CN115651414B - Preparation method of liquid complex-phase SiBCN ceramic precursor and SiBCN ceramic - Google Patents
Preparation method of liquid complex-phase SiBCN ceramic precursor and SiBCN ceramic Download PDFInfo
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- 239000007788 liquid Substances 0.000 title claims abstract description 54
- 239000000919 ceramic Substances 0.000 title claims abstract description 46
- 239000012700 ceramic precursor Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920001709 polysilazane Polymers 0.000 claims abstract description 20
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 19
- VEWFZHAHZPVQES-UHFFFAOYSA-N boron;n,n-diethylethanamine Chemical compound [B].CCN(CC)CC VEWFZHAHZPVQES-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000376 reactant Substances 0.000 claims abstract description 15
- XSDCTSITJJJDPY-UHFFFAOYSA-N chloro-ethenyl-dimethylsilane Chemical compound C[Si](C)(Cl)C=C XSDCTSITJJJDPY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000006227 byproduct Substances 0.000 claims abstract description 8
- 238000004821 distillation Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 17
- 238000004132 cross linking Methods 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 10
- 238000005336 cracking Methods 0.000 claims description 9
- 239000002981 blocking agent Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000002243 precursor Substances 0.000 abstract description 22
- 229920000642 polymer Polymers 0.000 abstract description 16
- 238000005470 impregnation Methods 0.000 abstract description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 8
- 229910052796 boron Inorganic materials 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000011153 ceramic matrix composite Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- NAURARPAILHOKJ-UHFFFAOYSA-N ClC(Cl)[SiH2]CCB(CC[SiH2]C(Cl)Cl)CC[SiH2]C(Cl)Cl Chemical compound ClC(Cl)[SiH2]CCB(CC[SiH2]C(Cl)Cl)CC[SiH2]C(Cl)Cl NAURARPAILHOKJ-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZXSSXAUYKUTLBP-UHFFFAOYSA-N hexane;trichloroborane Chemical compound ClB(Cl)Cl.CCCCCC ZXSSXAUYKUTLBP-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Ceramic Products (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The application relates to a liquid complex phase SiBCN ceramic precursor and a preparation method thereof, comprising the following steps: under the protection of inert atmosphere, uniformly mixing boron trichloride, methylhydrogen dichlorosilane and dimethylvinylchlorosilane according to a certain proportion to obtain a mixed reactant; dropwise adding excessive hexamethyldisilazane into the mixed reactant in a cooling state, and carrying out room-temperature reaction under a stirring condition for a first preset time after the dropwise adding is finished; removing solvent and byproducts from the reacted solution through reduced pressure distillation to obtain liquid vinyl-containing polysilazane; adding borane triethylamine into liquid vinyl-containing polysilazane, and uniformly mixing to obtain a liquid complex-phase SiBCN ceramic precursor. The liquid complex phase SiBCN ceramic precursor and the preparation method thereof aim to solve the problem that the existing polymer precursor ceramic can not simultaneously meet the requirements of ceramic yield and impregnation efficiency.
Description
Technical Field
The application relates to the technical field of ceramic material preparation, in particular to a liquid complex phase SiBCN ceramic precursor and a preparation method of SiBCN ceramic.
Background
The SiBCN ceramic has better high-temperature oxidation resistance in an air environment below 1500 ℃, and keeps excellent structural stability in an inert atmosphere below 2000 ℃, so that the highest use temperature of the silicon-based ceramic material is obviously improved. At present, a series of SiBCN ceramic precursors have been developed that can be used to prepare SiBCN ceramic fibers, porous materials, coatings, blocks and composites. The continuous fiber reinforced SiBCN ceramic matrix composite is mainly prepared by a precursor impregnation-pyrolysis (PIP) process, and has wide application prospect in the field of aerospace thermal structural materials along with the gradual maturity of related preparation technologies.
The research of the precursor conversion method for preparing SiBCN ceramic is carried out by Japanese Takamizawa et al at the earliest time, and the SiBCN ceramic fiber is successfully spun into filaments, and the prepared SiBCN ceramic fiber can still keep an amorphous state under the inert condition of 1500 ℃. The addition reaction of borane and double bond is utilized by R.Riedel et al, university of German damm Shi Da, to introduce boron element into polysilazane molecule to prepare SiBCN ceramic which can keep weight not lost below 2000 ℃. The slow rainbow subject group of the national academy of sciences chemistry reports a method for preparing a liquid SiBCN ceramic precursor by adopting chlorosilane, boron trichloride and hexamethyldisilazane as raw materials through a one-pot method, and the method has the advantages of simplicity in operation and convenience in separation. The research team of national defense science and technology university adopts boron trichloride, methylhydrogen dichlorosilane and hexamethyldisilazane as raw materials to prepare the SiBCN ceramic precursor capable of being melt spun. The same method is adopted in Hashi, and tris (dichloromethylsilylethyl) borane, boron trichloride and hexamethyldisilazane are used as raw materials to prepare the spinnable SiBCN ceramic precursor. The research team of Donghua university uses boron trichloride, trichlorosilane and methylamine as raw materials to carry out copolymerization, and then carries out amino exchange reaction to obtain the ceramic precursor for SiBCN fiber with high ceramic yield.
The existing polymer SiBCN ceramic precursors mainly adopt the types for preparing SiBCN fibers, the polymer precursors suitable for SiBCN matrix preparation are few, the low-viscosity polymer precursor ceramic yield is generally low, the polymer precursors with high ceramic yield are generally high in viscosity, and the impregnation efficiency is low.
Therefore, the inventor provides a liquid complex phase SiBCN ceramic precursor and a preparation method of SiBCN ceramic.
Disclosure of Invention
(1) Technical problem to be solved
The embodiment of the application provides a liquid complex phase SiBCN ceramic precursor and a preparation method of SiBCN ceramic, which solve the technical problem that the existing polymer precursor ceramic can not simultaneously meet the requirements of ceramic yield and impregnation efficiency.
(2) Technical proposal
The application provides a liquid complex phase SiBCN ceramic precursor, which consists of a component A and a component B, wherein the structural formula of the component A is as follows:
the component B is borane triethylamine.
The application also provides a preparation method of the liquid complex phase SiBCN ceramic precursor, which comprises the following steps:
under the protection of inert atmosphere, uniformly mixing boron trichloride, methylhydrogen dichlorosilane and dimethylvinylchlorosilane according to a certain proportion to obtain a mixed reactant;
dropwise adding excessive hexamethyldisilazane into the mixed reactant in a cooling state, and carrying out room-temperature reaction under a stirring condition for a first preset time after the dropwise adding is finished;
removing solvent and byproducts from the reacted solution through reduced pressure distillation to obtain liquid vinyl-containing polysilazane;
and adding borane triethylamine into the liquid vinyl-containing polysilazane, and uniformly mixing to obtain the liquid complex-phase SiBCN ceramic precursor.
Further, the molar ratio of the boron trichloride to the methylhydrogen dichlorosilane is 1 (0.25-10); the dimethylvinylchlorosilane is used as a blocking agent, and the molar dosage is 2.5-30% of the total molar dosage of the boron trichloride and the methylhydrogen dichlorosilane.
Further, the molar ratio of the boron trichloride to the methylhydrogen dichlorosilane to the dimethylvinyl chlorosilane is 1:1:0.15.
Further, the first preset time is 24-48 hours.
Further, the amount of hexamethyldisilazane is 2 to 4 times the molar amount of the mixed reactants.
Further, the usage amount of the borane triethylamine is 10-75% of the mass of the liquid vinyl polysilazane.
The application also provides a preparation method of the SiBCN ceramic with the liquid complex phase SiBCN ceramic precursor, which comprises the following steps:
crosslinking the liquid complex phase SiBCN ceramic precursor to obtain a crosslinked product;
and (3) putting the crosslinked product into a high-temperature cracking furnace for cracking to obtain the SiBCN ceramic.
Further, the reaction time of the crosslinking is 2 to 6 hours.
Further, the crosslinking temperature is 100 to 200 ℃.
(3) Advantageous effects
In summary, the complex phase precursor of the application has lower viscosity due to the inclusion of a large amount of borane strong base complex with low molecular weight, in addition, unsaturated bonds of polymer components can undergo a boron-hydrogen addition reaction with B-H bonds between 100 ℃ and 200 ℃, and B-H and N-H bonds can undergo a dehydrogenation coupling reaction, so that the precursor can be crosslinked and solidified at relatively low temperature, thereby reducing the escape of small molecules in the cracking process and improving the ceramic yield of the complex phase precursor. The precursor has the characteristics of lower viscosity and higher ceramic yield, and the boron element content in the ceramic product is higher, so that the precursor has excellent high-temperature oxidation resistance, and is suitable for being used as matrix resin for PIP technology and used for preparing SiBCN-based composite materials. In addition, the preparation steps of the liquid complex phase SiBCN ceramic precursor are simple, the regulation and control are convenient, the cost is low, and the large-scale popularization and application are easy.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments of the present application will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort to a person of ordinary skill in the art.
FIG. 1 is a schematic flow chart of a method for preparing a liquid complex phase SiBCN ceramic precursor according to an embodiment of the present application;
FIG. 2 is a graph showing the thermal weight loss of a liquid complex phase SiBCN ceramic precursor prepared in example 1 of the present application;
FIG. 3 is a morphology graph of a pyrolysis product of a liquid complex phase SiBCN ceramic precursor prepared in example 1 of the present application.
Detailed Description
Embodiments of the present application are described in further detail below with reference to the accompanying drawings and examples. The following detailed description of the embodiments and the accompanying drawings are provided to illustrate the principles of the application and are not intended to limit the scope of the application, i.e., the application is not limited to the embodiments described, but covers any modifications, substitutions and improvements in parts, components and connections without departing from the spirit of the application.
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The application will be described in detail below with reference to the drawings in connection with embodiments.
The embodiment of the application provides a liquid complex phase SiBCN ceramic precursor, which consists of two components A and B, wherein the structural formula A is as follows:
component B is borane Triethylamine (TEAB).
Fig. 1 is a schematic flow chart of a method for preparing a liquid complex phase SiBCN ceramic precursor according to an embodiment of the present application, where the method may include the following steps:
s101, uniformly mixing boron trichloride, methylhydrogen dichlorosilane and dimethylvinylchlorosilane according to a certain proportion under the protection of inert atmosphere to obtain a mixed reactant;
s102, dropwise adding excessive hexamethyldisilazane into the mixed reactant in a cooling state, and carrying out room-temperature reaction under a first preset time under a stirring condition after the dropwise adding is finished;
s103, removing a solvent and byproducts from the reacted solution through reduced pressure distillation to obtain liquid vinyl-containing polysilazane;
and S104, adding borane triethylamine into the liquid vinyl-containing polysilazane, and uniformly mixing to obtain a liquid complex-phase SiBCN ceramic precursor.
In the embodiment, the prepared liquid complex phase SiBCN ceramic precursor can regulate and control the boron element content in the SiBCN ceramic cracking product by regulating and controlling the monomer proportion and the borane triethylamine dosage, and can be used for preparing SiBCN ceramic with the boron element content higher than 20wt%.
The two components of the prepared liquid complex phase SiBCN ceramic precursor containing vinyl liquid polysilazane and borane triethylamine can be separately stored, and the two components are compounded according to a certain proportion when in use, so that the good storage stability of the precursor can be ensured.
The prepared liquid complex phase SiBCN ceramic precursor can be used for preparing SiBCN ceramic powder, siBCN ceramic coating, siBCN complex phase ceramic and SiBCN ceramic matrix composite material matrix.
The reaction raw materials are common commercial chemical raw materials, the raw materials are low in unit price, and the method is suitable for large-scale popularization and application.
In step S102, the dripping speed is controlled at the beginning of the reaction, and the mixed reactant is subjected to ice-water bath, so that white vaporous byproducts appear at the beginning of the reaction. Because the reaction is exothermic, the reaction can be overheated when the dropping speed is too fast at the beginning, and the dropping speed can be improved when the white vaporific byproducts gradually disappear. After the mixed solution is dripped, the ice water bath can be removed, and the room temperature reaction is carried out for a first preset time under the stirring condition.
In step S103, reduced pressure distillation should be performed at 150-180 ℃, the distillation temperature is too low, and the target polymer has more byproducts and unreacted raw materials, and too high distillation temperature can cause the precursor polymer to crosslink and solidify itself, thus causing inseparable separation.
In step S104, a certain proportion of borane triethylamine liquid is added into the liquid vinyl-containing polysilazane and mixed uniformly, and the mixture is ensured not to be layered up and down, so that the liquid complex phase SiBCN ceramic precursor is prepared.
As an alternative embodiment, the molar ratio of the boron trichloride to the methylhydrogen dichlorosilane is 1 (0.25-10); the dimethyl vinyl chlorosilane is used as a blocking agent, and the molar dosage of the dimethyl vinyl chlorosilane is 2.5-30% of the total molar weight of the boron trichloride and the methyl hydrogen dichlorosilane.
Wherein, boron trichloride and methyl hydrogen dichlorosilane are used as comonomers, and boron trichloride is used as a boron source, and a certain amount of boron-containing structure is introduced into the precursor, so that the high-temperature structural stability and oxidation resistance of the precursor-derived ceramic are improved. Methyl hydrogen dichlorosilane is used as an indispensable carbon source and a silicon source on one hand, and can play a role in regulating and controlling the viscosity of the precursor polymer on the other hand, and the too low introduction amount can cause the too high viscosity of the precursor polymer. On one hand, the dimethyl vinyl chlorosilane is used as a blocking agent, the molecular weight of the polymer can be regulated and controlled, the viscosity of the polymer is not too high, and on the other hand, a crosslinkable group is provided, so that the ceramic yield is improved. However, too much of it may result in too high a content of derivatized ceramic carbon, which is detrimental to its high temperature oxidation resistance.
As an alternative embodiment, the molar ratio of boron trichloride, methylhydrogen dichlorosilane and dimethylvinyl chlorosilane is 1:1:0.15. Wherein, the molar ratio can lead the prepared precursor polymer to have lower viscosity, more balanced silicon, boron, carbon and nitrogen element proportion and a certain cross-linking group vinyl.
As an alternative embodiment, the first preset time is 24 h-48 h. Wherein, too short a reaction time may result in insufficient reaction progress, while too long a reaction time may be detrimental to the precursor polymer preparation efficiency.
As an alternative embodiment, hexamethyldisilazane is used in an amount of 2 to 4 times the molar amount of the mixed reactants. Wherein, the excessively low dosage can lead to insufficient reaction of B-Cl bond and Si-Cl bond, and the existence of residual chlorine element is unfavorable for the high-temperature structural stability of the derivative ceramics; if the dosage is too high, the preparation cost is increased, which is unfavorable for the economy of the technology.
As an alternative embodiment, the borane triethylamine is used in an amount of 10% to 75% by mass of the liquid vinyl polysilazane. On one hand, the borane triethylamine can have a boron-hydrogen addition reaction with vinyl in vinyl polysilazane in a cracking process and have a dehydrogenation coupling reaction with N-H bond of polysilazane to crosslink, so that the escaping proportion of the borane triethylamine as small molecules is reduced, and the ceramic yield of the vinyl polysilazane is greatly improved; on the other hand, borane triethylamine is also the boron source and carbon source for the precursor polymer. However, too high an amount of borane triethylamine can also cause too high a content of small molecules, so that the degree of crosslinking of the complex phase ceramic is insufficient, and the ceramic yield is greatly reduced.
The embodiment of the application also provides a preparation method of the SiBCN ceramic with the liquid complex phase SiBCN ceramic precursor, which comprises the following steps:
s201, crosslinking a liquid complex phase SiBCN ceramic precursor to obtain a crosslinked product;
s202, placing the crosslinked product into a high-temperature cracking furnace for cracking to obtain SiBCN ceramic.
As an alternative embodiment, the SiBCN composite ceramic is crosslinked at 100-200 ℃ for 2-6 hours. Wherein, too low reaction temperature or too short crosslinking time is unfavorable for the sufficient crosslinking of the precursor and the removal of partial low-boiling components, too high reaction temperature can cause too fast crosslinking reaction to cause insufficient crosslinking, and both are unfavorable for the improvement of ceramic yield; and the long crosslinking time is unfavorable for the efficiency and the economy of the technology for preparing ceramics.
Example 1
The preparation process of the liquid complex phase SiBCN ceramic precursor specifically comprises the following steps:
1) Under the protection of inert atmosphere, 1000ml of boron trichloride n-hexane solution (1 mol/L), 115g of methyl hydrogen dichlorosilane (1 mol) and 18g of dimethyl vinyl chlorosilane (0.15 mol) are uniformly mixed;
2) Then 960g of hexamethyldisilazane (3 mol) is added into the mixed reactant dropwise, the mixed reactant is cooled, and the mixed reactant reacts for 24 hours at room temperature under the stirring condition after the mixed solution is added dropwise;
3) Vacuum distilling the reacted solution at 150 ℃ to remove solvent and trimethylchlorosilane byproducts to prepare liquid vinyl-containing polysilazane, adding borane triethylamine with the mass of 50wt% of the polysilazane into the liquid vinyl-containing polysilazane, and uniformly mixing to obtain a liquid complex phase SiBCN ceramic precursor;
4) The liquid complex phase SiBCN ceramic precursor is crosslinked for 4 hours at 150 ℃, and then is cracked at 1200 ℃ to obtain SiBCN ceramic, wherein the ceramic yield can reach 63wt%.
In the above embodiment, as shown in fig. 2, after the temperature of the liquid complex phase SiBCN ceramic precursor exceeds 700 ℃, the thermal loss starts to delay, and the thermal loss curve is flattened; as shown in fig. 3, the morphology of the pyrolysis product SiBCN ceramic of the liquid complex phase SiBCN ceramic precursor.
It should be understood that, in the present specification, each embodiment is described in an incremental manner, and the same or similar parts between the embodiments are all referred to each other, and each embodiment is mainly described in a different point from other embodiments. The application is not limited to the specific steps and structures described above and shown in the drawings. Also, a detailed description of known method techniques is omitted here for the sake of brevity.
The above is only an example of the present application and is not limited to the present application. Various modifications and alterations of this application will become apparent to those skilled in the art without departing from the scope of this application. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the application are to be included in the scope of the claims of the present application.
Claims (5)
1. The preparation method of the liquid complex phase SiBCN ceramic precursor is characterized by comprising the following steps of:
under the protection of inert atmosphere, uniformly mixing boron trichloride, methylhydrogen dichlorosilane and dimethylvinylchlorosilane according to a certain proportion to obtain a mixed reactant;
dropwise adding excessive hexamethyldisilazane into the mixed reactant in a cooling state, and carrying out room-temperature reaction under a stirring condition for a first preset time after the dropwise adding is finished;
removing solvent and byproducts from the reacted solution through reduced pressure distillation to obtain liquid vinyl-containing polysilazane;
adding borane triethylamine into the liquid vinyl-containing polysilazane, and uniformly mixing to obtain the liquid complex-phase SiBCN ceramic precursor;
the molar ratio of the boron trichloride to the methylhydrogen dichlorosilane is 1 (0.25-10); the dimethylvinylchlorosilane is used as a blocking agent, and the molar amount of the dimethylvinylchlorosilane is 2.5% -30% of the total molar amount of the boron trichloride and the methylhydrogen dichlorosilane;
the dosage of the hexamethyldisilazane is 2-4 times of the molar quantity of the mixed reactant;
the consumption of the borane triethylamine is 10% -75% of the mass of the liquid vinyl polysilazane; the first preset time is 24-48 hours;
the liquid complex phase SiBCN ceramic precursor consists of a component A and a component B, wherein the structural formula of the component A is as follows:
；
the component B is borane triethylamine.
2. The method for preparing the liquid complex phase SiBCN ceramic precursor according to claim 1, wherein the molar ratio of the boron trichloride, the methylhydrogen dichlorosilane and the dimethylvinyl chlorosilane is 1:1:0.15.
3. A method of preparing a SiBCN ceramic having a liquid complex phase SiBCN ceramic precursor according to claim 1, comprising the steps of:
crosslinking the liquid complex phase SiBCN ceramic precursor to obtain a crosslinked product;
and (3) putting the crosslinked product into a high-temperature cracking furnace for cracking to obtain the SiBCN ceramic.
4. The preparation method of SiBCN ceramic according to claim 3, wherein the reaction time of the crosslinking is 2-6 hours.
5. The method for preparing SiBCN ceramic according to claim 3, wherein the cross-linking temperature is 100-200 ℃.
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