CN104974352A - Preparation method of SiBCN ceramic precursor containing borazine structure - Google Patents
Preparation method of SiBCN ceramic precursor containing borazine structure Download PDFInfo
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- CN104974352A CN104974352A CN201510355139.2A CN201510355139A CN104974352A CN 104974352 A CN104974352 A CN 104974352A CN 201510355139 A CN201510355139 A CN 201510355139A CN 104974352 A CN104974352 A CN 104974352A
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Abstract
A preparation method of a SiBCN ceramic precursor containing a borazine structure belongs to the field of inorganic non-metal materials. The preparation method comprises the following steps of: firstly, preparing methylchlorosilane into a Grignard reagent, and taking the Grignard reagent to react with chlorine-containing borazine to obtain a micro-molecular structure containing the borazine structure; and furthermore, carrying out aminolysis on a micro-molecular product containing a Si-CI group to obtain a corresponding polymer product. A micro-molecule and a polymer are SiBCN ceramic precursors. The problems of an existing preparation method that a process is difficult to control, the product is difficult to prepare in batches and the like are solved. According to the preparation method provided by the invention, the cost of raw materials is low, the product with higher purity is easy to obtain and the product can be prepared in batches.
Description
Technical field
The invention belongs to field of inorganic nonmetallic material, relate to a kind of preparation method of the SiBCN ceramic forerunner containing borazine structure.
Background technology:
Continuous Fiber Reinforced Ceramic Matrix Composites not only has the advantages such as high temperature resistant, corrosion-resistant, wear-resistant, the excellent in mechanical performance of traditional ceramics, also overcome the shortcomings such as the fragility of traditional ceramics itself and calamity damage simultaneously, demonstrate excellent toughness and reliability, have broad application prospects in the field such as the energy, Aeronautics and Astronautics.
In various ceramic matric composite preparation method, equipment requirements is low, easy to operate owing to having for polymer infiltration and pyrolysis technique, ceramic matrix designability strong and be easy to the advantages such as preparation complex shaped components, is subject to the extensive concern of investigator.In this preparation method, the synthesis and structure of presoma controls to be crucial.In recent years, at SiC and Si
3n
4on the basis of ceramic forerunner, grow up a kind of polynary pottery newly---SiBCN pottery, compared with the above two demonstrate more excellent over-all properties (1, Pengfei Zhang, DechangJia, Zhihua Yang, et al.Progress of anovel non-oxide Si-B-C-N ceramic and its matrix composites.Journal of AdvancedCeramics, 2012,1:157-178; 2, CN1145348A).M Jansen etc. (3, T.J ¨ aschke, M.Jansen.Improved durability of Si/B/N/C random inorganic networks.Journal of the EuropeanCeramic Society, 2005,25:211 – 220) compared for the SiBCN ceramic forerunner of various structures, find that the SiBCN ceramic performance that the presoma containing borazine structure obtains is more excellent, its thermal stability is more than 2000 DEG C.Its synthetic route is: first prepare boryl chlorosilane by grignard reaction, then carries out cyclization with hexamethyldisilazane and prepares the small molecules containing borazine, last ammonia solution or the polymkeric substance of aminolysis preparation containing borazine structure.But this synthetic route exists technology controlling and process difficulty, is difficult to the problems such as preparation in enormous quantities, be difficult to realize the widespread use in SiBCN ceramic matric composite.
Summary of the invention:
The object of the present invention is to provide a kind of technology controlling and process preparation method that is simple, the easily SiBCN ceramic forerunner containing borazine structure prepared in enormous quantities.
Technical solution of the present invention is,
The preparation method of described a kind of SiBCN ceramic forerunner containing borazine structure comprises the following steps:
1) in anhydrous and oxygen-free environment, added by magnesium in reaction flask, add ether or tetrahydrofuran (THF) makes its submergence magnesium, then add 1 ~ 2 iodine, the chloromethyl silane of instillation amount of initiator causes grignard reaction, makes Grignard reagent.
2) in anhydrous and oxygen-free environment, by step 1) Grignard reagent of gained reacts with the chloride borazine being dissolved in anhydrous solvent, removing anhydrous solvent and by product, obtain the small molecules product containing borazine structure, the molar ratio of Grignard reagent and chloride borazine is 1-20:1-20, and the consumption of described solvent is 1 ~ 10 times of described chloromethyl silane and described chloride borazine total mass; Grignard reagent is-80 ~ 80 DEG C with the temperature of reaction of the chloride borazine being dissolved in anhydrous solvent, and the reaction times is 1 ~ 24 hour.
3) in anhydrous and oxygen-free environment, by step 2) in containing being dissolved in anhydrous solvent containing the small molecules product of Si-Cl group in the small molecules product of borazine structure, then react with ammonia or organic amine, except desolventizing and by product, obtain the polymer product containing borazine structure.The consumption of described solvent is 1 ~ 10 times of the described small molecules product quality containing Si-Cl group; Described ammonia or the consumption of organic amine are 1 ~ 10 times of described micromolecular Si-Cl group mole number, the described small molecules product containing Si-Cl group and ammonia or organic amine temperature of reaction are-80 ~ 80 DEG C, reaction times is 1 ~ 24 hour, obtains the polymer product containing borazine structure.
Step 1) in, described magnesium is at least one in magnesium powder, magnesium chips, magnesium rod etc.
Step 1) in, described chloromethyl silane is the mixing of one or more in Chloromethyltrichlorosilane, chloromethylmethyldichlorsilane, CMDMCS chloromethyl dimethyl chlorosilane, chloromethyl methyl chlorosilane, chloromethyl methyl-monosilane or chloromethyl trimethyl silane.
Step 2) in, described chloride borazine is selected from trichlorine borazine, dialkyl group chlorine borazine or alkyl dichloro borazine, and the alkyl that described alkyl is hydrogen, the total number of carbon atoms is 1-6, the total number of carbon atoms are the alkenyl of 2-4, the total number of carbon atoms is at least one in the aryl of 6-10.
Step 2) in, the aromatic hydrocarbons that described solvent is selected from alkane that the total number of carbon atoms is 6-10, the total number of carbon atoms is 6-8, the total number of carbon atoms are the ether of 4-8 and at least one of furans, specifically comprise at least one in hexane, toluene, dimethylbenzene, ether, tetrahydrofuran (THF).
Step 1) described in chloromethyl silane and step 2) in the molar ratio of Grignard reagent and chloride borazine be preferred 1-5:1-5; The consumption of anhydrous solvent is described chloromethyl silane and described chloride borazine total mass preferably 2 ~ 4 times.
Step 3) in, described organic amine is selected from least one in methylamine, ethamine, quadrol, propylamine, aniline and Ursol D; Described ammonia or the consumption of organic amine are described micromolecular Si-Cl group mole number preferably 2 ~ 4 times.
Feature of the present invention:
The present invention is low with cost, that be easy to a large amount of preparation, and chloride borazine is raw material, grignard reaction is adopted directly to obtain SiBCN ceramic forerunner small molecules, or ammonia (amine) separates acquisition SiBCN ceramic forerunner polymkeric substance further, there is technology controlling and process difficulty, be difficult to the problems such as preparation in enormous quantities in the synthetic route avoiding employing at present.
Advantage of the present invention comprises: 1) raw materials cost is low; 2) be easy to obtain the higher product of purity; 3) preparation in enormous quantities can be realized; 4) the final SiBCN pottery excellent heat stability obtained, can be directly used in preparation SiBCN ceramic matric composite.
Accompanying drawing explanation
Fig. 1 is that the SiBCN ceramic forerunner containing borazine structure in embodiment 1 is micromolecular
1h-NMR spectrogram.
Fig. 2 is that the SiBCN ceramic forerunner containing borazine structure in embodiment 1 is micromolecular
13c-NMR spectrogram.
Embodiment:
Below in conjunction with embodiment, the invention will be further described.
1) in anhydrous and oxygen-free environment, added by magnesium in reaction flask, add ether or tetrahydrofuran (THF) makes its submergence magnesium, then add 1 ~ 2 iodine, the chloromethyl silane of instillation initiator magnitude causes grignard reaction, makes Grignard reagent.
2) in anhydrous and oxygen-free environment, by step 1) Grignard reagent of gained react with the chloride borazine being dissolved in anhydrous solvent, and removing anhydrous solvent and by product, obtain the small molecules product containing borazine structure.
3) in anhydrous and oxygen-free environment, by step 2) in containing being dissolved in anhydrous solvent containing the small molecules product of Si-Cl group in the small molecules product of borazine structure, then react with ammonia or organic amine, except desolventizing and by product, obtain the polymer product containing borazine structure.
In step 1) in, described magnesium is at least one in magnesium powder, magnesium chips, magnesium rod etc.
In step 1) in, described chloromethyl silane is the mixing of one or more in Chloromethyltrichlorosilane, chloromethylmethyldichlorsilane, CMDMCS chloromethyl dimethyl chlorosilane, chloromethyl methyl chlorosilane, chloromethyl methyl-monosilane or chloromethyl trimethyl silane.
In step 2) in, described chloride borazine is selected from trichlorine borazine, dialkyl group chlorine borazine or alkyl dichloro borazine, and the alkyl that described alkyl is hydrogen, the total number of carbon atoms is 1-6, the total number of carbon atoms are the alkenyl of 2-4, the total number of carbon atoms is at least one in the aryl of 6-10.
In step 2) in, the aromatic hydrocarbons that described solvent is selected from alkane that the total number of carbon atoms is 6-10, the total number of carbon atoms is 6-8, the total number of carbon atoms are the ether of 4-8 and at least one of furans, specifically comprise at least one in hexane, toluene, dimethylbenzene, ether, tetrahydrofuran (THF).
In step 1) described in chloromethyl silane and step 2) in the molar ratio of Grignard reagent and chloride borazine be preferred 1-5:1-5; The consumption of anhydrous solvent is described chloromethyl silane and described chloride borazine total mass preferably 2 ~ 4 times.
In step 2) in, described temperature of reaction is-80 ~ 80 DEG C, and the reaction times is 1 ~ 24 hour.
In step 3) in, described organic amine is selected from least one in methylamine, ethamine, quadrol, propylamine, aniline and Ursol D; Described ammonia or the consumption of organic amine are described micromolecular Si-Cl group mole number preferably 2 ~ 4 times.Described temperature of reaction is-80 ~ 80 DEG C, and the reaction times is 1 ~ 24 hour.
Embodiment 1
1) in anhydrous and oxygen-free environment, magnesium chips through activation is in advance put into Schlenk reaction flask, under nitrogen protection, add 15mL tetrahydrofuran (THF) and 1.3g chloromethyl methyl-monosilane, when tetrahydrofuran (THF) refluxes, under ice bath, dropwise add the mixing solutions of 20.5g chloromethyl methyl-monosilane and 30mL tetrahydrofuran (THF), then 60 DEG C of backflows 8 hours, obtain Grignard reagent;
2) in anhydrous and oxygen-free environment, to step 1 under ice bath) dropwise add the mixing solutions of 12.9g trichlorine borazine and 50mL toluene in the Grignard reagent of gained, then at room temperature stir 8 hours, except desolventizing and by product, obtain the small molecules product containing borazine structure; Adopt nmr analysis instrument to characterize its H respectively to compose and C spectrum, as illustrated in fig. 1 and 2.
Embodiment 2
1) in anhydrous and oxygen-free environment, magnesium chips through activation is in advance put into Schlenk reaction flask, under nitrogen protection, add 15mL ether and 1.5g chloromethylmethyldichlorsilane, when aether backflow, under ice bath, dropwise add the mixing solutions of 30.5g chloromethylmethyldichlorsilane and 50mL ether, then 80 DEG C of backflows 6 hours, obtain Grignard reagent;
2) in anhydrous and oxygen-free environment, to step 1 under ice bath) dropwise add the mixing solutions of 14.9g dichloro borazine and 50mL toluene in the Grignard reagent of gained, then at room temperature stir 8 hours, except desolventizing and by product, obtain the small molecules product containing borazine structure;
3) in anhydrous and oxygen-free environment, to step 2 at-30 DEG C) pass into ammonia in small molecular product, till system display alkalescence, now ammonia usage is about 2 times of the Si-Cl group mole number in small molecules, cross and filter ammonium chloride, underpressure distillation, except desolventizing, obtains the polymer product containing borazine structure.
Claims (7)
1., containing a preparation method for the SiBCN ceramic forerunner of borazine structure, it is characterized in that comprising the following steps:
1) in anhydrous and oxygen-free environment, added by magnesium in reaction flask, add ether or tetrahydrofuran (THF) makes its submergence magnesium, then add 1 ~ 2 iodine, instillation chloromethyl silane causes grignard reaction, makes Grignard reagent;
2) in anhydrous and oxygen-free environment, by step 1) Grignard reagent of gained reacts with the chloride borazine being dissolved in anhydrous solvent, removing anhydrous solvent and by product, obtain the small molecules product containing borazine structure, the molar ratio of Grignard reagent and chloride borazine is 1-20:1-20, and the consumption of described solvent is 1 ~ 10 times of described chloromethyl silane and described chloride borazine total mass; Grignard reagent is-80 ~ 80 DEG C with the temperature of reaction of the chloride borazine being dissolved in anhydrous solvent, and the reaction times is 1 ~ 24 hour;
3) in anhydrous and oxygen-free environment, by step 2) in containing being dissolved in anhydrous solvent containing the small molecules product of Si-Cl group in the small molecules product of borazine structure, then react with ammonia or organic amine, except desolventizing and by product, obtain the polymer product containing borazine structure.The consumption of described solvent is 1 ~ 10 times of the described small molecules product quality containing Si-Cl group; Described ammonia or the consumption of organic amine are 1 ~ 10 times of described micromolecular Si-Cl group mole number, the described small molecules product containing Si-Cl group and ammonia or organic amine temperature of reaction are-80 ~ 80 DEG C, reaction times is 1 ~ 24 hour, obtains the polymer product containing borazine structure.
2. the preparation method of a kind of SiBCN ceramic forerunner containing borazine structure according to claim 1, it is characterized in that, described magnesium is at least one in magnesium powder, magnesium chips, magnesium rod.
3. the preparation method of a kind of SiBCN ceramic forerunner containing borazine structure according to claim 1, it is characterized in that, described chloromethyl silane is the mixing of one or more in Chloromethyltrichlorosilane, chloromethylmethyldichlorsilane, CMDMCS chloromethyl dimethyl chlorosilane, chloromethyl methyl chlorosilane, chloromethyl methyl-monosilane or chloromethyl trimethyl silane.
4. the preparation method of a kind of SiBCN ceramic forerunner containing borazine structure according to claim 1, it is characterized in that, described chloride borazine is selected from trichlorine borazine, dialkyl group chlorine borazine or alkyl dichloro borazine, and the alkyl that described alkyl is hydrogen, the total number of carbon atoms is 1-6, the total number of carbon atoms are the alkenyl of 2-4, the total number of carbon atoms is at least one in the aryl of 6-10.
5. the preparation method of a kind of SiBCN ceramic forerunner containing borazine structure according to claim 1, it is characterized in that, the aromatic hydrocarbons that described solvent is selected from alkane that the total number of carbon atoms is 6-10, the total number of carbon atoms is 6-8, the total number of carbon atoms are the ether of 4-8 and at least one of furans, specifically comprise at least one in hexane, toluene, dimethylbenzene, ether, tetrahydrofuran (THF).
6. the preparation method of a kind of SiBCN ceramic forerunner containing borazine structure according to claim 1, is characterized in that, described in chloromethyl silane and step 2) molar ratio of middle Grignard reagent and chloride borazine is preferred 1-5:1-5; The consumption of anhydrous solvent is described chloromethyl silane and described chloride borazine total mass preferably 2 ~ 4 times.
7. the preparation method of a kind of SiBCN ceramic forerunner containing borazine structure according to claim 1, it is characterized in that, step 3) in, described organic amine is selected from least one in methylamine, ethamine, quadrol, propylamine, aniline and Ursol D; Described ammonia or the consumption of organic amine are described micromolecular Si-Cl group mole number preferably 2 ~ 4 times.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108707234A (en) * | 2018-04-26 | 2018-10-26 | 华东理工大学 | A kind of silicon boron azane ceramic forerunner polymer containing borazine, preparation method and applications |
| CN109251038A (en) * | 2018-10-15 | 2019-01-22 | 西北工业大学 | Polymer cracking containing phenyl ring converts SiBCN metal-free ceramic absorbing material and preparation method |
| CN115651414A (en) * | 2022-09-28 | 2023-01-31 | 中国航空制造技术研究院 | Liquid complex phase SiBCN ceramic precursor and preparation method of SiBCN ceramic |
| CN115651202A (en) * | 2022-09-28 | 2023-01-31 | 中国航空制造技术研究院 | Preparation method of modified polycarbosilane containing pyridine ring and wave-absorbing silicon carbide ceramic powder |
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| CN101182213A (en) * | 2007-11-16 | 2008-05-21 | 东华大学 | Method for preparing silicon-boron-nitrogen ceramic fiber precursor |
| CN101274941A (en) * | 2008-05-08 | 2008-10-01 | 中国人民解放军国防科学技术大学 | Preparation for polyborosilazanes precursor |
| CN104387078A (en) * | 2014-10-22 | 2015-03-04 | 华文蔚 | SiBCN composite material and preparation method thereof |
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| US20040039217A1 (en) * | 2000-09-12 | 2004-02-26 | Martin Jansen | High temperature-stabile silicon boron carbide nitride ceramics comprised of silylalkyl borazines,method for the production thereof, and their use |
| CN101182213A (en) * | 2007-11-16 | 2008-05-21 | 东华大学 | Method for preparing silicon-boron-nitrogen ceramic fiber precursor |
| CN101274941A (en) * | 2008-05-08 | 2008-10-01 | 中国人民解放军国防科学技术大学 | Preparation for polyborosilazanes precursor |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108707234A (en) * | 2018-04-26 | 2018-10-26 | 华东理工大学 | A kind of silicon boron azane ceramic forerunner polymer containing borazine, preparation method and applications |
| CN109251038A (en) * | 2018-10-15 | 2019-01-22 | 西北工业大学 | Polymer cracking containing phenyl ring converts SiBCN metal-free ceramic absorbing material and preparation method |
| CN115651414A (en) * | 2022-09-28 | 2023-01-31 | 中国航空制造技术研究院 | Liquid complex phase SiBCN ceramic precursor and preparation method of SiBCN ceramic |
| CN115651202A (en) * | 2022-09-28 | 2023-01-31 | 中国航空制造技术研究院 | Preparation method of modified polycarbosilane containing pyridine ring and wave-absorbing silicon carbide ceramic powder |
| CN115651414B (en) * | 2022-09-28 | 2023-11-03 | 中国航空制造技术研究院 | Preparation method of liquid complex-phase SiBCN ceramic precursor and SiBCN ceramic |
| CN115651202B (en) * | 2022-09-28 | 2023-12-01 | 中国航空制造技术研究院 | Preparation method of pyridine ring-containing modified polycarbosilane and wave-absorbing silicon carbide ceramic powder |
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