CN115216018A - Boron-containing ceramic precursor and preparation method and application thereof - Google Patents
Boron-containing ceramic precursor and preparation method and application thereof Download PDFInfo
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- CN115216018A CN115216018A CN202210906379.7A CN202210906379A CN115216018A CN 115216018 A CN115216018 A CN 115216018A CN 202210906379 A CN202210906379 A CN 202210906379A CN 115216018 A CN115216018 A CN 115216018A
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- boron
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- nitrogen
- containing ceramic
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- 229910052796 boron Inorganic materials 0.000 title claims abstract description 43
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000012700 ceramic precursor Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 30
- -1 boron hydride anions Chemical class 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229910052582 BN Inorganic materials 0.000 claims abstract description 15
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910010277 boron hydride Inorganic materials 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 230000035484 reaction time Effects 0.000 claims abstract description 9
- 239000005416 organic matter Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 21
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
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- 150000002367 halogens Chemical class 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 2
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical compound [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- ZQOBAJVOKBJPEE-UHFFFAOYSA-N [B].[C].[N].[Si] Chemical compound [B].[C].[N].[Si] ZQOBAJVOKBJPEE-UHFFFAOYSA-N 0.000 abstract description 12
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 238000002844 melting Methods 0.000 description 15
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- 229910052757 nitrogen Inorganic materials 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
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- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
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- 229910052708 sodium Inorganic materials 0.000 description 2
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- IJXPQKHXJCOFGH-UHFFFAOYSA-N 2,4,6-trichloro-1,3,5,2,4,6-triazatriborinane Chemical compound ClB1NB(Cl)NB(Cl)N1 IJXPQKHXJCOFGH-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YSMSEUODXDWEKM-UHFFFAOYSA-N NN1BNBNB1 Chemical compound NN1BNBNB1 YSMSEUODXDWEKM-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- ZILJFRYKLPPLTO-UHFFFAOYSA-N [C].[B].[Si] Chemical compound [C].[B].[Si] ZILJFRYKLPPLTO-UHFFFAOYSA-N 0.000 description 1
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
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- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
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- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
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- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/62—Nitrogen atoms
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/583—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on boron nitride
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
- C04B2235/486—Boron containing organic compounds, e.g. borazine, borane or boranyl
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
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Abstract
The invention discloses a boron-containing ceramic precursor and a preparation method and application thereof. Mixing an organic matter containing polyhedral boron hydride anions with a nitrogen-containing organic base monomer to obtain a mixed solution, and then reacting in a protective atmosphere to obtain a polyboroazane precursor, wherein the reaction temperature is 120-300 ℃, and the reaction time is 2-6 h. The boron nitride, boron carbonitride and silicon-boron-nitrogen carbon material prepared by the boron-containing precursor has high thermal stability, high temperature resistance, oxidation resistance, low density and high strength, and has great application prospect in the aspects of heat-resistant parts of engines and gas turbines, thermal protection coatings of aerospace vehicles, ablation-resistant materials, nuclear reactor protection materials and the like.
Description
Technical Field
The invention belongs to the field of chemical synthesis and composite materials, and particularly relates to a boron-containing ceramic precursor as well as a preparation method and application thereof.
Background
The boron nitride, boron carbonitride and silicon-boron-nitrogen carbon material has high thermal stability, thermal shock resistance and corrosion resistance, excellent dielectric property and electrical insulation property, and good composite compatibility with metal and ceramic, so that the boron nitride-boron-nitrogen carbon material has wide application prospect in the high and new technical fields of aviation, aerospace, electric power, electronics and the like.
Because boron nitride, boron carbonitride and silicon boron carbon nitride materials are typical covalent crystal structures, the inorganic method has many defects such as low activity, difficult forming and difficult compounding with other materials, and the Polymer precursor ceramic-to-ceramic (PDCs) method has the advantages of low sintering temperature and strong designability, is more suitable for manufacturing composite materials and the additive manufacturing aspect characterized by rapid forming and rapid manufacturing, and the continuous fiber prepared by the PDCs method is very suitable for manufacturing ceramic matrix composite materials with high fracture resistance.
In Taniguchi, a Japanese scholar in the last 80 years, N-phenyl-B-aminoborazine is used as a precursor for preparing boron nitride fibers by pyrolysis, but the aminoborazine has high price, strict preparation conditions, poor repeatability and difficult industrialization. In 1994, b. Bonnetot reported that boron trichloride and methylamine were used to synthesize a precursor containing carbon, nitrogen and boron, but the precursor synthesized by this method is a net structure and is difficult to form. In 2005, philippe Miele et al, in U.S. Pat. No. 6,967,179B 2, proposed a soluble and meltable precursor obtained by reacting 2,4,6-trichloroborazine with dimethylamine and triethylamine and then condensing with tris (methylamino) borane, but the soluble and meltable precursor was also expensive in raw materials and difficult to industrialize.
In Chinese patent ZL 200710048052.6, bcl is used by Erythrophloeum chinense et al 3 Aliphatic primary amine and secondary amine are used as raw materials to synthesize a polyborazine precursor, but the method needs to use BCl with high toxicity 3 The gas and the product have high activity, and need to react at low temperature, so the industrial production is difficult to carry out. In patent application No. 202110253953.9, published on 2021.6.29, shao chang wei et al, used decaborane as a raw material with a nitrogen source moleculeReacting to synthesize a boron carbonitride ceramic precursor, then dissolving the ceramic precursor in a mixed solution of N, N-dimethylformamide and tetrahydrofuran for spinning, and obtaining boron carbonitride or boron nitride ceramic fibers after pyrolysis, but the method uses the decaborane which has the disadvantages of high toxicity, high price, difficult synthesis, unstable synthesized precursor, only obtaining fibers with the diameter of less than 1 mu m, and incapability of obtaining continuous long fibers. Small molecule borane species tend to be insufficiently stable, pyrophoric in air, and highly toxic, even larger polyhedral boranes such as B 10 H 14 、B 18 H 22 、B 20 H 16 It is not stable enough and synthesis is difficult.
Disclosure of Invention
In view of the shortcomings of the prior art, it is a first object of the present invention to provide a method for preparing a boron-containing ceramic precursor.
The second purpose of the invention is to provide the boron-containing ceramic precursor prepared by the preparation method.
The third purpose of the invention is to provide the application of the boron-containing ceramic precursor prepared by the preparation method, the boron-containing ceramic precursor is subjected to non-melting and high-temperature cracking conversion to obtain boron nitride, boron nitride carbide material or silicon boron nitrogen carbon material, and the materials have good high-temperature stability and corrosion resistance, such as the silicon boron nitrogen carbon material can resist 1500 ℃ in air and resist 1800 ℃ in an inert atmosphere.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention relates to a preparation method of a boron-containing ceramic precursor, which comprises the steps of mixing organic matters containing polyhedral boron hydride anions with nitrogen-containing organic base monomers to obtain a mixed solution, and then reacting in a protective atmosphere to obtain the polyboroazane precursor, wherein the reaction temperature is 120-300 ℃, and the reaction time is 2-6 h.
The inventor finds that polyhedral boron hydride anions are stable and safe, the polyhedral boron hydride anions react with nitrogen-containing organic base monomers, the reaction time is short, the toxicity is low, the industrial production is easy to realize, and the obtained polyboroazane precursor has the characteristics of stable chemical property, high boron content, solubility and meltability, high ceramic yield and is suitable for preparing boron nitride, boron carbonitride or silicon boron nitrogen carbon materials.
The reaction provided by the invention is simple, the polyborazine precursor can be obtained only by controlling the reaction conditions, but the reaction temperature and the reaction time need to be effectively controlled, the reaction is incomplete due to too short reaction time, the molecular weight of the generated polyborazine is too small, the melting point is too low, the molecular weight of the polyborazine is too large and the melting point is too high due to too long reaction time, and the solubility is poor.
In the actual operation process, the organic matter of polyhedral boron hydride anions and the organic alkali monomer containing nitrogen can be directly mixed and reacted, and the organic alkali monomer containing nitrogen can also be added into an organic solvent such as dimethylbenzene for reaction.
Preferably, the reaction temperature is 210-240 ℃, and the reaction time is 4-5 h.
In a preferred embodiment, in the organic matter containing polyhedral boron hydride anions, the polyhedral boron hydride anions are selected from B 10 H 10 2- And/or B 12 H 12 2- 。
In a preferred embodiment, the organic substance containing polyhedral boron hydride anions is selected from [ Et 4 N] 2 B 10 H 10 And/or [ Et 4 N] 2 B 12 H 12 。
The inventors have found that the preferred organic compounds containing polyhedral boron hydride anions described above form closed boron cages with polyhedral boron hydrides, which are more stable than other nested or meshed structures and can withstand higher temperatures without decomposition.
In the present invention, [ Et ] 4 N] 2 B 10 H 10 And/or [ Et 4 N] 2 B 12 H 12 By pyrolysis with KBH 4 Or NaBH 4 As the basic raw material with Et 4 NCl or in the presence of triethylamine, chloroethane and a small amount of water.
In a preferred embodiment, the nitrogen-containing organic base monomer has the formula NR 1 R 2 (CH 2 )nNR 3 R 4 Wherein R is 1 ～R 4 Are all selected from at least one of H, alkyl and halogen.
Further preferably, the nitrogen-containing organic base monomer is at least one selected from ethylenediamine, propylenediamine, butylenediamine, and N, N' -tetramethylethylenediamine. The preferred organic base monomers each contain two amino groups which can be the same as [ B ] 10 H 10 ] 2- Or [ B 12 H 12 ] 2- Form stable polymer, and the monomer contains only C, H and N elements, and after high temperature cracking, H will run off and more B may be remained 4 C. BN inorganic substance.
Still more preferably, the nitrogen-containing organic base monomer is at least one selected from ethylenediamine, N' -tetramethylethylenediamine.
According to the preferable scheme, after the reaction is finished, the reaction product is naturally cooled to room temperature, then the obtained product is dissolved by adopting a mixed solution containing N, N-dimethylformamide and tetrahydrofuran, the solvent is evaporated after the reaction product is filtered, and the polyboroazane precursor is obtained, wherein in the mixed solution containing N, N-dimethylformamide and tetrahydrofuran, the volume ratio of N, N-dimethylformamide to tetrahydrofuran is 3-8: 1.
the inventors have found that the mixture for dissolving the product is very important, and the mixture of the two solvents is required to be used in the above range, so that the mixture can be sufficiently dissolved, and if the mixture ratio is not reasonable, the product cannot be sufficiently dissolved.
The invention also provides a boron-containing ceramic precursor prepared by the preparation method.
The invention also provides application of the boron-containing ceramic precursor prepared by the preparation method, and the boron-containing ceramic precursor is converted to obtain a boron-containing material, wherein the boron-containing material is at least one of boron nitride, boron carbonitride and silicon boron nitrogen carbon materials.
In practical operation, the boron-containing ceramic precursor is subjected to processes of forming, non-melting and firing to obtain a boron-containing material, wherein the forming process includes, but is not limited to, spinning, coating, spraying, extruding, injecting, winding, casting and the like after being melted or dissolved in a solvent.
In the non-melting step, one or more gases such as air, oxygen, nitrogen, a rare gas, a nitrogen oxide, ammonia, chlorine, hydrogen, carbon monoxide, carbon dioxide, boron halide, borane, and steam may be used, or the non-melting may be performed by irradiation with an electron beam in the above-described atmosphere or under vacuum. Air and ammonia gas are preferably used for the non-melting treatment.
During the firing process, vacuum or one or more gases such as nitrogen, ammonia, noble gases, carbon monoxide, boron halides, borane, etc. can be used, and the products obtained from different gases are different, for example, the main product under ammonia is boron nitride, and the product under argon is BC 4 And a small amount of boron nitride.
The precursor can be mixed with other precursors for use, and the silicon-boron-nitrogen-carbon material can be prepared after the precursor is mixed like a polycarbosilane precursor.
Advantageous effects
The boron nitride, boron carbonitride and silicon boron nitrogen carbon material prepared by the boron-containing precursor has high thermal stability, high temperature resistance, oxidation resistance, low density and high strength, and simultaneously can be mixed with polycarbosilane for spinning to prepare silicon boron nitrogen carbon fibers with high temperature resistance and oxidation resistance, so that the thermal stability, high temperature resistance and oxidation resistance of SiC materials are improved.
Drawings
FIG. 1 is a schematic representation of a common structural type of polyhedral borane.
FIG. 2 is an infrared spectrum of the mixed precursor of example 2.
FIG. 3 XRD pattern of SiBOC-N-carbon fiber obtained in example 2.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the invention.
The following are examples:
preparation example 1: [ Et 4 N] 2 B 10 H 10 And [ Et 4 N] 2 B 12 H 12 The preparation of (1): after passing through high-purity N 2 To a three-necked flask of (2) was added 480 g of tetraethylammonium chloride (containing quartering crystal water) and 240 g of potassium borohydride, 180 ml of water, and the mixture was mixed to a slurry, heated in an oil bath, boiled at about 100 ℃ and discharged with triethylamine, heated to about 185. + -. 2 ℃ for about 40 minutes, and kept at that temperature for 20 hours to obtain 115g of a white solid containing [ Et ] 4 N] 2 B 10 H 10 78.3g and [ Et ] 4 N] 2 B 12 H 12 12.4g, total conversion 53.4%, where [ Et 4 N] 2 B 10 H 10 Conversion 46.5% (based on B), [ Et ] 4 N] 2 B 12 H 12 Conversion was 6.9% (based on B) and the product was further purified by recrystallization from methanol.
Preparation example 2: after passing through high-purity N 2 Into a three-necked flask of (2) was charged 200ml of anhydrous toluene, and heated under stirring to reflux, 115g of metallic sodium was charged, and stirring was started at 800 rpm to disperse the metallic sodium, and the stirring speed was maintained until the polymerization was terminated. A mixture of 302mL dichlorodimethylsilane and 1000mL anhydrous toluene was quickly added dropwise, with the exclusion of light, at 104 ℃ under reflux for 18h, cooled to room temperature, a mixture of 50mL anhydrous acetic acid and 50mL ethanol was slowly added, filtered, washed in a Buchner funnel with 200mL tetrahydrofuran and ethanol 1 mixture, the precipitate was then placed in a beaker, and 3000mL 10% NaHCO 3 The aqueous solution was stirred rapidly for 1h, filtered and the product dried under vacuum for 48h to give 108.5g of Polydimethylsilane (PDMS) white powder in 74.8% yield.
Preparation example 3: preparation of polycarbosilane: after passing through high-purity N 2 400g of PDMS prepared according to the method of preparation example 2 is added into the three-necked flask, the temperature is slowly raised to 300-550 ℃ at the speed of 100 ℃/h, PDMS steam enters a cracking column for gas phase cracking rearrangement, the temperature is kept for 1-8 hours until the temperature reaches 450-550 ℃, and a PCS crude product is obtained after cooling. The PCS crude product is heated and dissolved in anhydrous xylene, impurities are removed by filtration, and the xylene solvent is evaporated, so that 170g of polycarbosilane with the number average molecular weight of 650-2500 is obtained (yield is 42.5%).
Example 1:
[ Et ] of preparation example 1 4 N] 2 B 10 H 10 200g and 85g of ethylenediamine are added into a three-necked flask, the mixture is reacted for 5 hours at 210 ℃ under the protection of inert atmosphere, after the mixture is naturally cooled to normal temperature, the mixture is dissolved by 800ml of N, a mixed solution of N-dimethylformamide and tetrahydrofuran (volume ratio 3.
After the polyboroazane precursor is formed, the polyboroazane precursor can be infusibilized in air, heated to 150 ℃ at a heating rate of 10 ℃/hour, held for 2 hours, heated to 180 ℃ at a heating rate of 5 ℃/hour, and held for 1 hour at 180 ℃. And (3) placing the material which is not subjected to melting treatment in a graphite furnace, introducing argon, raising the temperature to 1100 ℃ at the heating rate of 200 ℃/h, preserving the temperature for 1h, and cooling to obtain the black boron carbonitride material.
After molding, ammonia gas can be used for non-melting treatment: heating to 120 ℃ at a heating rate of 10 ℃/h, preserving heat for 2h, heating to 150 ℃ at 5 ℃/h, and preserving heat for 2h at 150 ℃. And (3) putting the material which is not subjected to melting treatment into a graphite furnace, introducing ammonia gas, raising the temperature to 1000 ℃ at a heating rate of 200 ℃/hour, preserving the temperature for 1 hour, and cooling to obtain the white boron nitride material.
The test shows that the prepared boron nitride carbide material contains 67.0wt% of B, 17.4wt% of C, 14.5wt% of N, 0.9wt% of O, 65.0wt% of B, 1.3wt% of C, 32.8wt% of N and 0.5wt% of O (oxygen and nitrogen elements are measured by a HORIBA EMGA-820 type oxygen-nitrogen analyzer, and carbon elements are analyzed by a HORIBA EMIA-20P type carbon-sulfur analyzerThe content of B is measured by grinding the material into powder and then measuring the content of Na in the powder according to the same proportion 2 CO 3 And KNO 3 Melting at 1100 deg.C after mixing, completely dissolving the melt with hydrochloric acid, complexing element B with mannitol, and titrating with NaOH).
Example 2:
[ Et ] of preparation example 1 4 N] 2 B 10 H 10 200g and 140g of N, N' -tetramethylethylenediamine are added into a three-necked bottle, reacted for 4 hours at 240 ℃ under the protection of inert atmosphere, naturally cooled to normal temperature, dissolved by 900ml of a mixed solution of N, N-dimethylformamide and tetrahydrofuran (volume ratio: 8.
The obtained polyboroazane precursor and the polycarbosilane precursor with the melting point of 230 ℃ in preparation example 3 were uniformly mixed according to the ratio of 1 (the infrared spectrum of the mixed precursor is shown in fig. 2) and then melt-spun at the temperature of 280 ℃, and cooled fibrils were subjected to non-melting treatment in air: heating to 170 ℃ at a heating rate of 10 ℃/hour, preserving heat for 2 hours, heating to 190 ℃ at a heating rate of 5 ℃/hour, preserving heat for 2 hours at 190 ℃, and then cooling to room temperature. And (3) putting the fiber which is not melted into a graphite furnace, introducing argon, raising the temperature to 1250 ℃ at the heating rate of 200 ℃/h, and preserving the temperature for 1 h. And then heating the obtained fiber to 1900 ℃ at the speed of 100 ℃/hour under argon, preserving the temperature for 1 hour, sintering to obtain the silicon-boron-carbon-nitrogen fiber, and grinding into powder to obtain XRD (XRD) shown in figure 3.
The silicon-boron-carbon-nitrogen fiber prepared in the example has the Si content of 41.2wt%, the B content of 32.2wt%, the C content of 16.1wt%, the N content of 9.5wt%, the O content of 0.36wt% and the bulk density of 2.54g/cm 3 (oxygen and nitrogen are measured by a HORIBA EMGA-820 type oxygen-nitrogen analyzer, carbon is measured by a HORIBA EMIA-20P type carbon-sulfur analyzer, silicon content is measured by a potassium fluosilicate volumetric method, and B content is measured by a method of mannitol complexation after melting and dissolving and chemical titration). The diameter of the silicon-boron-carbon-nitrogen fiber prepared by the embodiment is about 11 mu m, and the tensile strength at room temperature is 1.84GPa, the tensile strength is 1.65GPa after being treated in air at 1500 ℃ for 1h, and the tensile strength is 1.8GPa after being treated in argon at 1800 ℃ for 1h, so that the high-temperature-resistant and high-temperature-resistant composite material has high temperature resistance and high oxidation resistance.
As comparative examples when cooled fibrils were melt spun in air using only polycarbosilane precursor with a melting point of 230 ℃ at a temperature of 300 ℃: heating to 170 ℃ at a heating rate of 10 ℃/h, preserving heat for 2h, heating to 190 ℃ at 5 ℃/h, preserving heat for 2h at 190 ℃, and then cooling to room temperature. Placing the fiber which is not melted in a graphite furnace, introducing argon, raising the temperature to 1250 ℃ at the heating rate of 200 ℃/hour, and preserving the heat for 1 hour to obtain the SiC fiber with the diameter of about 11 mu m and the tensile strength of 2.2GPa, wherein the bulk density is 2.58g/cm 3 The Si content was 55.8wt%, the C content was 32.9wt%, and the O content was 11.0wt%, but the strength of the fiber was zero after 1 hour at 1500 ℃ in air or 1 hour at 1800 ℃ in argon.
Comparative example 1:
decaborane B 10 H 14 Adding 64g and 85g of ethylenediamine into a three-necked bottle, reacting for 2 hours at 90 ℃ in 300ml of dimethylbenzene under the protection of inert atmosphere, and cooling to normal temperature after the reaction is finished to obtain 85.5g of polyboroazane precursor, wherein the precursor generates a large amount of bubbles after being heated unstably and cannot be molded to obtain a compact ceramic material.
Finally, it should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and those skilled in the art can make many similar changes without departing from the principle of the present invention and the claims, and these changes are all within the scope of the present invention.
Claims (9)
1. A preparation method of a boron-containing ceramic precursor is characterized by comprising the following steps: mixing an organic matter containing polyhedral boron hydride anions with a nitrogen-containing organic base monomer to obtain a mixed solution, and then reacting in a protective atmosphere to obtain a polyboroazane precursor, wherein the reaction temperature is 120-300 ℃, and the reaction time is 2-6 h.
2. The method of claim 1, wherein the method comprises: the reaction temperature is 210-240 ℃, and the reaction time is 4-5 h.
3. The method for producing a boron-containing ceramic precursor according to claim 1 or 2, wherein: in the organic matter containing polyhedral boron hydride anions, the polyhedral boron hydride anions are selected from B 10 H 10 2- And/or B 12 H 12 2- 。
4. The method of claim 3, wherein the method comprises: the organic matter containing polyhedral boron hydride anions is selected from [ Et 4 N] 2 B 10 H 10 And/or [ Et 4 N] 2 B 12 H 12 。
5. The method for producing a boron-containing ceramic precursor according to claim 1 or 2, wherein: the chemical formula of the nitrogen-containing organic base monomer is NR 1 R 2 (CH 2 )nNR 3 R 4 Wherein R is 1 ～R 4 Are all selected from at least one of H, alkyl and halogen.
6. The method of claim 5, wherein the boron-containing ceramic precursor is prepared by: the nitrogen-containing organic alkali monomer is at least one of ethylenediamine, propylenediamine, butylenediamine and N, N, N ', N' -tetramethylethylenediamine.
7. The method of claim 1, wherein the boron-containing ceramic precursor is prepared by: after the reaction is finished, naturally cooling to room temperature, dissolving the obtained product by adopting a mixed solution containing N, N-dimethylformamide and tetrahydrofuran, filtering, and evaporating to remove the solvent to obtain the polyboroazane precursor, wherein in the mixed solution containing N, N-dimethylformamide and tetrahydrofuran, the volume ratio of N, N-dimethylformamide to tetrahydrofuran is 3-8: 1.
8. a boron-containing ceramic precursor produced by the production method as set forth in any one of claims 1 to 7.
9. Use of a boron-containing ceramic precursor prepared by the method according to any one of claims 1 to 7 to convert the boron-containing ceramic precursor to obtain a boron-containing material selected from at least one of boron nitride, boron carbonitride, silicon boron carbonitride materials.
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