CN103881101A - Polycarbosilazane precursor for silicon carbonitride ceramic and preparation method thereof - Google Patents
Polycarbosilazane precursor for silicon carbonitride ceramic and preparation method thereof Download PDFInfo
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- CN103881101A CN103881101A CN201410101238.3A CN201410101238A CN103881101A CN 103881101 A CN103881101 A CN 103881101A CN 201410101238 A CN201410101238 A CN 201410101238A CN 103881101 A CN103881101 A CN 103881101A
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Abstract
The invention relates to a polycarbosilazane precursor for silicon carbonitride ceramic and a preparation method thereof. The structure of the precursor uses [-Si (R2)-NH-R1-NH-n] as a main chain, wherein R1 is an organic carbon chain, and R2 is a pendant group bonded on a silicon atom; the R1 is an organic carbon chain, and the structure is straight chain alkyl-(CH2)n-, n is greater than or equal to 2, or phenyl-(C6H4)-; and R2 is hydrogen or alkyl. The preparation method comprises the following steps of with diamine as a nitrogen source, performing a condensation reaction with chlorosilane, wherein all operations and processes are performed under anhydrous, anaerobic and inert gas protection conditions; dissolving the chlorosilane in a solvent to obtain a uniform solution, and dissolving the diamine and a deacid reagent in the solvent to obtain a uniform solution, and then mixing the chlorosilane solution with the uniform solution under a stirring condition, filtering to remove a hydrochloride by-product after the reaction, and distilling to remove the solvent to obtain polycarbosilazane finally. The method is simple and easy to control, and the reaction can be regulated and controlled to obtain a variety of polycarbosilazane. The obtained silicon carbonitride ceramic has application potential in such fields as high temperature insulation, thermal protection, energy and environment, etc.
Description
Technical field
The present invention relates to a kind of polycarbosilazanes presoma and preparation method thereof, can be used for preparing silicon carbonitride ceramic, belong to the synthetic field of high temperature precursor ceramic and organosilicon.
Background technology
Precursor ceramic is the class new ceramic material being formed through pyrolysis by polymer precursor.Different from the polycrystalline ceramic body that conventional powder sintering forms, precursor ceramic has the three-dimensional net structure of strong covalent bond and ionic linkage formation, not containing low melting point phase, not only have excellent mechanics, high-temperature behavior, contained nano-carbon layer structure is given again the functional performances such as its electricity, calorifics and electrochemistry.Precursor process is a kind of ceramic desirable novel method of preparing, and it has without agglutinant, mixes without powder, can be in advantages such as lesser temps (600～1000 ℃) and normal pressure one-step moulding; Meanwhile, utilize the presoma of liquid phase can prepare the ceramic component of complicated shape, small ceramic component and high performance composite.Therefore, precursor ceramic is with a wide range of applications at aspects such as high-temperature field, matrix material and functional devices as structure and function material, is subject to the extensive concern of domestic and international researcher and research institution.
Silicon carbonitride ceramic is the important precursor ceramic of a class, can be formed through pyrolysis by polysilazane.Common silicon carbonitride ceramic has the three-dimensional amorphous network structure being made up of Si, C and N, forms Si in higher temperature (being greater than 1400 degree) pyrolysis
3n
4with SiC nanocomposite structure.Silicon carbonitride ceramic has excellent high-temperature behavior and mechanical property, and more than inert environments is stabilized to 1600 degree, more than air ambient is stabilized to 1300 degree, creep resistance temperature is greater than 1550 degree, and breaking tenacity is greater than 1GPa, and Vickers' hardness is greater than 15GPa.On the other hand, because the organic functions group in polysilazane forms nano-carbon layer structure in pyrolytic process, this gives silicon carbonitride ceramic some functional performances, as adjustable electroconductibility, thermal conductivity and chemical property.Therefore, silicon carbonitride ceramic can be applicable to the fields such as high temperature insulating, high-temperature oxidation resistant and corrosive environment as structured material, be applied to the fields such as the energy, environment and electrochemistry as functional materials.
Conventionally prepare silicon carbonitride ceramic polysilazane precursor used and be take silicon-nitrogen as main chain, key connects inertia or active lateral group (as – CH on Siliciumatom
3， – H ， – CH=CH
2) a class organosilicon polymer.The molecular structure of polysilazane precursor has directly determined structure and the performance of the silicon carbonitride ceramic that pyrolysis obtains.Therefore, the molecular designing of polysilazane precursor is the focus and emphasis of silicon carbonitride ceramic area research with synthesizing.In general, polysilazane take ammonia or methylamine as nitrogenous source and chlorosilane carry out dehydrochlorination condensation reaction and make.This class polysilazane, take Si – N repeating unit as main chain, can show to show for – [SiR
1r
2nR
3]
n–, wherein R
1, R
2=CH
3, H, CH=CH
2deng, R
3=H and CH
3.External existing industrialization polysilazane commodity selling, but it carries out blockade on new techniques and product embargo to China, although Beijing chemistry institute of the recent year Chinese Academy of Sciences and the National University of Defense technology have carried out independent research in this field, at the aspect such as stability and diversity of industrialization, product, also with abroad there is a big difference for it.Therefore, Development of Novel polysilazane precursor and technology of preparing thereof have important technological value and application value for obtaining high performance carbon silicon nitride ceramics.
Summary of the invention
The object of the present invention is to provide a kind of polycarbosilazanes presoma and preparation method thereof, can be used for preparing high temperature carbonization and nitrification silicon pottery.The technological approaches of preparing this presoma is take diamine as nitrogenous source, carries out aminolysis condensation reaction with chlorosilane, after filtration, distillation and synthesis go out polycarbosilazanes.
Technical scheme of the present invention is as follows:
A kind of silicon carbonitride ceramic polycarbosilazanes presoma; Structure be with [– Si (R2) – NH – R1 – NH –]
nfor main chain, wherein R1 is organic carbochain, and R2 is the side group that on Siliciumatom, key connects; R1 is organic carbochain, and structure is straight-chain alkyl ((CH
2)
n-), n is more than or equal to 2, or phenyl-(C
6h
4)-; R2 is hydrogen or is alkyl.
Described R1 is ethylidene-CH
2cH
2-, propylidene-CH
2cH
2cH
2-, butylidene-CH
2cH
2cH
2cH
2-, hexylidene-CH
2cH
2cH
2cH
2cH
2cH
2-or phenyl-(C
6h
4)-.
The preparation method of polycarbosilazanes presoma of the present invention, take diamine as nitrogenous source, carries out condensation reaction with chlorosilane, and all operations and process are carried out under anhydrous and oxygen-free, logical inertia protection gas condition; Chlorosilane is dissolved in to solvent and obtains homogeneous solution, again diamine and Fu acid agent is dissolved in to solvent and obtains homogeneous solution, then under agitation condition by chlorosilane solution and two hybrid reactions, after reaction through removing by filter hydrochloride by product, remove desolventizing through distillation again, finally obtain polycarbosilazanes.
The chlorosilane adding and the chlorine of diamine and nitrogen-atoms mol ratio are 1:1, and Fu's acid agent and diamine mol ratio are 2.0～2.3:1.
Described diamine is the straight chain primary amine containing two amidos, and structural formula is NH
2r1NH
2; R1 group in the corresponding main chain of R1; Diamine is quadrol, propylene diamine, butanediamine, hexanediamine or phenylenediamine.
Described chlorosilane is that structural formula is Si (R2) containing one or more of the chlorosilane of two or three chlorine atoms
4-ncl
n; Wherein n=2 or 3, R2 are hydrogen or are alkyl; Alkyl is methyl, ethyl, propyl group, vinyl or phenyl.
Be described as follows:
The preparation method of polycarbosilazanes presoma, take diamine as nitrogenous source, carries out prepared by condensation reaction with chlorosilane.All operations and process are all carried out under anhydrous and oxygen-free, logical inertia protection gas condition.Specifically chlorosilane is dissolved in to solvent and obtains homogeneous solution, again diamine and Fu acid agent is dissolved in to solvent and obtains homogeneous solution, then under agitation condition, chlorosilane solution is dropped in diamine solution, or diamine solution is dropped in chlorosilane solution, after reaction through removing by filter hydrochloride by product, remove desolventizing through distillation again, finally obtain polycarbosilazanes.Wherein, the chlorosilane that requirement adds and chlorine and the nitrogen-atoms mol ratio of diamine are 1:1, and Fu's acid agent and diamine mol ratio are 2.0-2.3:1.
R1 group in polycarbosilazanes on main chain comes from diamine, and R2 side group comes from chlorosilane.
The described diamine of preparing polycarbosilazanes is the straight chain primary amine containing two amidos, uses general formula NH
2r1NH
2represent; R1 is organic carbochain, the R1 group in corresponding main chain; R1 can be straight-chain alkyl ((CH
2)
n-), n is more than or equal to 2, comprises ethylidene-CH
2cH
2-, propylidene-CH
2cH
2cH
2-, butylidene-CH
2cH
2cH
2cH
2-, hexylidene-CH
2cH
2cH
2cH
2cH
2cH
2-, can be also phenyl ((C
6h
4)-); Preferred diamine is quadrol, propylene diamine, butanediamine, hexanediamine and phenylenediamine.
The described chlorosilane of preparing polycarbosilazanes is the chlorosilane containing two or three chlorine atoms, can be that one can be also multiple, with general formula Si (R2)
4-ncl
nrepresent; Wherein n=2 or 3, R2 are hydrogen, alkyl; Alkyl is methyl, ethyl, propyl group, vinyl or phenyl.
Described Fu's acid agent of preparing polycarbosilazanes is that adsorbable hydrogenchloride forms hydrochloride and by the tertiary amine removing by filter; Preferably triethylamine and pyridine.
The described solvent of preparing polycarbosilazanes is aliphatic hydrocarbon, aromatic hydrocarbon and heterocyclic hydrocarbon; Preferably toluene, benzene and tetrahydrofuran (THF).
The invention provides one and prepare polycarbosilazanes presoma and preparation method thereof, have important theory significance and using value for Development of Novel refractory ceramics.This polycarbosilazanes is a kind of with [– Si – NH – R1 – NH –]
nfor the polysilazane of main chain, carbon containing functional group in main chain, this is different from common polysilazane with [– Si – N –]
nfor main chain.Technical characterictic of the present invention is to replace common ammonia and methylamine as nitrogenous source take diamine, carries out aminolysis condensation reaction with chlorosilane, after filtration, distillation and synthesis go out polycarbosilazanes.The method simply, easily control, can obtain the polycarbosilazanes of different the Nomenclature Composition and Structure of Complexes by changing chlorosilane and diamine kind.Synthetic polycarbosilazanes presoma can high ceramic yield conversion form silicon carbonitride ceramic, the pottery of formation is with the SiN of rich nitrogen
4structure is main, and this structure is also different from common polysilazane precursor and transforms the pottery forming, and this is relevant with the introducing of carbon functional group in main chain.Diamine is introduced directly into carbon atom on silicon nitrogen main chain in reaction process, and pyrolysis obtains the silicon carbonitride ceramic of rich carbon, has conduction, leads the functional performances such as thermal and electrochemical.
Therefore the present invention not only can be applicable to the civilian hi-tech high temperature insulating in aerospace, national defense and military, nuclear energy and middle and high end and thermal protection field, also can be applicable to the functional areas such as the energy, environment and electrochemistry.
Accompanying drawing explanation
Fig. 1: the infrared spectrum of polycarbosilazanes prepared by the invention process example 1.
Fig. 2: the liquid phase hydrogen spectrogram of polycarbosilazanes prepared by the invention process example 1.
Fig. 3: the liquid phase carbon spectrogram of polycarbosilazanes prepared by the invention process example 1.
Fig. 4: the thermogravimetric analysis curve of polycarbosilazanes prepared by the invention process example 1.
Embodiment
A kind of polycarbosilazanes presoma the present invention relates to, can be used for preparing silicon carbonitride ceramic; It is characterized in that structure be with [– Si (R2) – NH – R1 – NH –]
nfor main chain, on Siliciumatom, key connects R2 side group.
The preparation method of polycarbosilazanes presoma for the silicon carbonitride ceramic that the present invention relates to, is characterized in that take diamine as nitrogenous source, carries out prepared by condensation reaction with chlorosilane.All operations and process are all carried out under anhydrous and oxygen-free, logical inertia protection gas condition.Specifically chlorosilane is dissolved in to solvent and obtains homogeneous solution, again diamine and Fu acid agent is dissolved in to solvent and obtains homogeneous solution, then under agitation condition, chlorosilane solution is dropped in diamine solution, or diamine solution is dropped in chlorosilane solution, after reaction through removing by filter hydrochloride by product, remove desolventizing through distillation again, finally obtain polycarbosilazanes.Wherein, the chlorosilane that requirement adds and chlorine and the nitrogen-atoms mol ratio of diamine are 1:1, and Fu's acid agent and diamine mol ratio are 2.0-2.3:1.
Described diamine is the straight chain primary amine containing two amidos, uses general formula NH
2r1NH
2represent; R1 is organic carbochain, and the R1 group in corresponding polycarbosilazanes main chain can be straight-chain alkyl ((CH
2)
n-), n is more than or equal to 1, is preferably methylene radical-CH
2-, ethylidene-CH
2cH
2-, propylidene-CH
2cH
2cH
2-; Also can be phenyl ((C
6h
4)-); Preferably diamine is methanediamine, quadrol, propylene diamine and phenylenediamine.
Described chlorosilane is the chlorosilane containing two or three chlorine atoms, can be a kind of, can be also several; With general formula (R2)
4-nsiCl
nrepresent; Wherein the R2 side group in the corresponding polycarbosilazanes of n=2 or 3, R2, is hydrogen or alkyl, comprises methyl, ethyl, propyl group, vinyl or phenyl.
Described Fu acid agent is that adsorbable hydrogenchloride forms hydrochloride and by the tertiary amine removing by filter; Preferably triethylamine and pyridine.
Described solvent is aliphatic hydrocarbon, aromatic hydrocarbon and heterocyclic hydrocarbon; Preferably toluene, benzene and tetrahydrofuran (THF).
Below lift exemplary explanation:
Embodiment 1: adopt and mix dichlorosilane and reacting ethylenediamine, take toluene as solvent, triethylamine is acid binding agent, synthetic polycarbosilazanes.Detailed process is: argon shield; under room temperature, by vinyl dimethyl dichlorosilane (DMCS) (10.2g, 72mmol), dimethyl dichlorosilane (DMCS) (8.3g; 72mmol) be uniformly mixed with 50ml toluene, obtain the toluene solution of the dichlorosilane of achromaticity and clarification.Under magnetic agitation, above-mentioned solution is slowly added drop-wise in the 150ml toluene solution of quadrol (8.6g, 144mmol) and triethylamine (30.3g, 300mmol), in dropping process, adularescent flocks forms, for triethylamine hydrochloride by product, after dropwising, react again 1h, remove precipitation by filtration, collect flaxen filtrate, steaming except toluene solvant finally by underpressure distillation, obtain polycarbosilazanes, is yellow honey shape thick liquid.Fourier infrared spectrograph (RAYLEIGHWQF-510 type, Beijing) and Liquid NMR (Varian Inove500MHz, USA, CDCl
3for solvent) prove that polycarbosilazanes is with [– Si – N – C – C – N –]
nfor main chain, Jian Lian – CH=CH on Siliciumatom
2， – H is with – CH
3three kinds of side groups, the mol ratio of these three kinds of side groups is 1:1:2, with add dichlorosilane in group than consistent.In silver nitrate solution titration measuring polycarbosilazanes, there is no residual chlorine atom.It is high polymer but not oligopolymer that gel permeation chromatography (Waters1525binary HPLC pump equipped, the U.S.) is analyzed polycarbosilazanes, and its number-average molecular weight is 28281, and weight-average molecular weight is 39622, mean polymerisation degree～246.Fig. 1, Fig. 2 and Fig. 3 are respectively infrared spectrum, liquid phase hydrogen spectrum and the liquid phase carbon spectrograms of polycarbosilazanes.As can be seen from the figure in spectrogram, there is Si – N, the characteristic peak of N – H and N – C – C – N group, provable Xing Cheng – Si – N – C – C – N – main chain; Also find out and have Si – CH=CH
2, Si – H and Si – CH
3group characteristic peak is side groups according to these groups of reaction; The synthetic presoma of deducibility is with [– Si – N – C – C – N – accordingly]
nfor main chain, Jian Lian – CH=CH on Siliciumatom
2， – H is with – CH
3three kinds of side groups are identical with expected structure.
Embodiment 2: adopt the identical method of example 1, replace and mix silicon source take dimethyl dichlorosilane (DMCS) as single silicon source, other condition is constant.Argon shield, under room temperature, by quadrol (8.6g; 144mmol) and triethylamine (30.3g; 300mmol) and 100ml toluene by being uniformly mixed, then be added drop-wise in the 30ml toluene solution of dimethyl dichlorosilane (DMCS) (16.6g, 144mmol); after dropwising, stir again 1h; remove white flocks by filtration, collect filtrate, steam and desolventize finally by underpressure distillation; obtaining polycarbosilazanes, is colourless viscous liquid.Fourier infrared spectrograph (RAYLEIGHWQF-510 type, Beijing) proves that the side group Wei – H of polycarbosilazanes is with – CH
3.
Embodiment 3: adopt the identical method of example 1, take phenylmethyldichloroislane as silicon source, other condition is constant.Argon shield, under room temperature, by phenylmethyldichloroislane (13.8g; 72mmol) and 30ml toluene by being uniformly mixed; be added drop-wise to again in the 100ml toluene solution of quadrol (4.3g, 72mmol) and triethylamine (15.1g, 150mmol); after dropwising, stir again 1h; remove white flocks by filtration, collect filtrate, steam and desolventize finally by underpressure distillation; obtaining the polycarbosilazanes of side group containing phenyl, is colourless viscous liquid.
Embodiment 4: adopt the identical method of example 1, take vinyl trichloro silane as silicon source, other condition is constant.Argon shield, under room temperature, by vinyl trichloro silane (23.2g; 144mmol) and 30ml toluene by being uniformly mixed; be added drop-wise to again in the 100ml toluene solution of quadrol (12.9g, 216mmol) and triethylamine (30.3g, 300mmol); after dropwising, stir again 1h; remove white flocks by filtration, collect filtrate, steam and desolventize finally by underpressure distillation; obtaining the polycarbosilazanes that side group only has vinyl, is white solid.
Embodiment 5: adopt the identical method of example 1, replace toluene as solvent take tetrahydrofuran (THF), change the addition of dichlorosilane, other condition is constant.Argon shield, under room temperature, by dimethyl dichlorosilane (DMCS) (14.5g, 90mmol), vinyl dimethyl dichlorosilane (DMCS) (8.5g, 60mmol) be uniformly mixed with 30ml tetrahydrofuran (THF), under magnetic agitation, be added drop-wise to quadrol (9.0g, 150mmol) and triethylamine (48g, in 100ml tetrahydrofuran solution 475mmol), in dropping process, adularescent flocks forms, for triethylamine hydrochloride by product, after dropwising, react again 1h, remove precipitation by filtration, collect filtrate, underpressure distillation is steamed and is desolventized, obtain polycarbosilazanes, for yellow honey shape thick liquid.Fourier infrared spectrograph (RAYLEIGH WQF-510 type, Beijing) and Liquid NMR (Varian Inove500MHz, USA, CDCl
3for solvent) prove that polycarbosilazanes is take – Si – N – C – C – N – as main chain, Jian Lian – CH=CH on Siliciumatom
2， – H is with – CH
3three kinds of side groups, the mol ratio of these three kinds of side groups is 2:3:5, with add dichlorosilane in group than consistent.
Embodiment 6: adopt the identical method of example 2, take propylene diamine as nitrogenous source, other condition is constant.Argon shield, under room temperature, by dimethyl dichlorosilane (DMCS) (16.6g; 144mmol) and 50ml toluene by being uniformly mixed; be added drop-wise to again in the 150ml toluene solution of propylene diamine (10.7g, 144mmol) and triethylamine (30.3g, 300mmol); after dropwising, stir again 1h; remove white triethylamine hydrochloride precipitation by filtration, collect filtrate, desolventize finally by crossing air distillation steaming; obtaining polycarbosilazanes, is colourless viscous liquid.
Embodiment 7: adopt the identical method of example 2, take phenylenediamine as nitrogenous source, other condition is constant.Argon shield, under room temperature, by dimethyl dichlorosilane (DMCS) (16.6g; 144mmol) and 50ml toluene by being uniformly mixed; be added drop-wise to again in the 150ml toluene solution of phenylenediamine (15.5g, 144mmol) and triethylamine (30.3g, 300mmol); after dropwising, stir again 1h; remove white triethylamine hydrochloride precipitation by filtration, collect filtrate, desolventize finally by crossing air distillation steaming; obtaining polycarbosilazanes, is colourless viscous liquid.
Embodiment 8: adopt the identical method of example 2, the acid agent take pyridine as Fu, other condition is constant.Argon shield, under room temperature, by dimethyl dichlorosilane (DMCS) (16.6g; 144mmol) and 30ml toluene by being uniformly mixed; be added drop-wise to again in the 100ml toluene solution of quadrol (8.6g, 144mmol) and pyridine (23.7g, 300mmol); after dropwising, stir again 1h; remove white pyridine hydrochloride precipitation by filtration, collect filtrate, desolventize finally by crossing air distillation steaming; obtaining polycarbosilazanes, is colourless viscous liquid.
Embodiment 9: by obtain polycarbosilazanes for the preparation of silicon carbonitride ceramic.Linking agent is joined in the polycarbosilazanes of embodiment 1,80 degree heating 2 hours, then be placed on High Temperature Furnaces Heating Apparatus, and in argon gas stream, rising to 1000 degree insulation 1 hour with 5 ℃/min, pyrolysis obtains silicon carbonitride ceramic.The ceramic yield that thermogravimetric differential thermal analyzer (Netzsch STA449C, Germany) is analyzed polycarbosilazanes is higher, and in argon gas atmosphere, the ceramic conversion rate of 1000 degree is 76wt.%.Fig. 4 is that synthetic presoma rises to 10 degree/point speed the thermogravimetric analysis curve that 1200 degree obtain in argon gas atmosphere.Thermogravimetric analysis silicon carbonitride ceramic can be stabilized to 1500 degree.Using the silicon carbonitride ceramic obtaining as cathode of lithium battery, metal lithium sheet is anodal, is assembled into button cell, electrochemical workstation test, and when current density is 40mA/g, first charge-discharge capacity 608 – 754mAh/g, stablize capacity 170 – 230mAh/g.Equally, polycarbosilazanes pyrolysis in 1000 degree ar gas environments that embodiment 2-8 obtains all can obtain silicon carbonitride ceramic.
Claims (10)
1. a silicon carbonitride ceramic polycarbosilazanes presoma; It is characterized in that structure be with [– Si (R2) – NH – R1 – NH –]
nfor main chain, wherein R1 is organic carbochain, and R2 is the side group that on Siliciumatom, key connects; R1 is organic carbochain, and structure is straight-chain alkyl-(CH
2)
n-, or be phenyl-(C
6h
4)-, n is more than or equal to 2; R2 is hydrogen or is alkyl.
2. presoma as claimed in claim 1, is characterized in that described R1 is ethylidene-CH
2cH
2-, propylidene-CH
2cH
2cH
2-, butylidene-CH
2cH
2cH
2cH
2-, hexylidene-CH
2cH
2cH
2cH
2cH
2cH
2-or phenyl-(C
6h
4)-.
3. the preparation method of the polycarbosilazanes presoma of claim 1, is characterized in that take diamine as nitrogenous source, carries out condensation reaction with chlorosilane, and all operations and process are carried out under anhydrous and oxygen-free, logical inertia protection gas condition; Chlorosilane is dissolved in to solvent and obtains homogeneous solution, again diamine and Fu acid agent is dissolved in to solvent and obtains homogeneous solution, then under agitation condition by chlorosilane solution and two hybrid reactions, after reaction through removing by filter hydrochloride by product, remove desolventizing through distillation again, finally obtain polycarbosilazanes.
4. method as claimed in claim 3, is characterized in that the chlorosilane that adds and chlorine and the nitrogen-atoms mol ratio of diamine are 1:1, and Fu's acid agent and diamine mol ratio are 2.0～2.3:1.
5. method as claimed in claim 3, is characterized in that described diamine is the straight chain primary amine containing two amidos, and structural formula is NH
2r1NH
2; R1 group in the corresponding main chain of R1; Diamine is quadrol, propylene diamine, butanediamine, hexanediamine or phenylenediamine.
6. method as claimed in claim 3, is characterized in that described chlorosilane is that structural formula is Si (R2) containing one or more of the chlorosilane of two or three chlorine atoms
4-ncl
n; Wherein n=2 or 3, R2 are hydrogen or are alkyl; Alkyl is methyl, ethyl, propyl group, vinyl or phenyl.
7. method as claimed in claim 3, is characterized in that described Fu acid agent is that absorption hydrogenchloride forms hydrochloride and by the tertiary amine removing by filter.
8. method as claimed in claim 7, is characterized in that described Fu's acid agent is triethylamine or pyridine.
9. method as claimed in claim 3, is characterized in that described solvent is aliphatic hydrocarbon, aromatic hydrocarbon and heterocyclic hydrocarbon.
10. method as claimed in claim 9, is characterized in that described solvent is toluene, benzene or tetrahydrofuran (THF).
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| US9969756B2 (en) | 2014-09-23 | 2018-05-15 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés George Claude | Carbosilane substituted amine precursors for deposition of Si-containing films and methods thereof |
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| CN115605530A (en) * | 2020-05-07 | 2023-01-13 | 默克专利有限公司（De） | Polycarbosilazanes, compositions comprising the same, and methods of making silicon-containing films using the same |
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| US9969756B2 (en) | 2014-09-23 | 2018-05-15 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés George Claude | Carbosilane substituted amine precursors for deposition of Si-containing films and methods thereof |
| CN104591741A (en) * | 2015-02-17 | 2015-05-06 | 哈尔滨工业大学 | Method for preparing SiNCB ceramic material |
| US10544506B2 (en) | 2015-03-30 | 2020-01-28 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Method of forming a silicon nitride film using Si—N containing precursors |
| CN104830230A (en) * | 2015-05-13 | 2015-08-12 | 江西科技师范大学 | Space environment damage prevention protective coating as well as preparation method and application thereof |
| US11407922B2 (en) | 2016-03-23 | 2022-08-09 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Si-containing film forming compositions and methods of making and using the same |
| CN115605530A (en) * | 2020-05-07 | 2023-01-13 | 默克专利有限公司（De） | Polycarbosilazanes, compositions comprising the same, and methods of making silicon-containing films using the same |
| CN114456389A (en) * | 2022-01-26 | 2022-05-10 | 江西信达航科新材料科技有限公司 | Modified organic polysilazane and preparation method thereof |
| CN114456392A (en) * | 2022-03-14 | 2022-05-10 | 江西信达航科新材料科技有限公司 | Benzoyl polysilazane and preparation method thereof |
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