High-temperature-resistant zirconium-titanium-carbon ceramic precursor and preparation method thereof

Abstract

The invention provides a high-temperature-resistant zirconium-titanium-carbon ceramic precursor and a preparation method thereof, and belongs to the technical field of ceramic materials.The method comprises the steps that a zirconium carbide ceramic precursor is prepared; preparing a sodium cyclopentadiene solution; preparing titanocene dichloride; preparing a titanium intermediate 1 and a titanium intermediate 2; uniformly mixing the titanium intermediate 1, the titanium intermediate 2 and an organic solvent, and reacting at 58-62 DEG C for 1.6-4.3 hours to obtain a titanium carbide ceramic precursor; uniformly mixing the zirconium carbide ceramic precursor, the titanium carbide ceramic precursor and an organic solvent, and reacting to obtain the high-temperature-resistant composite zirconium-titanium-carbon ceramic precursor. According to the invention, the uniformity of the high-temperature-resistant composite zirconium-titanium-carbon ceramic precursor and the stability of high-temperature mechanical properties can be improved.

Description

Technical Field

[0001] The invention relates to the technical field of ceramic materials, and in particular to a high-temperature resistant zirconium-titanium-carbon ceramic precursor and a preparation method thereof. Background Art

[0002] High temperature resistant ceramics are materials that can maintain their physical and chemical properties under high temperature conditions and have broad application prospects, such as in aviation, aerospace, nuclear energy, energy conservation and environmental protection. Zirconium-titanium-carbon ceramics are a relatively new high-performance ceramic material with the advantages of high strength, high hardness, and high thermal stability. In order to prepare zirconium-titanium-carbon ceramics, it is necessary to first prepare its precursor and then sinter it at high temperature to obtain the final ceramic material.

[0003] Currently, there are many methods for preparing zirconium-titanium-carbon ceramic precursors, such as sol-gel method, hydrothermal method, polymer initiation method, etc., but these methods have some problems: for example, zirconium-titanium-carbon ceramic precursors are easy to precipitate or aggregate, resulting in a decrease in the stability of their high-temperature mechanical properties, thereby affecting the uniformity and performance of the final ceramic material; the preparation process is cumbersome and time-consuming. Summary of the invention

[0004] In view of this, one of the purposes of the present invention is to overcome the shortcomings of the above-mentioned prior art and provide a method for preparing a high-temperature resistant composite zirconium-titanium-carbon ceramic precursor, which can improve the uniformity of the high-temperature resistant composite zirconium-titanium-carbon ceramic precursor and the stability of the high-temperature mechanical properties to meet the high-temperature application scenarios in the aerospace field.

[0005] A second object of the present invention is to provide a high temperature resistant composite zirconium-titanium-carbon ceramic precursor.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] A method for preparing a high temperature resistant composite zirconium-titanium-carbon ceramic precursor, the preparation method comprising the following steps:

[0008] Step S1, in a nitrogen atmosphere, zirconium tetrachloride and an organic solvent are uniformly mixed, and then ethylenediamine and diallylamine are added to react at a temperature of 20 to 100° C. for 1 to 2 hours, and then thermally cured and dried in sequence to obtain a zirconium carbide ceramic precursor;

[0009] In the step S1, the mass ratio of ethylenediamine, zirconium tetrachloride and diallylamine is 1-10:1-5:1;

[0010] The mass ratio of the organic solvent to zirconium tetrachloride is 5 to 10:1;

[0011] Step S2, mixing metallic sodium, cyclopentadiene and an organic solvent uniformly, and reacting at -10 to -5°C for 1.8 to 2.2 hours to obtain a sodium cyclopentadiene solution;

[0012] In the step S2, the mass ratio of the metallic sodium to cyclopentadiene is 1-3:3-1;

[0013] The mass ratio of the organic solvent to the metallic sodium is 1 to 10:1;

[0014] Step S3, mixing titanium tetrachloride and an organic solvent uniformly and stirring them into a suspension, and slowly dripping a sodium cyclopentadienyl solution into the suspension at a temperature of -10 to -5°C under a nitrogen atmosphere, then removing the residue, heating and recovering the organic solvent, and purifying to obtain dichlorotitanocene;

[0015] In the step S3, the mass ratio of titanium tetrachloride, sodium cyclopentadiene and organic solvent is 1:2-6:2-30;

[0016] Step S4, stirring and dispersing dichlorotitanocene and an organic solvent to obtain a first mixed solution; and adding reagent 1 dropwise to the first mixed solution at a temperature of -10 to -5°C under nitrogen protection, heating the mixture to a temperature of 0 to 50°C after the addition is complete, reacting for 2 to 6 hours, removing the residue, and obtaining a titanium intermediate 1;

[0017] In the step S4, the mass ratio of the dichlorotitanium, the organic solvent and the reagent 1 is 1:1-120:1-30;

[0018] Step S5, stirring and dispersing dichlorotitanocene and an organic solvent to obtain a second mixed solution; adding reagent 2 dropwise to the second mixed solution at a temperature of -25 to -20°C, then introducing hydrogen, continuing stirring for 3.8 to 4.2 hours, removing the residue, adding a polyolefin with a molecular weight of 2000 to 500000, slowly heating to 78 to 83°C and reacting for 1.8 to 2.2 hours to obtain a titanium intermediate 2;

[0019] In the step S5, the mass ratio of the dichlorotitanium, the organic solvent, the reagent 2 and the polyolefin is 1:1-400:1-20:2-10;

[0020] Step S6, uniformly mixing titanium intermediate 1, titanium intermediate 2 and an organic solvent, and reacting at 58-62° C. for 1.6-4.3 hours to obtain a titanium carbide ceramic precursor;

[0021] In the step S6, the mass ratio of the titanium intermediate 1, the titanium intermediate 2 and the organic solvent is 1-10:1:4-50;

[0022] Step S7, according to the mass ratio of 1-10:1:8-90, the zirconium carbide ceramic precursor, the titanium carbide ceramic precursor and the organic solvent are mixed uniformly, and reacted at 50-70° C. for 3-5 hours, and then heated to 80-100° C. to recover the organic solvent to obtain a high temperature resistant composite zirconium titanium carbon ceramic precursor.

[0023] Furthermore, in the step S1, the thermal curing temperature is 150 to 300° C. and the time is 1 to 10 hours;

[0024] In the step S1, the drying temperature is 150-300°C and the drying time is 3-8 hours.

[0025] Furthermore, in the step S1, the thermal curing temperature is 190 to 260° C. and the time is 4 to 8 hours;

[0026] In the step S1, the drying temperature is 170-240° C. and the drying time is 5-7 hours.

[0027] Furthermore, in the steps S1 to S7, the organic solvent includes one or more of benzene, toluene, dichloromethane, tetrahydrofuran, anhydrous ether, DMF, anhydrous methanol, anhydrous ethanol, ethyl acetate and N-methylpyrrolidone.

[0028] Further, in step S4, the reagent 1 is one or more of formic acid, tetrahydrofuran, acetone, chloroform, dichloromethane, chloroform, acetylacetone, n-hexane, cyclohexane, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, carbon tetrachloride, methanol, ethanol, isopropane, tert-butanol, toluene and xylene.

[0029] Further, in step S5, the reagent 2 includes one or more of methyl lithium, ethyl lithium, propyl lithium, butyl lithium, vinyl magnesium bromide, n-propenyl magnesium bromide, isopropenyl magnesium bromide, n-butenyl magnesium bromide, isobutenyl magnesium bromide, n-pentenyl magnesium bromide, and isopentenyl magnesium bromide.

[0030] Furthermore, in the step S5, the molecular weight of the polyolefin is 8,000 to 300,000.

[0031] Furthermore, in the step S5, the molecular weight of the polyolefin is 10,000 to 200,000.

[0032] Furthermore, in step S5, the polyolefin includes one or more of polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, poly-1-pentene, poly-1-hexene and poly-1-octene.

[0033] In order to achieve the second objective above, the present invention adopts the following technical solution:

[0034] A high temperature resistant composite zirconium-titanium-carbon ceramic precursor is prepared by the above-mentioned preparation method.

[0035] The beneficial effects of the present invention are:

[0036] The invention obtains a zirconium carbide ceramic precursor by reacting ethylenediamine, zirconium tetrachloride and diallylamine in an organic solvent and a nitrogen atmosphere; obtains dichlorotitanocene by reacting sodium cyclopentadienyl and titanium tetrachloride in an organic solvent; obtains titanium intermediate 1 by using dichlorotitanocene, an organic solvent and a reagent 1; obtains titanium intermediate 2 by using dichlorotitanocene, an organic solvent, a reagent 2 and a polyolefin; obtains titanium carbide ceramic precursor by mixing titanium intermediate 1, titanium intermediate 2 and an organic solvent; and then mixes the zirconium carbide ceramic precursor, the titanium carbide ceramic precursor and an organic solvent, performs polymer precursor impregnation cracking, and obtains zirconium titanium carbon ceramic. Ceramic precursor materials can achieve the structure and morphology control of the precursor, improve the uniformity of the high-temperature resistant composite zirconium-titanium-carbon ceramic precursor and the stability of the high-temperature mechanical properties to meet the high-temperature application scenarios in the aerospace field; the present invention improves the preparation efficiency, reduces the cost, improves the material performance, and promotes the technology development and application promotion in this field; the present invention improves the multi-phase ceramic precursor material, the process is simple, the cost is low, and the ceramic yield is high, the thermal stability is good, the oxidation resistance, heat resistance and corrosion resistance are excellent, and it shows more excellent performance in corrosion resistance, oxidation resistance and other aspects, and has good practical application value in the field of ultra-high temperature ceramics. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is a scanning electron microscope image of the high temperature resistant composite zirconium titanium carbon precursor 1400°C ceramic product in Example 1;

[0038] Figure 2 This is a TGA curve diagram of the high temperature resistant composite zirconium titanium carbon precursor in Example 1;

[0039] Figure 3 This is the DSC curve of the high temperature resistant composite zirconium-titanium-carbon precursor in Example 1. DETAILED DESCRIPTION

[0040] The present invention will be further described below in conjunction with specific implementation modes.

[0041] Embodiment 1:

[0042] (1) Under nitrogen protection, zirconium tetrachloride and organic solvent tetrahydrofuran are mixed uniformly to obtain a mixed solution, and then ethylenediamine and diallylamine are added to the mixed solution to react at 20°C for 2 hours, and finally, after thermal curing at 150°C for 1 hour, it is dried at 150°C for 1 hour to obtain a zirconium carbide ceramic precursor. The mass ratio of ethylenediamine, zirconium tetrachloride and diallylamine is 1:1:1. The mass ratio of tetrahydrofuran and zirconium tetrachloride is 10:1.

[0043] (2) Sodium and cyclopentadiene are reacted with an organic solvent, tetrahydrofuran, for 1.8 hours to obtain a sodium cyclopentadiene solution, wherein the mass ratio of metallic sodium to cyclopentadiene is 1:3, and the volume mass ratio of tetrahydrofuran to metallic sodium is 10:1.

[0044] (3) Under nitrogen protection, titanium tetrachloride and organic solvent tetrahydrofuran are mixed uniformly in a three-necked flask, stirred into a suspension, and sodium cyclopentadienyl solution is added dropwise at -10°C. After the addition is completed, the residue is removed, and the organic solvent tetrahydrofuran is recovered by heating, and purified to obtain dichlorotitanocene. The volume mass ratio of titanium tetrachloride, sodium cyclopentadienyl in the sodium cyclopentadienyl solution, and tetrahydrofuran is 1:3:10.

[0045] (4) Titanocene dichloride and an organic solvent, tetrahydrofuran, were stirred and dispersed in a three-necked flask to obtain a first mixed solution. Formic acid was slowly added dropwise at -10°C under nitrogen protection, and then the temperature was raised to 0°C for reaction for 2 hours. After removing the residue, titanium intermediate 1 was obtained. The mass ratio of titanocene dichloride, tetrahydrofuran and formic acid was 1:4:1.

[0046] (5) Titanocene dichloride and tetrahydrofuran were stirred and dispersed to obtain a second mixed solution; methyl lithium was slowly added dropwise to the second mixed solution at -25°C, and then hydrogen was introduced, and stirring was continued for 4 hours until the reaction was complete. After removing the residue, 2000 g of polyethylene was added to the reaction solution, and the temperature was slowly raised to 80°C (78-83°C) for reaction for 2 hours to obtain titanium intermediate 2. The mass ratio of titanocene dichloride, tetrahydrofuran, methyl lithium and polyethylene was 1:100:1:2.

[0047] (6) Under anhydrous and oxygen-free conditions, titanium intermediate 1, titanium intermediate 2 and organic solvent tetrahydrofuran are mixed evenly in a three-necked flask, and reacted at 60° C. for 4 hours to obtain a titanium carbide ceramic precursor. The mass ratio of titanium intermediate 1, titanium intermediate 2 and tetrahydrofuran is 1:1:4.

[0048] (7) The obtained zirconium carbide ceramic precursor, titanium carbide ceramic precursor and organic solvent tetrahydrofuran are stirred evenly in a reaction kettle, and a zirconium titanium carbon ceramic precursor is obtained after the reaction is complete. The mass ratio of the zirconium carbide ceramic precursor, the titanium carbide ceramic precursor and tetrahydrofuran is 1:1:10.

[0049] In an argon atmosphere, the obtained zirconium-titanium-carbon ceramic precursor was cured and then subjected to pyrolysis tests at 1400°C and 1600°C, respectively. The ceramic yields at 1400°C and 1600°C were calculated to be 45.31% and 38.63%, respectively. The bending strengths of the zirconium-titanium-carbon ceramic precursor at 900°C and 1600°C were 521MPa and 607MPa, respectively. The scanning electron microscope, TGA curve and DSC curve of the high temperature resistant composite zirconium-titanium-carbon precursor 1400°C ceramic product of this embodiment are shown in Figure 2. Figure 1 , 2 and 3.

[0050] Embodiment 2:

[0051] (1) Under nitrogen protection, zirconium tetrachloride and organic solvent benzene are mixed uniformly to obtain a mixed solution, and then ethylenediamine and diallylamine are added to the mixed solution to react at 100°C for 1 hour, and finally, after thermal curing at 300°C for 10 hours, the mixture is dried at 300°C for 10 hours to obtain a zirconium carbide ceramic precursor. The mass ratio of ethylenediamine, zirconium tetrachloride and diallylamine is 10:5:1. The mass ratio of benzene to zirconium tetrachloride is 5:1.

[0052] (2) Sodium, cyclopentadiene and organic solvent benzene are mixed evenly and reacted at -5°C for 2.2 hours to obtain a sodium cyclopentadiene solution, wherein the mass ratio of metallic sodium to cyclopentadiene is 3:1, and the volume mass ratio of benzene to metallic sodium is 1:1.

[0053] (3) Under nitrogen protection, titanium tetrachloride and organic solvent benzene are mixed uniformly in a three-necked flask, stirred into a suspension, and sodium cyclopentadienyl solution is added dropwise at -5°C. After the addition is completed, the residue is removed, and the organic solvent tetrahydrofuran is recovered by heating, and purified to obtain dichlorotitanocene. The volume mass ratio of titanium tetrachloride, sodium cyclopentadienyl in the sodium cyclopentadienyl solution and benzene is 1:2:2.

[0054] (4) Titanocene dichloride and an organic solvent, benzene, were stirred and dispersed in a three-necked flask to obtain a first mixed solution. Acetone was slowly added dropwise at -5°C under nitrogen protection, and then the temperature was raised to 50°C for reaction for 6 hours. After removing the residue, titanium intermediate 1 was obtained. The mass ratio of titanocene dichloride, benzene and acetone was 1:120:30.

[0055] (5) Titanocene dichloride and benzene were stirred and dispersed to obtain a second mixed solution; ethyl lithium was slowly added dropwise to the second mixed solution at -20°C, and then hydrogen was introduced, and stirring was continued for 3.8 hours until the reaction was complete. After removing the residue, 500,000 polypropylene was added to the reaction solution, and the temperature was slowly raised to 80°C for reaction for 2 hours to obtain titanium intermediate 2. The mass ratio of titanocene dichloride, benzene, ethyl lithium and polypropylene was 1:400:20:10.

[0056] (6) Under anhydrous and oxygen-free conditions, titanium intermediate 1, titanium intermediate 2 and organic solvent benzene are mixed evenly in a three-necked flask, and reacted at 62° C. for 4.3 h to obtain a titanium carbide ceramic precursor. The mass ratio of titanium intermediate 1, titanium intermediate 2 and benzene is 10:1:50.

[0057] (7) The obtained zirconium carbide ceramic precursor, titanium carbide ceramic precursor and organic solvent benzene are stirred evenly in a reaction kettle, and a zirconium-titanium-carbon ceramic precursor is obtained after the reaction is complete. The mass ratio of the zirconium carbide ceramic precursor, the titanium carbide ceramic precursor and benzene is 10:1:90.

[0058] In an argon atmosphere, the prepared zirconium-titanium-carbon ceramic precursor was cured and then subjected to pyrolysis tests at 1400°C and 1600°C, and the ceramic yields at 1400°C and 1600°C were calculated to be 45.87% and 38.48%, respectively. The bending strengths of the zirconium-titanium-carbon ceramic precursor at 900°C and 1600°C were 526MPa and 605MPa, respectively.

[0059] Embodiment 3:

[0060] (1) Under nitrogen protection, zirconium tetrachloride and organic solvent toluene are mixed uniformly to obtain a mixed solution, and then ethylenediamine and diallylamine are added to the mixed solution to react at 60°C for 2 hours, and finally, after thermal curing at 200°C for 5 hours, it is dried at 200°C for 5 hours to obtain a zirconium carbide ceramic precursor. The mass ratio of ethylenediamine, zirconium tetrachloride and diallylamine is 5:3:1. The mass ratio of toluene and zirconium tetrachloride is 7:1.

[0061] (2) Sodium, cyclopentadiene and an organic solvent, toluene, are mixed evenly and reacted at -8°C for 2 hours to obtain a sodium cyclopentadiene solution, wherein the mass ratio of metallic sodium to cyclopentadiene is 1:1, and the volume mass ratio of toluene to metallic sodium is 5:1.

[0062] (3) Under nitrogen protection, titanium tetrachloride and organic solvent toluene are uniformly mixed in a three-necked flask, stirred to form a suspension, and sodium cyclopentadienyl solution is added dropwise at -8°C. After the addition is completed, the residue is removed, and the organic solvent tetrahydrofuran is recovered by heating, and purified to obtain dichlorotitanocene. The volume mass ratio of titanium tetrachloride, sodium cyclopentadienyl in the sodium cyclopentadienyl solution and benzene is 1:3:30.

[0063] (4) Titanocene dichloride and an organic solvent, toluene, were stirred and dispersed in a three-necked flask to obtain a first mixed solution, and tetrahydrofuran was slowly added dropwise at -8°C under nitrogen protection, and then the temperature was raised to 30°C for reaction for 4 hours, and the residue was removed to obtain a titanium intermediate 1. The mass ratio of titanocene dichloride, benzene and tetrahydrofuran was 1:60:15.

[0064] (5) Titanocene dichloride and toluene were stirred and dispersed to obtain a second mixed solution; propyl lithium was slowly added dropwise to the second mixed solution at -22°C, and then hydrogen was introduced, and stirring was continued for 4.2 hours until the reaction was complete. After removing the residue, it was added to the reaction solution, and the temperature was slowly raised to 82°C for reaction for 2.2 hours to obtain titanium intermediate 2. The mass ratio of titanocene dichloride, toluene, propyl lithium and poly-1-butene was 1:200:10:6.

[0065] (6) Under anhydrous and oxygen-free conditions, titanium intermediate 1, titanium intermediate 2 and organic solvent toluene were mixed evenly in a three-necked flask, and reacted at 58° C. for 1.6 h to obtain a titanium carbide ceramic precursor. The mass ratio of titanium intermediate 1, titanium intermediate 2 and toluene was 5:1:30.

[0066] (7) The obtained zirconium carbide ceramic precursor, titanium carbide ceramic precursor and organic solvent toluene are stirred evenly in a reactor, and a zirconium-titanium-carbon ceramic precursor is obtained after the reaction is complete. The mass ratio of the zirconium carbide ceramic precursor, the titanium carbide ceramic precursor and benzene is 5:1:8.

[0067] In an argon atmosphere, the prepared zirconium-titanium-carbon ceramic precursor was cured and then subjected to pyrolysis tests at 1400°C and 1600°C, and the ceramic yields at 1400°C and 1600°C were calculated to be 45.81% and 38.89%, respectively. The bending strengths of the zirconium-titanium-carbon ceramic precursor at 900°C and 1600°C were 530MPa and 610MPa, respectively.

[0068] Embodiment 4:

[0069] (1) Under nitrogen protection, zirconium tetrachloride and organic solvent dichloromethane are mixed uniformly to obtain a mixed solution, and then ethylenediamine and diallylamine are added to the mixed solution to react at 80°C for 1.5 hours, and finally, after thermal curing at 200°C for 5 hours, it is dried at 250°C for 8 hours to obtain a zirconium carbide ceramic precursor. The mass ratio of ethylenediamine, zirconium tetrachloride and diallylamine is 8:2:1. The mass ratio of dichloromethane and zirconium tetrachloride is 6:1.

[0070] (2) Sodium, cyclopentadiene and an organic solvent, dichloromethane, are mixed evenly and reacted at -6°C for 2 hours to obtain a sodium cyclopentadiene solution, wherein the mass ratio of metallic sodium to cyclopentadiene is 3:2, and the volume mass ratio of dichloromethane to metallic sodium is 8:1.

[0071] (3) Under nitrogen protection, titanium tetrachloride and organic solvent dichloromethane are mixed uniformly in a three-necked flask, stirred into a suspension, and sodium cyclopentadienyl solution is added dropwise at -6°C. After the addition is completed, the residue is removed, and the organic solvent tetrahydrofuran is recovered by heating, and purified to obtain dichlorotitanocene. The volume mass ratio of titanium tetrachloride, sodium cyclopentadienyl in the sodium cyclopentadienyl solution and dichloromethane is 1:6:20.

[0072] (4) Titanocene dichloride and organic solvent dichloromethane were stirred and dispersed in a three-necked flask to obtain a first mixed solution, and chloroform was slowly added dropwise at -6°C under nitrogen protection, and then the temperature was raised to 10°C for reaction for 3 hours. After removing the residue, titanium intermediate 1 was obtained. The mass ratio of titanocene dichloride, dichloromethane and chloroform was 1:60:15.

[0073] (5) Titanocene dichloride and dichloromethane were stirred and dispersed to obtain a second mixed solution; butyl lithium was slowly added dropwise to the second mixed solution at -22°C, and then hydrogen was introduced, and stirring was continued for 4.1 hours until the reaction was complete. After removing the residue, 200,000 poly-4-methyl-1-pentene was added to the reaction solution, and the temperature was slowly raised to 80°C for reaction for 2 hours to obtain titanium intermediate 2. The mass ratio of titanocene dichloride, dichloromethane, butyl lithium and poly-4-methyl-1-pentene was 1:300:15:8.

[0074] (6) Under anhydrous and oxygen-free conditions, titanium intermediate 1, titanium intermediate 2 and organic solvent dichloromethane are mixed evenly in a three-necked flask, and reacted at 60° C. for 2 h to obtain a titanium carbide ceramic precursor. The mass ratio of titanium intermediate 1, titanium intermediate 2 and dichloromethane is 8:1:40.

[0075] (7) The obtained zirconium carbide ceramic precursor, titanium carbide ceramic precursor and organic solvent dichloromethane are stirred evenly in a reaction kettle, and a zirconium titanium carbon ceramic precursor is obtained after the reaction is complete. The mass ratio of the zirconium carbide ceramic precursor, the titanium carbide ceramic precursor and benzene is 8:1:60.

[0076] In an argon atmosphere, the prepared zirconium-titanium-carbon ceramic precursor was cured and then subjected to pyrolysis tests at 1400°C and 1600°C, respectively. The ceramic yields at 1400°C and 1600°C were calculated to be 45.35% and 38.51%, respectively. The bending strengths of the zirconium-titanium-carbon ceramic precursor at 900°C and 1600°C were 535MPa and 615MPa, respectively.

[0077] The above examples are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the best embodiment, a person skilled in the art should understand that the technical solution of the present invention can still be modified or replaced by equivalents, and these modifications or equivalent replacements cannot cause the modified technical solution to deviate from the spirit and scope of the technical solution of the present invention.

Claims

1. A method for preparing a high temperature resistant composite zirconium-titanium-carbon ceramic precursor, characterized in that: The preparation method comprises the following steps: Step S1, in a nitrogen atmosphere, zirconium tetrachloride and an organic solvent are uniformly mixed, and then ethylenediamine and diallylamine are added to react at a temperature of 20 to 100° C. for 1 to 2 hours, and then thermally cured and dried in sequence to obtain a zirconium carbide ceramic precursor; In the step S1, the mass ratio of ethylenediamine, zirconium tetrachloride and diallylamine is 1-10:1-5:1; The mass ratio of the organic solvent to zirconium tetrachloride is 5 to 10:1; Step S2, mixing metallic sodium, cyclopentadiene and an organic solvent uniformly, and reacting at -10 to -5°C for 1.8 to 2.2 hours to obtain a sodium cyclopentadiene solution; In the step S2, the mass ratio of the metallic sodium to cyclopentadiene is 1-3:3-1; The mass ratio of the organic solvent to the metallic sodium is 1 to 10:1; Step S3, mixing titanium tetrachloride and an organic solvent uniformly and stirring them into a suspension, and slowly dripping a sodium cyclopentadienyl solution into the suspension at a temperature of -10 to -5°C under a nitrogen atmosphere, then removing the residue, heating and recovering the organic solvent, and purifying to obtain dichlorotitanocene; In the step S3, the mass ratio of titanium tetrachloride, sodium cyclopentadiene and organic solvent is 1:2-6:2-30; Step S4, stirring and dispersing dichlorotitanocene and an organic solvent to obtain a first mixed solution; and adding reagent 1 dropwise to the first mixed solution at a temperature of -10 to -5°C under nitrogen protection, heating the mixture to a temperature of 0 to 50°C after the addition is complete, reacting for 2 to 6 hours, removing the residue, and obtaining a titanium intermediate 1; In the step S4, the mass ratio of the dichlorotitanium, the organic solvent and the reagent 1 is 1:1-120:1-30; Step S5, stirring and dispersing dichlorotitanocene and an organic solvent to obtain a second mixed solution; adding reagent 2 dropwise to the second mixed solution at a temperature of -25 to -20°C, then introducing hydrogen, continuing stirring for 3.8 to 4.2 hours, removing the residue, adding a polyolefin with a molecular weight of 2000 to 500000, slowly heating to 78 to 83°C and reacting for 1.8 to 2.2 hours to obtain a titanium intermediate 2; In the step S5, the mass ratio of the dichlorotitanium, the organic solvent, the reagent 2 and the polyolefin is 1:1-400:1-20:2-10; Step S6, uniformly mixing titanium intermediate 1, titanium intermediate 2 and an organic solvent, and reacting at 58-62° C. for 1.6-4.3 hours to obtain a titanium carbide ceramic precursor; In the step S6, the mass ratio of the titanium intermediate 1, the titanium intermediate 2 and the organic solvent is 1-10:1:4-50; Step S7, according to the mass ratio of 1-10:1:8-90, the zirconium carbide ceramic precursor, the titanium carbide ceramic precursor and the organic solvent are mixed uniformly, and reacted at 50-70° C. for 3-5 hours, and then heated to 80-100° C. to recover the organic solvent to obtain a high temperature resistant composite zirconium titanium carbon ceramic precursor.

2. The preparation method according to claim 1, characterized in that: In the step S1, the thermal curing temperature is 150-300°C and the time is 1-10 hours; In the step S1, the drying temperature is 150-300°C and the drying time is 3-8 hours.

3. The preparation method according to claim 2, characterized in that: In the step S1, the thermal curing temperature is 190-260° C. and the time is 4-8 hours; In the step S1, the drying temperature is 170-240° C. and the drying time is 5-7 hours.

4. The preparation method according to claim 3, characterized in that: In the steps S1 to S7, the organic solvent includes one or more of benzene, toluene, dichloromethane, tetrahydrofuran, anhydrous ether, DMF, anhydrous methanol, anhydrous ethanol, ethyl acetate and N-methylpyrrolidone.

5. The preparation method according to any one of claims 1 to 4, characterized in that: In step S4, the reagent 1 is one or more of formic acid, tetrahydrofuran, acetone, chloroform, dichloromethane, chloroform, acetylacetone, n-hexane, cyclohexane, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, carbon tetrachloride, methanol, ethanol, isopropane, tert-butanol, toluene and xylene.

6. The preparation method according to claim 5, characterized in that: In step S5, the reagent 2 includes one or more of methyl lithium, ethyl lithium, propyl lithium, butyl lithium, vinyl magnesium bromide, n-propenyl magnesium bromide, isopropenyl magnesium bromide, n-butenyl magnesium bromide, isobutenyl magnesium bromide, n-pentenyl magnesium bromide, and isopentenyl magnesium bromide.

7. The preparation method according to claim 6, characterized in that: In the step S5, the molecular weight of the polyolefin is 8,000 to 300,000.

8. The preparation method according to claim 6, characterized in that: In the step S5, the molecular weight of the polyolefin is 10,000 to 200,000.

9. The preparation method according to claim 8, characterized in that: In the step S5, the polyolefin includes one or more of polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, poly-1-pentene, poly-1-hexene and poly-1-octene.

10. A high temperature resistant composite zirconium titanium carbon ceramic precursor, characterized in that: The high temperature resistant composite zirconium-titanium-carbon ceramic precursor is prepared by the preparation method described in any one of claims 1 to 9.

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