CN115894940B - Preparation method of Zr-C-Si main chain-containing single-source ultrahigh-temperature ceramic precursor - Google Patents
Preparation method of Zr-C-Si main chain-containing single-source ultrahigh-temperature ceramic precursor Download PDFInfo
- Publication number
- CN115894940B CN115894940B CN202111168434.9A CN202111168434A CN115894940B CN 115894940 B CN115894940 B CN 115894940B CN 202111168434 A CN202111168434 A CN 202111168434A CN 115894940 B CN115894940 B CN 115894940B
- Authority
- CN
- China
- Prior art keywords
- main chain
- ceramic precursor
- source
- reaction solvent
- active species
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention relates to a preparation method of a Zr-C-Si main chain-containing single-source ultrahigh-temperature ceramic precursor, which comprises the following molecular chain structure:the main chain structural unit is Zr-C-Si, n represents the polymerization degree, and the preparation method comprises the following steps: first utilize Cp 2 ZrCl 2 With reducing metal Mg to form Cp of low oxidation state 2 Zr (II) equivalent active species, then adding (CH) 3 ) 2 Si(CH 2 Cl) 2 And copolymerizing at 110 deg.c, filtering to eliminate magnesium salt as the reaction side product, vacuum concentrating and eliminating solvent to obtain orange color poly-zirconium-carbosilane precursor. The preparation method provided by the invention has the advantages of novel scheme and simple equipment process, the obtained precursor can be dissolved in toluene, THF and other organic solvents, the softening point is 140-185 ℃, and the good dissolution melting property is beneficial to subsequent molding processing and functional application.
Description
Technical Field
The invention relates to the technical field of ceramic materials, in particular to a preparation method of a single-source ultrahigh-temperature ceramic precursor containing a Zr-C-Si main chain.
Background
The ultra-high temperature resistant ceramic has excellent performances of high temperature resistance, oxidation resistance, high strength and the like, is an ultra-high temperature environment service candidate structural material with great competitive power, and has wide application prospect in the fields of aerospace, nuclear energy and the like. However, the low-temperature oxidation product of the binary ultra-high temperature ceramic has a loose and porous structure, cannot prevent oxygen from penetrating, and limits the application of the binary ultra-high temperature ceramic as a high-temperature structural material. The complex phase ceramic is prepared by introducing Si element into the ceramic to form a reinforcing phase, which is an important means for improving the oxidation resistance of the superhigh temperature ceramic.
The preparation method of the ultra-high temperature ceramic material mainly comprises Hot Pressing (HP) technology, plasma spark sintering (SPS), chemical Vapor Deposition (CVD) method and precursor conversion (PDCs). The precursor conversion method can obtain various ceramic systems with uniform disperse phase, specific microstructure and performance through molecular design, and therefore, the method has received extensive attention.
The synthesis of the existing Si-containing single-source superhigh temperature ceramic precursor mainly comprises two schemes of side chain grafting and monomer copolymerization.
The side chain grafting is mainly to chemically modify Si-containing polymers such as polycarbosilane by using refractory metal M (M=Zr, hf, ta, ti) organic compounds, and then ceramic to obtain MC (N)/SiC complex-phase ceramic, but the scheme has the defects that the refractory metal M is limited in introduction amount, and meanwhile, the side group is large in volume, the dissolution and melting performances of a precursor are influenced, and the like, so that the functional application of the precursor and the ultrahigh temperature resistance of the ceramic are limited.
The monomer copolymerization method is a method for copolymerizing refractory metal M source monomers and Si source monomers, and the refractory metal M and antioxidant component Si are simultaneously introduced into a polymer main chain through copolymerization reaction, so that the synthesized polymer precursor has certain linearity while the content of M and Si is ensured, and the polymer precursor has good dissolution and melting properties by regulating and controlling reaction conditions and side chain modification, thereby being convenient for subsequent processing, forming and functional application.
Disclosure of Invention
The invention provides a preparation method of a Zr-C-Si main chain single-source superhigh temperature ceramic precursor, wherein the single source refers to the superhigh temperature ceramic precursor provided by the invention is a polymer precursor with a single molecular structure, and the main chain refers to a Zr-C-Si chain segment with the single molecular structure. The preparation method of the invention belongs to the category of monomer copolymerization, zr and Si are simultaneously introduced into a polymer main chain, wherein the introduction of a flexible chain segment Si can effectively regulate and control the flexibility of a Zr-C structure molecular chain, so that the preparation method is expected to prepare the ultrahigh-temperature ceramic fiber.
The technical scheme of the invention is that the Zr-C-Si main chain-containing single-source ultrahigh-temperature ceramic precursor comprises the following molecular chain structures:
wherein the precursor structural unit is a Zr-C-Si chain, n represents the polymerization degree, and the ultra-high temperature refers to the use temperature of ceramic obtained by the single-source ultra-high temperature ceramic precursor containing a Zr-C-Si main chain is above 1600 ℃; the softening point of the Zr-C-Si main chain containing single source superhigh temperature ceramic precursor is 140-185 ℃.
More importantly, the invention provides a preparation method of the Zr-C-Si main chain containing single-source ultrahigh temperature ceramic precursor, which comprises the following steps:
s1, preparation of Cp 2 Zr (ii) equivalent active species: cp is Cp 2 ZrCl 2 Adding the mixture and Mg scraps into a first reaction solvent according to a preset molar ratio, fully stirring, reacting for 1-6 hours at the temperature of between room temperature and 60 ℃, cooling to the room temperature, and filtering to remove excessive reactant magnesium scraps to obtain black and purple Cp 2 Zr (ii) equivalent active species solution;
s2, preparing a PZCS ceramic precursor: at Cp 2 Adding a certain proportion of ClCH into Zr (II) solution 2 Si(CH 3 ) 2 CH 2 And (3) stirring Cl and a second reaction solvent uniformly at room temperature, heating to 110-130 ℃ for reaction, preserving heat for 4-24 hours, naturally cooling to room temperature, filtering to remove magnesium salt, and concentrating in vacuum to obtain orange super-high temperature ceramic precursor powder containing Zr-C-Si main chain structure.
Further, in step S1, cp 2 ZrCl 2 Molar ratio to Mg flake = 1: (2-6).
Further, in step S1, cp 2 ZrCl 2 Molar ratio to Mg flake = 1:6.
further, in step S1, the first reaction solvent is anhydrous THF or anhydrous DMF.
Further, in step S2, the second reaction solvent is one of toluene, xylene, and DMF.
Further, in step S2, cp 2 Zr (II) active species and ClCH 2 Si(CH 3 ) 2 CH 2 The molar ratio of the Cl monomers is 5 (4-6).
Further, in step S2, cp 2 Zr (II) active species and ClCH 2 Si(CH 3 ) 2 CH 2 The molar ratio of Cl monomers was 5:4.
Further, the second solvent is added in one of the following ways:
a. when the second reaction solvent and the first reaction solvent are the same substance, a certain proportion of (CH) 3 ) 2 Si(CH 2 Cl) 2 Fully stirring the monomers, and heating to 110-130 ℃ for copolymerization;
b. when the second reaction solvent and the first reaction solvent are different substances, cp is obtained 2 Placing the Zr (II) active species solution in a three-necked flask, and vacuum concentrating at room temperature to remove not less than 1/3 of the first reaction solvent; by means of a dropping funnel to the remainder Cp 2 Injecting a second reaction solvent into the Zr (II) active species solution, stirring to make Cp 2 The Zr (II) active species solution is uniformly dispersed in the mixed solvent, and then the reaction monomer (CH) is slowly dripped into the solution by using a disposable injector 3 ) 2 Si(CH 2 Cl) 2 Fully stirring and heating to 110-130 ℃ for copolymerization.
The reaction formula of the step S1 in the preparation process is as follows:
the reaction formula of step S2 is:
compared with the prior art, the method has the beneficial effects that:
1) The invention provides a Zr-C-Si containing main chain single-source superhigh temperature ceramic precursor, which comprises a zirconocene structure, a flexible silicon chain segment and a main chain containing Zr-C-Si formed by combining C chains, and has the advantages and characteristics of no oxygen in theory, good molecular chain flexibility, good solubility in toluene, softening point of 140-185 ℃ and the like.
2) The invention provides a preparation method of a single-source superhigh temperature ceramic precursor containing Zr-C-Si main chain, which comprises the following steps of firstly preparing Cp 2 ZrCl 2 Reacts with Mg scraps in a solvent to obtain Cp 2 Zr (II) equivalent active species, then adding part of toluene/xylene as a second-stage reaction solvent, increasing the reaction temperature, reducing the kinetic influence of the reaction, and adding ClCH 2 Si(CH 3 ) 2 CH 2 Cl as Si Source and active species Cp 2 And (3) copolymerizing Zr (II), and finally heating to 110-130 ℃ to polymerize to obtain the Zr-C-Si main chain single source superhigh temperature ceramic precursor.
3) The synthesis equipment and the operation in the preparation method are simple.
Drawings
In order to more clearly clarify the technical problems of the present invention, a detailed description will be given of the technical solutions in the embodiments of the present invention with reference to the accompanying drawings.
FIG. 1 is an optical photograph of a PZCS precursor obtained in example 1 of the present invention;
FIG. 2 is an infrared spectrum of the PZCS precursor obtained in example 1 of the present invention;
FIG. 3 is a XPS spectrum of the precursor of PZCS obtained in example 1 of the present invention;
FIG. 4 is a Gel Permeation Chromatography (GPC) chart of the PZCS precursor obtained in example 1 of the present invention.
Detailed Description
The technical problems of the present invention will be described in more detail below with reference to the following examples and the accompanying drawings of the examples, and it is apparent that the examples are only some of the examples of the present invention. Based on the embodiments of the present invention, those skilled in the art may not make any other embodiments without inventive work.
The solvents used in the present invention are all anhydrous solvents (water removal treatment), and the reagents used are all commercially available unless otherwise specified.
Example 1:
the embodiment provides a preparation method of a Zr-C-Si main chain single-source ultra-high temperature ceramic precursor, which comprises the following steps:
(1) Preparation of Cp 2 Zr (II) active species
S11: determination of Cp 2 ZrCl 2 Reaction molar ratio with Mg scrap.
S12: adding zirconocene dichloride and magnesium chips into THF according to a molar ratio of 1:6, fully stirring, heating to 60 ℃ for reaction for 4 hours, cooling to room temperature, and filtering to remove excessive reactant magnesium chips to obtain a black and purple reactive monomer solution.
(2) Preparation of PZCS ceramic precursor
Vacuum concentrating to remove Cp 2 About 1/3 of the THF solvent of the Zr (II) active species solution was slowly added dropwise (CH 3 ) 2 Si(CH 2 Cl) 2 Monomer (molar ratio Cp) 2 Zr(Ⅱ)：(CH 3 ) 2 Si(CH 2 Cl) 2 =5: 4) Mixing with toluene as a reaction solvent at room temperature, stirring uniformly, heating to 110 ℃ for reaction, preserving heat for 16 hours, naturally cooling to room temperature, filtering to remove magnesium salt, and concentrating in vacuum to obtain orange-yellow PZCS ultra-high temperature ceramic precursor containing Zr-C-Si main chain structure. The ceramic yield of the precursor at 900 ℃ is 43.985% (the mass percentage of the final residual product is that the 900 ℃ residual product/original product is equal to the ceramic yield of the precursor at 900 ℃ when the precursor is heated to 900 ℃ in an inert atmosphere), and the softening point is 140-185 ℃.
The morphology of the precursor obtained in this example is shown in fig. 1, and the precursor obtained is in the form of powder. The infrared structure of the precursor is shown in FIG. 2, in which-CH is shown 3 Cp (C-H) and Si-CH 3 The existence of the isostructure indicates that the chemical structures of two monomers exist in the PZCS precursor. From the XPS spectroscopy analysis of figure 3,the precursor consists essentially of C, si, cl, zr and O, where the presence of O may be caused by oxygen uptake during sample storage or transfer. Gel Permeation Chromatography (GPC) is an important method for measuring the molecular weight of polymers, and as can be seen from FIG. 4, the number average molecular weight of the precursor obtained in this example is 848g/mol, and the weight average molecular weight is 1002g/mol, indicating that copolymerization between the two monomers occurs, resulting in a PZCS polymer precursor.
Example 2:
the embodiment provides a preparation method of a Zr-C-Si main chain single-source ultra-high temperature ceramic precursor, which comprises the following steps:
(1) Preparation of Cp 2 Zr (II) active species
S11: determination of Cp 2 ZrCl 2 Reaction molar ratio with Mg scrap.
S12: adding zirconocene dichloride and magnesium chips into THF according to a molar ratio of 1:6, fully stirring, heating to 60 ℃ for reaction for 8 hours, cooling to room temperature, and filtering to remove excessive reactant magnesium chips to obtain a black and purple reactive monomer solution.
(2) Preparation of PZCS ceramic precursor
Vacuum concentrating to remove Cp 2 About 1/3 of the THF solvent of the Zr (II) active species solution was slowly added dropwise (CH 3 ) 2 Si(CH 2 Cl) 2 Monomer (Cp) 2 Zr(Ⅱ)：(CH 3 ) 2 Si(CH 2 Cl) 2 =5: 4) And (3) uniformly stirring the mixture with toluene serving as a reaction solvent at room temperature, heating to 110 ℃ for reaction, preserving heat for 4 hours, naturally cooling to room temperature, filtering to remove magnesium salt, and concentrating in vacuum to obtain a yellow PZCS superhigh temperature ceramic precursor containing Zr-C-Si main chain structures.
This example is mainly to investigate the effect of reaction temperature on the properties of the precursor, and shows that the resulting precursor has a ceramic yield of 45.077% at 900 ℃, a softening point > 250 ℃, and the precursor does not melt within 250 ℃ although having a higher ceramic yield.
Example 3:
the embodiment provides a preparation method of a Zr-C-Si main chain single-source ultra-high temperature ceramic precursor, which comprises the following steps:
(1) Preparation of Cp 2 Zr (II) active species
S11: determination of Cp 2 ZrCl 2 Reaction molar ratio with Mg scrap.
S12: adding zirconocene dichloride and magnesium chips into THF according to a molar ratio of 1:6, fully stirring, heating to 60 ℃ for reaction for 4 hours, cooling to room temperature, and filtering to remove excessive reactant magnesium chips to obtain a black and purple reactive monomer solution.
(2) Preparation of PZCS ceramic precursor
Vacuum concentrating to remove Cp 2 About 1/3 of the THF solvent of the Zr (II) active species solution was slowly added dropwise (CH 3 ) 2 Si(CH 2 Cl) 2 Monomer (Cp) 2 Zr(Ⅱ)：(CH 3 ) 2 Si(CH 2 Cl) 2 =5: 4) And (3) uniformly stirring the mixture with toluene serving as a reaction solvent at room temperature, heating to 110 ℃ for reaction, preserving heat for 8 hours, naturally cooling to room temperature, filtering to remove magnesium salt, and concentrating in vacuum to obtain a yellow PZCS superhigh temperature ceramic precursor containing Zr-C-Si main chain structures.
This example is mainly to investigate the effect of reaction temperature on the properties of the precursor, and shows that the resulting precursor has a ceramic yield of 45.783% at 900 ℃, a softening point > 250 ℃, and the precursor does not melt within 250 ℃ although having a higher ceramic yield.
Example 4:
the embodiment provides a preparation method of a Zr-C-Si main chain single-source ultra-high temperature ceramic precursor, which comprises the following steps:
(1) Preparation of Cp 2 Zr (II) active species
S11: determination of Cp 2 ZrCl 2 Reaction molar ratio with Mg scrap.
S12: adding zirconocene dichloride and magnesium chips into DMF according to a molar ratio of 1:6, fully stirring, heating to 60 ℃ for reaction for 4 hours, cooling to room temperature, and filtering to remove excessive reactant magnesium chips to obtain a black and purple reactive monomer solution.
(2) Preparation of PZCS ceramic precursor
Slowly drop-wise into the reaction flask using syringe (CH 3 ) 2 Si(CH 2 Cl) 2 l monomer (molar ratio Cp) 2 Zr(Ⅱ)：(CH 3 ) 2 Si(CH 2 Cl) 2 =5: 4) Stirring uniformly at room temperature, heating to 120 ℃ for reaction, preserving heat for 16 hours, naturally cooling to room temperature, filtering to remove magnesium salt, and concentrating in vacuum to obtain brown PZCS superhigh temperature ceramic precursor containing Zr-C-Si main chain structure.
This example is mainly to demonstrate the effect of different reaction solvents on the properties of the final precursor, and shows that when the reaction solvent is changed to DMF, the ceramic yield of the resulting precursor at 900℃is 35.235%, the softening point is 150-200℃and the resulting precursor is fusible but the ceramic yield is lower.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (8)
1. A preparation method of a single-source superhigh temperature ceramic precursor containing Zr-C-Si main chain is characterized by comprising the following steps:
s1, preparation of Cp 2 Zr (ii) equivalent active species: cp is Cp 2 ZrCl 2 Adding the mixture and Mg scraps into a first reaction solvent according to a preset molar ratio, fully stirring, reacting for 1-6 hours at room temperature to 60 ℃, cooling to room temperature, and filtering to remove excessive reactant magnesium scraps to obtain black and purple Cp 2 Zr (ii) equivalent active species solution;
s2, preparing a PZCS ceramic precursor: at Cp 2 Adding a certain proportion of (CH) into Zr (II) equivalent active species solution 3 ) 2 Si(CH 2 Cl) 2 And a second reaction solvent, stirring uniformly at room temperature, heating to 110-130 ℃ for reaction, preserving heat for 4-24 hours, naturally cooling to room temperature, filtering to remove magnesium salt, and concentrating in vacuum to obtain orange super-high Wen Tao containing Zr-C-Si main chain structureCeramic precursor powder;
the resulting product comprises the following molecular chain structure:
，
wherein the main chain structural unit is a Zr-C-Si chain, and n represents the polymerization degree; the ultra-high temperature refers to that the use temperature of ceramics obtained by a single-source ultra-high temperature ceramic precursor containing a Zr-C-Si main chain is above 1600 ℃; the softening point of the Zr-C-Si main chain-containing single-source ultra-high temperature ceramic precursor is 140-185 ℃.
2. The method for preparing a single-source ultra-high temperature ceramic precursor containing a Zr-C-Si backbone according to claim 1, wherein in step S1, cp is 2 ZrCl 2 Molar ratio to Mg flake = 1: (2-6).
3. The method for preparing a single-source ultra-high temperature ceramic precursor containing Zr-C-Si main chain according to claim 1 or 2, wherein in step S1, cp is 2 ZrCl 2 Molar ratio to Mg flake = 1:6.
4. the method for preparing a single-source superhigh temperature ceramic precursor with a Zr-C-Si backbone according to claim 1, wherein in step S1, the first reaction solvent is anhydrous THF or anhydrous DMF.
5. The method for preparing a single-source superhigh temperature ceramic precursor with a Zr-C-Si main chain according to claim 1, wherein in step S2, the second reaction solvent is one of toluene, xylene, and anhydrous DMF.
6. The method for preparing a single-source ultra-high temperature ceramic precursor containing a Zr-C-Si backbone according to claim 1, wherein in step S2, cp is 2 Zr (II) equivalent active species solution and (CH) 3 ) 2 Si(CH 2 Cl) 2 The molar ratio of the monomers is 5 (4-6).
7. The method for preparing a single-source ultra-high temperature ceramic precursor containing Zr-C-Si main chain according to claim 1 or 6, wherein in step S2, cp 2 Zr (II) equivalent active species solution and (CH) 3 ) 2 Si(CH 2 Cl) 2 The molar ratio of the monomers was 5:4.
8. The method for preparing a single-source superhigh temperature ceramic precursor with a Zr-C-Si main chain according to claim 1, wherein the second reaction solvent is added in one of the following ways:
a. when the second reaction solvent and the first reaction solvent are the same substance, a certain proportion of (CH) 3 ) 2 Si(CH 2 Cl) 2 Fully stirring the monomers, and heating to 110-130 ℃ for copolymerization;
b. when the second reaction solvent and the first reaction solvent are different substances, cp is obtained 2 Placing the Zr (II) equivalent active species solution in a three-necked flask, and vacuum concentrating at room temperature to remove the first reaction solvent not lower than 1/3; by means of a dropping funnel to the remainder Cp 2 Injecting a second reaction solvent into the Zr (II) equivalent active species solution, stirring to make Cp 2 Uniformly dispersing Zr (II) equivalent active species solution in the mixed solvent, and slowly dripping the reaction monomer (CH) into the solution by using a disposable injector 3 ) 2 Si(CH 2 Cl) 2 Stirring for 30 min fully, and heating to 110-130 ℃ for copolymerization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111168434.9A CN115894940B (en) | 2021-09-30 | 2021-09-30 | Preparation method of Zr-C-Si main chain-containing single-source ultrahigh-temperature ceramic precursor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111168434.9A CN115894940B (en) | 2021-09-30 | 2021-09-30 | Preparation method of Zr-C-Si main chain-containing single-source ultrahigh-temperature ceramic precursor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115894940A CN115894940A (en) | 2023-04-04 |
| CN115894940B true CN115894940B (en) | 2023-09-15 |
Family
ID=86493916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111168434.9A Active CN115894940B (en) | 2021-09-30 | 2021-09-30 | Preparation method of Zr-C-Si main chain-containing single-source ultrahigh-temperature ceramic precursor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115894940B (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5204431A (en) * | 1991-01-26 | 1993-04-20 | Solvay Deutschland, Gmbh | Polycarbosilanes containing a hetero element |
| CN103275326A (en) * | 2013-06-15 | 2013-09-04 | 厦门大学 | Method for preparing liquid anaerobic polyzirconocarbosilane |
| CN103588484A (en) * | 2013-10-23 | 2014-02-19 | 航天材料及工艺研究所 | Machinable Si/C/Zr ceramic precursor and preparation method thereof |
| CN103772709A (en) * | 2014-01-03 | 2014-05-07 | 航天材料及工艺研究所 | Si/C/Zr ceramic precursor and preparation method thereof |
| CN104211967A (en) * | 2014-08-14 | 2014-12-17 | 中国科学院过程工程研究所 | Polymetalcarbosilane, and preparation method and application thereof |
| CN105669983A (en) * | 2016-01-22 | 2016-06-15 | 中国人民解放军国防科学技术大学 | Zirconium-containing organic metal polymer ceramic precursor, method for preparing same and application of zirconium-containing organic metal polymer ceramic precursor |
| CN106348759A (en) * | 2016-08-18 | 2017-01-25 | 中国人民解放军国防科学技术大学 | Normal-temperature and normal-pressure synthesizing method of Zr-Si-C ceramic precursor |
| CN109054026A (en) * | 2018-10-10 | 2018-12-21 | 中国人民解放军国防科技大学 | Preparation method of HfC-SiC ultrahigh-temperature ceramic precursor |
| CN110028639A (en) * | 2019-04-17 | 2019-07-19 | 厦门理工学院 | A kind of photosensitivity Zr-B-Si-C ceramic forerunner and its in-situ preparation method |
| CN110424068A (en) * | 2019-08-06 | 2019-11-08 | 江西嘉捷信达新材料科技有限公司 | Mix ultrahigh temperature ceramic composite preparation SiC fiber and its methods and applications |
| CN112958146A (en) * | 2019-12-12 | 2021-06-15 | 中国科学院大连化学物理研究所 | MFI molecular sieve nanosheet-loaded zirconium-based catalyst and application thereof in butadiene preparation reaction |
| CN114058019A (en) * | 2021-11-15 | 2022-02-18 | 中国人民解放军国防科技大学 | Ultrahigh-temperature ceramic precursor capable of being melt-spun, and preparation method and application thereof |
-
2021
- 2021-09-30 CN CN202111168434.9A patent/CN115894940B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5204431A (en) * | 1991-01-26 | 1993-04-20 | Solvay Deutschland, Gmbh | Polycarbosilanes containing a hetero element |
| CN103275326A (en) * | 2013-06-15 | 2013-09-04 | 厦门大学 | Method for preparing liquid anaerobic polyzirconocarbosilane |
| CN103588484A (en) * | 2013-10-23 | 2014-02-19 | 航天材料及工艺研究所 | Machinable Si/C/Zr ceramic precursor and preparation method thereof |
| CN103772709A (en) * | 2014-01-03 | 2014-05-07 | 航天材料及工艺研究所 | Si/C/Zr ceramic precursor and preparation method thereof |
| CN104211967A (en) * | 2014-08-14 | 2014-12-17 | 中国科学院过程工程研究所 | Polymetalcarbosilane, and preparation method and application thereof |
| CN105669983A (en) * | 2016-01-22 | 2016-06-15 | 中国人民解放军国防科学技术大学 | Zirconium-containing organic metal polymer ceramic precursor, method for preparing same and application of zirconium-containing organic metal polymer ceramic precursor |
| CN106348759A (en) * | 2016-08-18 | 2017-01-25 | 中国人民解放军国防科学技术大学 | Normal-temperature and normal-pressure synthesizing method of Zr-Si-C ceramic precursor |
| CN109054026A (en) * | 2018-10-10 | 2018-12-21 | 中国人民解放军国防科技大学 | Preparation method of HfC-SiC ultrahigh-temperature ceramic precursor |
| CN110028639A (en) * | 2019-04-17 | 2019-07-19 | 厦门理工学院 | A kind of photosensitivity Zr-B-Si-C ceramic forerunner and its in-situ preparation method |
| CN110424068A (en) * | 2019-08-06 | 2019-11-08 | 江西嘉捷信达新材料科技有限公司 | Mix ultrahigh temperature ceramic composite preparation SiC fiber and its methods and applications |
| CN112958146A (en) * | 2019-12-12 | 2021-06-15 | 中国科学院大连化学物理研究所 | MFI molecular sieve nanosheet-loaded zirconium-based catalyst and application thereof in butadiene preparation reaction |
| CN114058019A (en) * | 2021-11-15 | 2022-02-18 | 中国人民解放军国防科技大学 | Ultrahigh-temperature ceramic precursor capable of being melt-spun, and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| Stepwise synthesis of a Zr-C-Si main chain polymer precursor for ZrC/SiC/C composite ceramics;Qiang Gao 等;《RSC advances》;第12卷(第4期);第2253-2261页 * |
| Synthesis of a meltable polyzirconosilane precursor for SiZrNC multinary ceramics;Qiang Gao 等;《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》;第42卷(第6期);第2577-2585页 * |
| 含锆超高温非氧化物陶瓷材料的研究进展;王明存 等;《陶瓷学报》;第36卷(第3期);第217-221页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115894940A (en) | 2023-04-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0152704B1 (en) | Polyhydridosilanes and their conversion to pyropolymers | |
| US4869854A (en) | Process for manufacturing organic silazane polymers and ceramics therefrom | |
| CN112088174B (en) | Polyethylene and chlorinated polyethylene thereof | |
| Yu et al. | Preparation, cross-linking and ceramization of AHPCS/Cp2ZrCl2 hybrid precursors for SiC/ZrC/C composites | |
| CN112088175B (en) | Polyethylene and chlorinated polyethylene thereof | |
| CN109867793B (en) | Preparation method of high-temperature-resistant polymer containing carborane and silane structures and application of high-temperature-resistant polymer in oxidation-resistant coating | |
| CN104211967A (en) | Polymetalcarbosilane, and preparation method and application thereof | |
| JP5011350B2 (en) | Polycarbosilane and method for producing the same | |
| CN111057244B (en) | ZrC/SiC/C composite ceramic precursor material and preparation method thereof | |
| CN106832083B (en) | Fluorine-containing syndiotactic polystyrene and preparation method thereof | |
| Long et al. | Synthesis of soluble and meltable pre‐ceramic polymers for Zr‐containing ceramic nanocomposites | |
| CN115894940B (en) | Preparation method of Zr-C-Si main chain-containing single-source ultrahigh-temperature ceramic precursor | |
| CN111548497B (en) | Silyne hybrid resin, cured product, ceramic material, composite material and preparation method | |
| Seyferth et al. | Poly (vinylsilane),[CH2CH (SiH3)] n: preparation, characterization, and utilization as a preceramic polymer | |
| Ganapathiappan et al. | New initiators for the ring-opening thermal polymerization of hexachlorocyclotriphosphazene: synthesis of linear poly (dichlorophosphazene) in high yields | |
| JPH07216094A (en) | Polyborosilazanes as preceramics, their preparation, and ceramic materials derived from them | |
| Zhao et al. | Synthesis and characterization of meltable and soluble reticulating polysilazane modified via melamine toward SiCN ternary ceramics | |
| CN114715861B (en) | Synthesis method of linear macromolecule BN precursor | |
| CN114058019B (en) | Ultrahigh-temperature ceramic precursor capable of being melt-spun, and preparation method and application thereof | |
| US4946713A (en) | Poly(alkenylpentaborane) ceramic precursors | |
| CN110256622B (en) | Reinforced and toughened syndiotactic polystyrene and preparation method thereof | |
| CN111499857B (en) | Conjugated diene and epoxy compound block copolymer and preparation method thereof | |
| US5202399A (en) | Poly(b-alkenyl-borazine) ceramic precursors | |
| CN105669983B (en) | One kind precursor of polymer-ceramic containing zirconium metal-organic and the preparation method and application thereof | |
| CN112126074B (en) | HfC/C ceramic precursor polymer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |