CN109438712A - A kind of boron modification Polycarbosilane resin and preparation method thereof - Google Patents
A kind of boron modification Polycarbosilane resin and preparation method thereof Download PDFInfo
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- CN109438712A CN109438712A CN201811249968.2A CN201811249968A CN109438712A CN 109438712 A CN109438712 A CN 109438712A CN 201811249968 A CN201811249968 A CN 201811249968A CN 109438712 A CN109438712 A CN 109438712A
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- 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
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/08—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing boron
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Abstract
The present invention relates to a kind of preparation methods of boron modification Polycarbosilane, belong to new ceramic material preparation technical field.Reaction raw materials of the present invention are general chemical raw material；Feed material price is low, preparation process simple process；It is low-viscosity (mobile) liquid under novel SiBC ceramic forerunner room temperature prepared by the present invention, viscosity 10-500mPa.S has extraordinary processing performance；Contain Si-H, B-H and C=C isoreactivity group and unsaturated bond in novel SiBC ceramic forerunner prepared by the present invention, can be solidified with self-crosslinking, curing exotherm is small, and solidification is weightless low, and ceramic yield is high under high temperature, up to 60-70%；The each element content ratio of novel SiBC ceramic forerunner prepared by the present invention can be adjusted by feed ratio；Novel SiBC ceramic forerunner prepared by the present invention can be used for ultra-temperature ceramic-based composite material impregnation matrix, also can be used for the preparation of the high performance materials such as ceramic coating, fiber, tool has been widely used.
Description
Technical field
The present invention relates to a kind of preparation methods of boron modification Polycarbosilane, belong to new ceramic material preparation technical field.
Background technique
Ceramic Matrix Composites Reinforced by Carbon Fibers be a kind of high temperature resistant, low-density, high-strength tenacity heat structure material
Material.It is for example advanced in high-tech sector with the excellent properties such as high-modulus, high-modulus, high temperature resistant, anticorrosive, anti-oxidant, low-density
Aerospace vehicle structure member, high-temperature engine, turbine, atomic reactor wall, pyrostat etc. have extensive use
On the way.In recent years, major technological breakthrough is continuously obtained in terms of Ceramic Matrix Composites Reinforced by Carbon Fibers and Parts development,
It realizes from small size block to large size, thin walled great-leap-forward development.But there are still high expensive, mechanical property, inoxidizability
Energy etc. waits the problem of optimization.Based on this, cost effective and high performance is the important directions of next-generation composite material development.?
Heterogeneous element boron is introduced in Ceramic Matrix Composites Reinforced by Carbon Fibers, and it is multiple that carbon fibre reinforced silicon carbide ceramic base can be improved
The high-temperature mechanics and antioxygenic property of condensation material, but the prior art, using the methods of boron powder or boracic colloidal sol is introduced, there are boron members
The deficiencies of element is unevenly distributed in the base, introduces low efficiency.
Summary of the invention
Technology of the invention solves the problems, such as: overcome the deficiencies in the prior art, proposes a kind of boron modification Polycarbosilane resin
And preparation method thereof.
A kind of boron modification Polycarbosilane resin, the structural formula of the boron modification Polycarbosilane resin are as follows:
Wherein:
R: the unsaturated groups such as alkynyl, propargyl or allyl；
N is positive integer, and n >=1.
A kind of the step of preparation method of boron modification Polycarbosilane resin, this method includes:
Organic solvent is added in boron resin, then stirs at a temperature of 20 DEG C~140 DEG C to being completely dissolved, obtains transparent
Solution；In obtained clear solution be added low molecular weight liquid Polycarbosilane, heating stirring reaction, reaction temperature be 50~
120 DEG C, the reaction time is 1~100h；It is cooled to room temperature after the reaction was completed, then obtains yellowish-brown after rotary evaporation organic solvent
Transparent liquid resin, i.e., novel boron modification Polycarbosilane resin, the resin solidification and Pintsch process, obtain the unformed pottery of Si/B/C
Porcelain.
The boron modification Polycarbosilane resin to prepare reaction equation as follows:
The curing process mode uses tube furnace, curing cycle are as follows: 100 DEG C of heat preservation 2h, 150 DEG C of heat preservation 2h, 180 DEG C
Keep the temperature 4h, heating rate be 1~5 DEG C/min, curing atmosphere be inertia (such as: N2, Ar) atmosphere；
The Pintsch process process are as follows: with the heating rate of 5~10 DEG C/min under inert atmosphere, be warming up to 1300 DEG C~
1500 DEG C, keep the temperature 0.5~10h；
The organic solvent is toluene, dimethylbenzene, n-hexane or tetrahydrofuran；
The boron resin and organic solvent mass ratio are as follows: 1:2~10；
The boron resin and low molecular weight liquid Polycarbosilane mass ratio are as follows: 1:0.5~10；
The preparation method of the low molecular weight liquid Polycarbosilane:
(1) magnesium chips is added in the tetrahydrofuran solvent of purge drying, obtains mixed system；
(2) tetrahydrofuran, unsaturated enpara and chlorosilane monomer are mixed, obtains mixed solution；
(3) mixed solution that step (2) obtains is added dropwise in the mixed system that step (1) obtains, is stirred 5-30 hours,
Reaction temperature is -30~60 DEG C, obtains reaction head product；
(4) petroleum ether, deionized water and concentrated hydrochloric acid, control reaction temperature are added in the reaction head product that step (3) obtains
Degree is -20~15 DEG C, is sufficiently stirred 0.5-5 hours, stands 0.5-20 hours, split-phase takes upper organic phase and is dried, revolves
Steaming obtains low molecular weight liquid Polycarbosilane.
In the step (1), the mass ratio of magnesium chips and tetrahydrofuran is 1:1-2；
In the step (2), chlorosilane monomer is chloromethyl dichlorosilane or Chloromethyltrichlorosilane；Unsaturated chlorine alkane
Hydrocarbon is acetylene chloride, propargyl chloride or allyl chloride；The mass ratio of chlorosilane monomer and tetrahydrofuran is 1:2~10；It is unsaturated
Enpara and the mass ratio of chlorosilane monomer are 1:10~20；
In the step (3), when mixed solution is added dropwise in mixed system, the mass ratio of magnesium chips and chlorosilane monomer
For 1:5~10；
In the step (4), it is 1:1~10:0.1 that petroleum ether, deionized water and the volume ratio of concentrated hydrochloric acid three, which is added,；
In the step (4), the petroleum ether of addition, the volume of deionized water and concentrated hydrochloric acid three and with react head product
Volume ratio be 1~2:1；
The preparation method of the boron resin:
(1) boron trichloride gas is added in the n-hexane of purge drying, obtains solution；
(2) methylvinyl-chlorosilanes monomer is added in the solution that step (1) obtains, and is passed through ammonia, stir 10-
30 hours, reaction temperature was -10~30 DEG C, and obtained solution carries out filters pressing by filter press, and the solution after filters pressing is using rotation
Steaming obtains boron resin.
In the step (1), the mass ratio of boron trichloride gas and n-hexane is 1:5-8；
In the step (2), the mass ratio of methylvinyl-chlorosilanes monomer and boron chloride is 1:0.5-4；
In the step (2), the mass ratio of the quality of boron chloride and the ammonia being passed through is 1:5-8.
The present invention has the advantage that
(1) reaction raw materials of the present invention are general chemical raw material；Feed material price is low, preparation process simple process；
It (2) is low-viscosity (mobile) liquid, viscosity 10- under novel SiBC ceramic forerunner room temperature prepared by the present invention
500mPa.S has extraordinary processing performance；
(3) contain Si-H, B-H and C=C isoreactivity group and unsaturation in novel SiBC ceramic forerunner prepared by the present invention
Key can be solidified with self-crosslinking, and curing exotherm is small, and solidification is weightless low, and ceramic yield is high under high temperature, up to 60-70%；
(4) each element content ratio of novel SiBC ceramic forerunner prepared by the present invention can be adjusted by feed ratio
Section；
(5) novel SiBC ceramic forerunner prepared by the present invention can be used for ultra-temperature ceramic-based composite material impregnation matrix,
Also it can be used for the preparation of the high performance materials such as ceramic coating, fiber, tool has been widely used.
Detailed description of the invention
Fig. 1 is SiBC ceramic forerunner gel permeation chromatogram prepared by the embodiment of the present invention 1；
Fig. 2 is the thermogravimetric map of SiBC ceramic forerunner prepared by the embodiment of the present invention 1.
Specific embodiment
The present invention is described in further detail in the following with reference to the drawings and specific embodiments:
The present invention has carried out characterization research to the SiBC ceramic forerunner correlated performance of preparation, using rotor viscosity apparatus to preceding
The rheological property of body is characterized: viscosity test uses Broodfield rotary viscometer and No. 31 rotors, turns in 100rpm
Speed, torque test the viscosity characteristics of presoma under the conditions of being 50%.
The present invention characterizes the heat resistance of SiBC ceramic forerunner using thermogravimetric analyzer.In nitrogen atmosphere, with 10 DEG C/
The heating rate of min is warming up to 900 DEG C, tests the heat resistance of its residual heavy characterization SiBC ceramic forerunner.
Embodiment 1
500ml three-necked flask is equipped with gas and imports piston, sealing plug, constant pressure funnel, condenser pipe, magnetic agitation
Device and heating circulation system.All operating process are carried out by Schlenk technology, build anhydrous and oxygen-free system.It takes offence becoming a mandarin
50g boron resin is added under atmosphere, 100g n-hexane then is added with syringe, 40 DEG C are warming up under stirring, stirring is until dissolved
Entirely.Then the low molecular weight liquid Polycarbosilane that 100g contains vinyl is added, is warming up to 50 DEG C, continues to be stirred to react 10h, so
Stop stirring afterwards, removes oil bath and stand 10-20h.Abstraction solvent obtains yellow transparent oily SiBC ceramic forerunner.Synthetic yield
It is 80.30%.The gel permeation chromatogram of obtained SiBC ceramic forerunner is as shown in Figure 1, thermogravimetric map is as shown in Figure 2；
Reaction equation is as follows:
TGA shows presoma in N2Lower 900 DEG C of residual weights are 70.46%, as shown in Fig. 2, viscosity test surface product viscosity
For 413mPa.S.
Gel permeation chromatography tests the molecular weight for showing resulting Polycarbosilane: Mn=752, Mw=2290.
Embodiment 2
500ml three-necked flask is equipped with gas and imports piston, sealing plug, constant pressure funnel, condenser pipe, magnetic agitation
Device and heating circulation system.All operating process are carried out by Schlenk technology, build anhydrous and oxygen-free system.It takes offence becoming a mandarin
100g boron resin is added under atmosphere, 500g dimethylbenzene then is added with syringe, 50 DEG C are warming up under stirring, stirring is until dissolved
Entirely.Then the low molecular weight liquid Polycarbosilane that 300g contains allyl is added, is warming up to 90 DEG C, continues to be stirred to react 10h, so
Stop stirring afterwards, removes oil bath and stand 10-20h.Abstraction solvent obtains yellow transparent oily SiBC ceramic forerunner.Synthetic yield
It is 75.30%.
Reaction equation is as follows:
TGA shows that presoma 900 DEG C of residual weights at N2 are 75%.Viscosity test surface product viscosity is 205mPa.S.
Gel permeation chromatography tests the molecular weight for showing resulting Polycarbosilane: Mn=816, Mw=2693.
Embodiment 3
500ml three-necked flask is equipped with gas and imports piston, sealing plug, constant pressure funnel, condenser pipe, magnetic agitation
Device and heating circulation system.All operating process are carried out by Schlenk technology, build anhydrous and oxygen-free system.It takes offence becoming a mandarin
50g boron resin is added under atmosphere, 100g tetrahydrofuran then is added with syringe, 40 DEG C are warming up under stirring, stirring is until dissolution
Completely.Then the low molecular weight liquid Polycarbosilane that 150g contains alkynyl is added, is warming up to 50 DEG C, continues to be stirred to react 10h, so
Stop stirring afterwards, removes oil bath and stand 10-20h.Abstraction solvent obtains yellow transparent oily SiBC ceramic forerunner.Synthetic yield
It is 70.30%.
Reaction equation is as follows:
TGA shows that presoma 900 DEG C of residual weights at N2 are 78%.Viscosity test surface product viscosity is 310mPa.S.
Gel permeation chromatography tests the molecular weight for showing resulting Polycarbosilane: Mn=755, Mw=2106.
Embodiment 4
500ml three-necked flask is equipped with gas and imports piston, sealing plug, constant pressure funnel, condenser pipe, magnetic agitation
Device and heating circulation system.All operating process are carried out by Schlenk technology, build anhydrous and oxygen-free system.It takes offence becoming a mandarin
100g boron resin is added under atmosphere, 200g dimethylbenzene then is added with syringe, 45 DEG C are warming up under stirring, stirring is until dissolved
Entirely.Then the low molecular weight liquid Polycarbosilane that 150g contains allyl is added, is warming up to 80 DEG C, continues to be stirred to react 10h, so
Stop stirring afterwards, removes oil bath and stand 10-20h.Abstraction solvent obtains yellow transparent oily SiBC ceramic forerunner.Synthetic yield
It is 71.30%.
Reaction equation is as follows:
TGA shows that presoma 900 DEG C of residual weights at N2 are 66%.Viscosity test surface product viscosity is 105mPa.S.
Gel permeation chromatography tests the molecular weight for showing resulting Polycarbosilane: Mn=620, Mw=2013.
The above, optimal specific embodiment only of the invention, but scope of protection of the present invention is not limited thereto,
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.
The content that description in the present invention is not described in detail belongs to the well-known technique of professional and technical personnel in the field.
Claims (10)
1. a kind of boron modification Polycarbosilane resin, it is characterised in that: the structural formula of the boron modification Polycarbosilane resin are as follows:
Wherein:
R: alkynyl, propargyl or allyl；
N is positive integer, and n >=1.
2. a kind of preparation method of boron modification Polycarbosilane resin, it is characterised in that the step of this method includes:
Organic solvent is added in boron resin, then stirs at a temperature of 20 DEG C~140 DEG C to being completely dissolved, obtains transparent molten
Liquid；Low molecular weight liquid Polycarbosilane, heating stirring reaction are added in obtained clear solution, reaction temperature is 50~120
DEG C, the reaction time is 1~100h；It is cooled to room temperature after the reaction was completed, it is poly- that boron modification is then obtained after rotary evaporation organic solvent
Carbon silane resin.
3. a kind of preparation method of boron modification Polycarbosilane resin according to claim 2, it is characterised in that:
The boron modification Polycarbosilane resin to prepare reaction equation as follows:
4. a kind of preparation method of boron modification Polycarbosilane resin according to claim 2, it is characterised in that: described organic
Solvent is toluene, dimethylbenzene, n-hexane or tetrahydrofuran；
The boron resin and organic solvent mass ratio are as follows: 1:2~10；
The boron resin and low molecular weight liquid Polycarbosilane mass ratio are as follows: 1:0.5~10.
5. a kind of preparation method of boron modification Polycarbosilane resin according to claim 2, it is characterised in that: described is low
The preparation method of molecular weight liquid Polycarbosilane:
(1) magnesium chips is added in the tetrahydrofuran solvent of purge drying, obtains mixed system；
(2) tetrahydrofuran, unsaturated enpara and chlorosilane monomer are mixed, obtains mixed solution；
(3) mixed solution that step (2) obtains is added dropwise in the mixed system that step (1) obtains, is stirred 5-30 hours, reaction
Temperature is -30~60 DEG C, obtains reaction head product；
(4) it is added petroleum ether, deionized water and concentrated hydrochloric acid in the reaction head product that step (3) obtains, control reaction temperature is-
It 20~15 DEG C, is sufficiently stirred 0.5-5 hours, stands 0.5-20 hours, split-phase takes upper organic phase and is dried, rotates
To low molecular weight liquid Polycarbosilane.
6. a kind of preparation method of boron modification Polycarbosilane resin according to claim 5, it is characterised in that: the step
Suddenly in (1), the mass ratio of magnesium chips and tetrahydrofuran is 1:1-2；
In the step (2), chlorosilane monomer is chloromethyl dichlorosilane or Chloromethyltrichlorosilane；Unsaturated enpara is
Acetylene chloride, propargyl chloride or allyl chloride；The mass ratio of chlorosilane monomer and tetrahydrofuran is 1:2~10；Unsaturated chlorine alkane
Hydrocarbon and the mass ratio of chlorosilane monomer are 1:10~20；
In the step (3), when mixed solution is added dropwise in mixed system, the mass ratio of magnesium chips and chlorosilane monomer is 1:
5~10；
In the step (4), it is 1:1~10:0.1 that petroleum ether, deionized water and the volume ratio of concentrated hydrochloric acid three, which is added,；
In the step (4), the petroleum ether of addition, the volume of deionized water and concentrated hydrochloric acid three and with the body that reacts head product
Product is than being 1~2:1.
7. a kind of preparation method of boron modification Polycarbosilane resin according to claim 2, it is characterised in that: the boron
The preparation method of resin:
(1) boron trichloride gas is added in the n-hexane of purge drying, obtains solution；
(2) methylvinyl-chlorosilanes monomer is added in the solution that step (1) obtains, and is passed through ammonia, stirring 10-30 is small
When, reaction temperature is -10~30 DEG C, and obtained solution carries out filters pressing by filter press, and solution after filters pressing is using rotating
To boron resin；
In the step (1), the mass ratio of boron trichloride gas and n-hexane is 1:5-8；
In the step (2), the mass ratio of methylvinyl-chlorosilanes monomer and boron chloride is 1:0.5-4；
In the step (2), the mass ratio of the quality of boron chloride and the ammonia being passed through is 1:5-8.
8. a kind of method for preparing the unformed ceramics of Si/B/C, it is characterised in that the step of this method includes: by the poly- carbon of boron modification
The silane resin resin solidify and Pintsch process, obtains the unformed ceramics of Si/B/C.
9. a kind of method for preparing the unformed ceramics of Si/B/C according to claim 8, it is characterised in that: when being solidified
Using tube furnace, curing cycle are as follows: 100 DEG C of heat preservation 2h, 150 DEG C of heat preservation 2h, 180 DEG C of heat preservation 4h, heating rate be 1~5 DEG C/
Min, curing atmosphere are inert atmosphere.
10. a kind of method for preparing the unformed ceramics of Si/B/C according to claim 8, it is characterised in that: the height
Anneal crack solution preocess are as follows: with the heating rate of 5~10 DEG C/min under inert atmosphere, it is warming up to 1300 DEG C~1500 DEG C, heat preservation 0.5~
10h。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109821264A (en) * | 2019-03-22 | 2019-05-31 | 中国人民解放军国防科技大学 | Method and device for evaporating and removing low content of polycarbosilane melt |
| CN111573678A (en) * | 2020-05-14 | 2020-08-25 | 湖南太子新材料科技有限公司 | Silicon carbide film forming device and preparation method of silicon carbide film |
| CN114573821A (en) * | 2022-03-03 | 2022-06-03 | 上海大学 | Liquid hyperbranched polycarbosilane, preparation method and application thereof |
| CN114957675A (en) * | 2021-11-29 | 2022-08-30 | 中国航空制造技术研究院 | Boron modified polycarbosilane powder and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050026769A1 (en) * | 2003-08-01 | 2005-02-03 | Jongsang Lee | Process for SiBCN based preceramic polymers and products derivable therefrom |
| EP2262849A1 (en) * | 2008-04-09 | 2010-12-22 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften E.V. | SILICON-BORON-CARBON-NITROGEN CERAMICS AND PRECURSOR COMPOUNDS, METHODS FOR THE SALT-FREE POLYMERIZATION OF RNHAL3-NSI - X - BRMHAL2-M& xA; |
| CN103938296A (en) * | 2014-03-18 | 2014-07-23 | 东华大学 | Method for preparation of SiBN(C) ceramic fiber precursor by one-pot technique |
| CN104093767A (en) * | 2011-12-09 | 2014-10-08 | 马普科技促进协会 | One-pot synthesis of SiBNC preceramic polymer |
| CN104790068A (en) * | 2015-04-22 | 2015-07-22 | 中国人民解放军国防科学技术大学 | Preparation method of boron-containing silicon carbide fiber |
| CN105377956A (en) * | 2013-05-30 | 2016-03-02 | 通用电气公司 | Polydisilazanes prepared from boron-containing additives |
| CN108129665A (en) * | 2017-12-27 | 2018-06-08 | 南昌嘉捷天剑新材料有限公司 | Hyperbranched polycarbosilanes of high softening-point and preparation method thereof |
-
2018
- 2018-10-25 CN CN201811249968.2A patent/CN109438712B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050026769A1 (en) * | 2003-08-01 | 2005-02-03 | Jongsang Lee | Process for SiBCN based preceramic polymers and products derivable therefrom |
| EP2262849A1 (en) * | 2008-04-09 | 2010-12-22 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften E.V. | SILICON-BORON-CARBON-NITROGEN CERAMICS AND PRECURSOR COMPOUNDS, METHODS FOR THE SALT-FREE POLYMERIZATION OF RNHAL3-NSI - X - BRMHAL2-M& xA; |
| CN101990553A (en) * | 2008-04-09 | 2011-03-23 | 马普科技促进协会 | Silicon-boron-carbon-nitrogen ceramics and precursor compounds, methods for the salt-free polymerization of rnhal3-nsi - x - brmhal2-m& xa |
| CN104093767A (en) * | 2011-12-09 | 2014-10-08 | 马普科技促进协会 | One-pot synthesis of SiBNC preceramic polymer |
| CN105377956A (en) * | 2013-05-30 | 2016-03-02 | 通用电气公司 | Polydisilazanes prepared from boron-containing additives |
| CN103938296A (en) * | 2014-03-18 | 2014-07-23 | 东华大学 | Method for preparation of SiBN(C) ceramic fiber precursor by one-pot technique |
| CN104790068A (en) * | 2015-04-22 | 2015-07-22 | 中国人民解放军国防科学技术大学 | Preparation method of boron-containing silicon carbide fiber |
| CN108129665A (en) * | 2017-12-27 | 2018-06-08 | 南昌嘉捷天剑新材料有限公司 | Hyperbranched polycarbosilanes of high softening-point and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| WANG, XZ ET AL: "Synthesis, characterization, and ceramic conversion of a liquid polymeric precursor to SiBCN ceramic via borazine-modified polymethylsilane", 《JOURNAL OF MATERIALS SCIENCE》 * |
| 孔杰等: "聚硼硅氮烷陶瓷前驱体分子结构设计和合成", 《化学进展》 * |
| 滕雅娣等: "SiBCN陶瓷先驱体的制备和应用研究进展", 《有机硅材料》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109821264A (en) * | 2019-03-22 | 2019-05-31 | 中国人民解放军国防科技大学 | Method and device for evaporating and removing low content of polycarbosilane melt |
| CN109821264B (en) * | 2019-03-22 | 2021-03-26 | 中国人民解放军国防科技大学 | Method and device for evaporating and removing low content of polycarbosilane melt |
| CN111573678A (en) * | 2020-05-14 | 2020-08-25 | 湖南太子新材料科技有限公司 | Silicon carbide film forming device and preparation method of silicon carbide film |
| CN114957675A (en) * | 2021-11-29 | 2022-08-30 | 中国航空制造技术研究院 | Boron modified polycarbosilane powder and preparation method thereof |
| CN114573821A (en) * | 2022-03-03 | 2022-06-03 | 上海大学 | Liquid hyperbranched polycarbosilane, preparation method and application thereof |
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