enyl, 1-propylvinyl, and 1-isopropylvinyl.

[0048] The term aryl is preferably "C 6-20 "Aryl" is understood to mean an aromatic monocyclic, bicyclic or polycyclic hydrocarbon ring having 6 to 20 carbon atoms. The term "C 6-10 "Aryl" is understood to mean preferably a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring ("C 6-14 or a ring having 9 carbon atoms ("C9 aryl"), for example indanyl or indenyl, or a ring having 10 carbon atoms ("C 10 "aryl"), for example tetrahydronaphthyl, dihydronaphthyl or naphthyl. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1These are SEM images of the corrosion-resistant and heat-resistant coating after ablation at 1000°C for 30 minutes; (A) is the SEM of the resin matrix after ablation in Comparative Example 1; (B) is the SEM of the polycarborane siloxane composite filler after ablation in Example 3. DETAILED DESCRIPTION

[0050] [Vinyl-functionalized branched polycarborane siloxane]

[0051] The vinyl functionalized branched polycarborane siloxane is obtained by reacting a carborane monomer derivative and an organic silane monomer under catalyst conditions.

[0052] According to an embodiment of the present invention, the structural formula of the carborane monomer derivative is shown in formula (A):

[0053]

[0054] In formula (A), M is selected from the residue of carborane, for example, -CB 10 H 10 C-; m is selected from 0 to 1000, for example, 1, 10, 100;

[0055] R1, R2, R3, R4, R5 are the same or different and are independently selected from H, unsubstituted or optionally substituted by one, two or more R a Substituted C 1-20 Alkyl, C 2-20 Alkenyl, C 3-20 At least one of cycloalkyl and aryl; preferably, said R1, R2, are independently selected from H, unsubstituted or optionally substituted by one, two or more R a Substituted C 1-10 Alkyl, C 2-10 Alkenyl, C 3-10 Cycloalkyl and C 6-20 at least one of aromatic groups;

[0056] Every R a The same or different, independently selected from halogen, -CN, C 1-20 Alkyl, C 2-20 Alkenyl, C 1-20 Alkoxy and C 3-20 At least one of cycloalkyl; preferably, R a Can be selected from halogen, -CN, C 1-10 Alkyl, C 2-10 Alkenyl and C 3-10 At least one of cycloalkyl; illustratively, R a It may be selected from at least one of F, Cl, Br, -CN, -CH3, -C2H5 and -CH=CH2;

[0057] For example, R1, R2, R3, R4, and R5 can be independently selected from at least one of methyl, ethyl, vinyl, phenyl, tolyl, and naphthyl.

[0058] Preferably, in formula (A), M is selected from the group consisting of an ortho-carborane residue, a meta-carborane residue, and a para-carborane residue.

[0059] Exemplarily, the structural formula of the meta-carborane residue is Where * is the connection point.

[0060] Illustratively, the structural formula of the residue of ortho-carborane is Where * is the connection point.

[0061] Exemplarily, the structural formula of the residue of para-carborane is Where * is the connection point.

[0062] According to an embodiment of the present invention, the carborane monomer derivative is, for example, at least one selected from the compounds having formulae (A-1) to (A-3):

[0063]

[0064] Here, m is selected from 0 to 1000, for example, 1, 10, or 100.

[0065] According to an embodiment of the present invention, the organic silane monomer is selected from one or more siloxanes such as 3,5-bis(dimethylsiloxy)-1,1,7,7-tetramethyl-3,5-diphenyltetrasiloxane, tetramethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, 3,5-bis(dimethylsiloxy)-1,1,7,7-tetramethyl-3,5-diphenyltetrasiloxane, etc.

[0066] According to an embodiment of the present invention, the molar ratio of the carborane monomer derivative to the organosilane monomer is 1:(0.2-2.5), for example, 1:0.5, 1:1, 1:1.5, or 1:2.

[0067] According to an exemplary embodiment of the present invention, the structure of the vinyl-functionalized branched polycarborane siloxane is selected from at least one of the following formulas (I-1) to (I-5):

[0068]

[0069]

[0070] In formula (I-1) to formula (I-5), n is selected from 1 to 10,000, for example, 10, 100, or 1,000; and m is selected from 0 to 1,000, for example, 1, 10, or 100.

[0071] [Synthesis method]

[0072] The present invention also provides a method for synthesizing the vinyl-functionalized branched polycarborane siloxane, which comprises the following steps:

[0073] A. Preparation of carborane monomer derivatives;

[0074] B. Prepare organosilane monomer;

[0075] C. Synthesis of vinyl-functionalized branched polycarborane siloxane: The carborane monomer derivative of step A is mixed with the organosilicon silane monomer of step B, a catalyst is added, and the mixture is reacted under an inert atmosphere to obtain the vinyl-functionalized branched polycarborane siloxane.

[0076] According to an embodiment of the present invention, in step A, the preparation method of the carborane monomer derivative can be any method known in the art, as long as the carborane monomer derivative can be obtained. The carborane monomer derivative has the meaning as described above.

[0077] According to an exemplary embodiment of the present invention, the preparation method of the carborane monomer derivative is as follows:

[0078] (1) Lithiating a carborane monomer with butyl lithium to obtain a first intermediate;

[0079] (2) reacting the first intermediate with chlorosilane under certain conditions to obtain a second intermediate;

[0080] (3) The second monomer is reacted with an appropriate amount of water to obtain a carborane monomer derivative through hydrolysis.

[0081] Preferably, the carborane monomer is selected from ortho-carborane, meta-carborane and para-carborane.

[0082] For example, the ortho-carborane is

[0083] Exemplarily, the meta-carborane is

[0084] Exemplarily, the para-carborane is

[0085] Preferably, the first intermediate is selected from at least one of the following structures:

[0086]

[0087] Preferably, the second intermediate is selected from at least one of the following structures:

[0088]

[0089] Preferably, in the method for preparing the carborane monomer derivative, in step (1), the reaction temperature is -10 to 50° C., and the reaction time is 30 min to 5 h.

[0090] Preferably, in the preparation method of the carborane monomer derivative, a reaction solvent can also be added in steps (1) to (3), and the reaction solvent is one or a mixed solution of n-hexane, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dioxane, tetrahydropyran, toluene, n-heptane, etc.

[0091] Preferably, in step (2), the reaction temperature is -10 to 80°C, and the reaction time is 30 min to 5 h.

[0092] Preferably, in step (3), the temperature of the hydrolysis reaction is -10 to 60° C., and the time of the hydrolysis reaction is 20 min to 5 h.

[0093] According to an embodiment of the present invention, in step B, the organosilane monomer has the meaning as described above, for example, one or more selected from silanes such as 3,5-bis(dimethylsiloxy)-1,1,7,7-tetramethyl-3,5-diphenyltetrasiloxane, tetramethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, 3,5-bis(dimethylsiloxy)-1,1,7,7-tetramethyl-3,5-diphenyltetrasiloxane, etc.

[0094] According to an embodiment of the present invention, in step C, the catalyst is selected from one or more of chloroplatinic acid, an isopropyl alcohol-coordinated Pt catalyst, tris(pentafluorophenyl)borane, and boron trifluoride. Exemplarily, the Pt catalyst can be a catalyst known in the art, such as a Karstedt catalyst.

[0095] According to an embodiment of the present invention, in step C, the solvent is one or more of toluene, xylene, heptane, dioxane, tetrahydrofuran, tetrahydropyran, n-hexane, petroleum ether, diethylene glycol dimethyl ether, and ethylene glycol dimethyl ether.

[0096] According to an embodiment of the present invention, in step C, the molar ratio of the carborane monomer derivative to the organosilicon silane monomer is 1:(0.2-2.5), for example, 1:0.5, 1:1, 1:1.5, or 1:2.

[0097] According to an embodiment of the present invention, in step C, the mass fraction of the catalyst is 0.1% to 8%.

[0098] According to an embodiment of the present invention, in step C, a solvent may be further added.

[0099] According to an embodiment of the present invention, in step C, the mass fraction of the solvent is 50% to 200%.

[0100] According to an embodiment of the present invention, in step C, the reaction conditions are: reaction temperature is -20°C to 150°C, and reaction time is 30 min to 24 h.

[0101] According to an embodiment of the present invention, the synthesis method further comprises: D. After the reaction of step C is completed, adding an organic solvent to the reaction system for extraction, standing to separate the layers, removing the solvent layer, and then adding water to wash and neutralize;

[0102] According to an embodiment of the present invention, the synthesis method further comprises: E. high-temperature vacuum drying: vacuum rotary evaporating the product obtained in step D, then subjecting it to high-temperature vacuum treatment, and cooling it to room temperature.

[0103] According to an embodiment of the present invention, in step D, the organic extractant is one or more of ethanol, methanol, toluene, diethanol, tetrahydrofuran, n-hexane, petroleum ether, etc.

[0104] According to an embodiment of the present invention, in step E, the vacuum rotary evaporation conditions can be selected from those known in the art, such as 40-100° C. for 0.5-2 h to remove the solvent.

[0105] According to an embodiment of the present invention, in step E, the high temperature vacuum conditions can be selected from methods known in the art, such as 110-160° C. and 1-24 h.

[0106] The technical solutions of the present invention will be described in further detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are encompassed within the scope of protection that the present invention is intended to protect.

[0107] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0108] Preparation Example 1

[0109] Hydroxyl-terminated linear polycarborane siloxane was prepared with reference to patent document CN102167832B as follows:

[0110] Dissolve 1 mol of carborane in an ether solution, stir thoroughly under nitrogen, and dropwise add a butyl lithium-hexane solution (2 mol of butyl lithium added). After the reaction is complete, add 2 mol of diorganodichlorosilane dropwise to the reaction solution while stirring and in an ice bath. After the reaction is complete, fractionate to obtain purified bis(diorganochlorosilane)carborane. Add excess water to the ether solution, stir thoroughly, and finally recrystallize and purify to obtain the corresponding bis(hydroxydiorganosilane)carborane, which is a hydroxyl-terminated linear polycarboranesiloxane. The reaction equation is as follows:

[0111]

[0112] Preparation Example 2

[0113] The preparation method of vinyl functionalized branched polycarborane siloxane is as follows:

[0114] A: The preparation method of the meta-carborane monomer derivative specifically includes:

[0115] (1) Under nitrogen protection, 11 ml of butyl lithium (2.4 mol / L) was placed in a 150 mL round-bottom flask, diluted with 50 mL of tetrahydrofuran, and 20 mL of a tetrahydrofuran solution of meta-carborane (1.44 g) was added dropwise at room temperature. After the addition was complete, the reaction was continued at room temperature for 3 h to obtain the first intermediate lithiated carborane;

[0116] (2) Then, dimethyldichlorosilane was added, and the molar ratio of meta-carborane to dimethyldichlorosilane was 1:2; the reaction was carried out at room temperature for 15 hours, and then 5 ml of deionized water was added and hydrolyzed at 0°C for 30 minutes to obtain the second intermediate hydroxycarborane. The reaction scheme is as follows: Figure 1 As shown; extraction, concentration of the organic phase and recrystallization can obtain 2.1g of the second intermediate hydroxycarborane;

[0117] (3) Then, 1.0 g of hydroxycarborane, 0.92 g of tetramethyldisiloxane, 0.3% of trifluoromethanesulfonic acid, and 30 ml of toluene were reacted at 80° C. for 15 h to obtain 2 g of the target product 1,7-bis(hydrogen tetramethyldisiloxane silyl)-carborane (HCB-2), which was recorded as a meta-carborane monomer derivative.

[0118] B: Prepare the organosilane monomer: select tetramethyltetravinylcyclotetrasiloxane;

[0119] C: Synthesis of silicone resin:

[0120] Separately, 1 g of the meta-carborane monomer derivative in step A and 1.2 g of the organosilane monomer in step B were mixed in a 25 ml single-necked bottle, and 0.5% Pt catalyst (Karstedt catalyst, commercially available) and 5 ml of toluene solvent were added. The mixture was stirred at 60 ° C. under N2 atmosphere for 5 h to obtain a crude vinyl-functionalized branched polycarborane siloxane.

[0121] D: Extraction and washing of products:

[0122] The crude vinyl-functionalized branched polycarboranesiloxane obtained in step C was washed three times with toluene and ethanol.

[0123] E: High temperature vacuum drying:

[0124] The product after washing in step D was subjected to rotary evaporation at 60° C. for 1 h to remove the solvent, and then placed in a vacuum oven at 80° C. for 4 h and cooled to obtain a vinyl-functionalized branched polycarborane siloxane with a viscosity of 1500 mPa.s, which was set aside.

[0125] Example 1

[0126] The preparation method of the corrosion-resistant and heat-resistant coating is as follows:

[0127] 5 g of hydroxyl-terminated linear polycarborane siloxane, 1 g of antioxidant and ablation-resistant powder filler aluminum oxide, and 0.05 g of KH—Cl curing agent were applied on a steel sheet using a 2 mm thick doctor blade and cured at 100° C. for 6 h to obtain the coating.

[0128] Example 2

[0129] 5 g of hydroxyl-terminated linear polycarborane siloxane, 1 g of antioxidant and ablation-resistant powder filler aluminum oxide, 1 g of glass powder, 0.5 g of ceramic powder filler hafnium carbide, and 0.05 g of KH-Cl curing agent were taken, and then coated on a steel sheet with a 2 mm thick scraping rod and cured at 80° C. for 4 hours to obtain the coating.

[0130] Example 3

[0131] 5 g of hydroxyl-terminated linear polycarborane siloxane, 1 g of aluminum oxide (anti-oxidation and ablation-resistant powder filler), 1 g of glass powder, 0.5 g of hafnium carbide (ceramic powder filler), 0.25 g of iron oxide, and 0.05 g of KH—Cl curing agent were taken, and then coated on a steel sheet with a 2 mm thick scraping rod and cured at 60° C. for 6 hours to obtain the coating.

[0132] Example 4

[0133] 5 g of vinyl-functionalized branched polycarborane siloxane, 1 g of antioxidant and ablation-resistant powder filler aluminum oxide, 0.5 g of ceramic powder filler hafnium carbide, and 0.05 g of KH—Cl curing agent were taken, and then coated on a steel sheet with a 2 mm thick doctor blade and cured at 110° C. for 2 h to obtain the coating.

[0134] Example 5

[0135] 5 g of vinyl-functionalized branched polycarborane siloxane, 1 g of antioxidant and ablation-resistant powder filler aluminum oxide, 0.5 g of ceramic powder filler hafnium carbide, and 0.015 g of Pt catalyst were taken, and then coated on a steel sheet with a 2 mm thick doctor blade and cured at 120° C. for 1 hour to obtain the coating.

[0136] Example 6

[0137] 5 g of vinyl-functionalized branched polycarborane siloxane, 1 g of talc powder (anti-oxidation and ablation-resistant filler), 0.5 g of kaolin, 0.5 g of hafnium nitride (ceramic powder filler), and 0.02 g of Pt catalyst were taken, and then coated on a steel sheet with a 2 mm thick doctor blade and cured at 60° C. for 5 h to obtain the coating.

[0138] Example 7

[0139] Take 5 g of vinyl-functionalized branched polycarborane siloxane, 0.5 g of mica powder as an antioxidant and ablation-resistant powder filler, 0.5 g of asbestos, 0.2 g of magnesium oxide, 0.5 g of ceramic powder filler zirconium carbide, and 0.04 g of Pt catalyst, then apply it on a steel sheet with a 2 mm thick doctor blade and cure it at 50° C. for 12 hours to obtain the coating.

[0140] Example 8

[0141] Take 5 g of vinyl-functionalized branched polycarborane siloxane, 1 g of anti-oxidation and ablation-resistant powder filler silicon aluminum carbon black, 0.4 g of sodium silicate, 0.5 g of feldspar powder, 0.5 g of ceramic powder filler tantalum carbide, 0.5 g of silicon carbide, and 0.05 g of Pt catalyst, then apply it on a steel sheet with a 2 mm thick scraping rod and cure it at 70°C for 10 hours to obtain the coating.

[0142] Comparative Example 1

[0143] 5 g of hydroxyl-terminated polydimethylsiloxane (90,000 g / mol), 1 g of aluminum oxide (anti-oxidation and ablation-resistant powder filler), 1 g of glass powder, 0.5 g of hafnium carbide (ceramic powder filler), 0.25 g of iron oxide, and 0.05 g of KH-Cl curing agent were taken, and then coated on a steel sheet with a 2 mm thick scraping rod and cured at 60° C. for 6 hours to obtain the coating.

[0144] Test Example 1

[0145] The coatings of Examples 1-8 were tested for TGA, ablation performance, and adhesion to steel sheets. The test results are recorded in Table 1, where:

[0146] 1) The test method for residual weight is: TGA at 800℃ and calculate the residual weight;

[0147] 2) Ablation performance: Calculate the residual weight of the sample after ablation at 800°C for 30 minutes;

[0148] The residual weight of the sample was calculated after ablation at 1000°C for 30 min;

[0149] 3) The adhesion test method is: use an adhesion tester to draw a circular line on the paint film sample, and evaluate the adhesion according to the integrity of the paint film within the range of the circular line scratch, which is divided into 1 to 7 levels, among which level 1 is the best, the paint film is intact; level 7 is the worst, the paint film is completely damaged.

[0150] Table 1

[0151]

[0152] The above describes exemplary embodiments of the present invention. However, the scope of protection of this application is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. An ablation-resistant heat-resistant coating, characterized in that: The raw materials of the ablation-resistant and heat-resistant coating include a carborane-siloxane resin matrix, a catalyst, an antioxidant and ablation-resistant powder filler, and a ceramic powder filler; The carborane-siloxane resin matrix is ​​selected from at least one of a hydroxyl-terminated linear polycarborane siloxane, a vinyl-functionalized branched polycarborane siloxane, and a poly(carborane-siloxy / silazane) polymer.

2. The ablation-resistant heat-resistant coating according to claim 1, characterized in that: The hydroxyl-terminated linear polycarborane siloxane is selected from at least one of the substances having the structure shown in Formula 1; In formula 1, R a and R b Independently selected from C 1-6 Alkyl, C 6-10 aryl; n is selected from 1 to 4; n is selected from 80 to 300. Preferably, the vinyl-functionalized branched polycarborane siloxane is obtained by reacting a carborane monomer derivative and an organosilane monomer in the presence of a Pt catalyst.

3. The ablation-resistant heat-resistant coating according to claim 1 or 2, characterized in that: The catalyst is selected from at least one of karsdet-Pt catalyst, isopropyl alcohol-Pt catalyst, tetraethyl orthosilicate, polysilazane, and KH-CL. Preferably, the antioxidant and ablation-resistant powder filler is selected from inorganic metal and oxide powders and / or non-metal and oxide powders. Preferably, the ceramic powder filler is selected from any one, two or more of silicon carbide, hafnium carbide, tantalum carbide and zirconium carbide.

4. The ablation-resistant heat-resistant coating according to any one of claims 1 to 3, characterized in that: The inorganic metal is selected from at least one of aluminum, iron, calcium and zirconium. Preferably, the non-metal is selected from at least one of Si, B and C.

5. The ablation-resistant heat-resistant coating according to any one of claims 1 to 4, characterized in that: The amount of the catalyst used is 0.01%-10% of the mass of the carborane-siloxane resin matrix. Preferably, in the antioxidant and ablation-resistant powder filler, the mass ratio of Al:B:Fe is 1:0.2-1.8:0.1-0.

9.

6. The ablation-resistant heat-resistant coating according to any one of claims 1 to 5, characterized in that: The mass fraction of the antioxidant and ablation-resistant powder filler in the carborane-siloxane resin matrix is ​​10% to 60%. Preferably, the mass fraction of the ceramic powder filler in the carborane-siloxane resin matrix is ​​5% to 45%.

7. The ablation-resistant heat-resistant coating according to any one of claims 1 to 6, characterized in that: The ablation-resistant and heat-resistant coating has a dense structure. Preferably, the ablation-resistant and heat-resistant coating has excellent ablation resistance. Preferably, the ablation-resistant heat-protective coating has good resistance to neutron and gamma-ray radiation. Preferably, the ablation-resistant heat-resistant coating still has more than 90% of its residual weight at 800° C. in an air atmosphere. Preferably, the ablation-resistant heat-protective coating still has a residual weight of more than 85% after ablation at 1000° C. for 30 minutes. Preferably, the ablation-resistant and heat-resistant coating has good adhesion to the steel sheet substrate.

8. The method for preparing the ablation-resistant and heat-resistant coating according to any one of claims 1 to 7, characterized in that: The preparation method comprises: mixing the raw materials of the ablation-resistant and heat-resistant coating, adding a curing agent and curing the mixture to obtain the resin matrix.

9. The preparation method according to claim 8, characterized in that The curing agent is selected from at least one of tetraethyl orthosilicate, methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, polysilazane, KH-Cl, and hydrogen-containing silicone oil. Preferably, the curing conditions are: curing temperature of 30° C.-120° C.; curing time of 15 min-24 h.

10. Use of the ablation-resistant and heat-resistant coating according to any one of claims 1 to 7 in the fields of aviation, aerospace, shipbuilding or nuclear power.

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