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CN109265687A - A kind of preparation method of the Polycarbosilane containing heterogeneous element - Google Patents

A kind of preparation method of the Polycarbosilane containing heterogeneous element Download PDF

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CN109265687A
CN109265687A CN201810937508.2A CN201810937508A CN109265687A CN 109265687 A CN109265687 A CN 109265687A CN 201810937508 A CN201810937508 A CN 201810937508A CN 109265687 A CN109265687 A CN 109265687A
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heterogeneous element
polycarbosilane
reaction
acetylacetonate
preparing
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CN109265687B (en
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莫高明
段杨鹏
何流
黄庆
陈海俊
卓万峰
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/398—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing boron or metal atoms

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Abstract

The invention discloses a kind of preparation methods of Polycarbosilane containing heterogeneous element.This method is using the poly- silicon-carbon silane of liquid low-molecular and the halide containing heterogeneous element or organic complex as raw material, raw material is placed in high-temperature high-voltage reaction device, under alkali metal silicoaluminate catalysts conditions, sealed after being vacuumized, then heat to 350-450 DEG C of confined reaction, it is cooled to room temperature after reaction, releases gas in reaction system, obtain the crude product of the Polycarbosilane containing heterogeneous element.This method can be shortened the reaction time, improve preparation efficiency, and the precursor branching prepared and cyclic structure are less, and Si-H content is higher, is conducive to oxygen content and structure control in the raising and ceramming process of precursor spinnability.

Description

A kind of preparation method of the Polycarbosilane containing heterogeneous element
Technical field
The invention belongs to silicon carbide precursor preparation technical fields, and in particular to a kind of preparation of the silane of carbon containing heterogeneous element Method.
Background technique
Continuous carbofrax fibre enhances carborundum based material (SiCf/ SiC) have density is small, high temperature resistant, it is corrosion-resistant, The features such as high-intensitive, is widely used in the neck such as heat-resistant part, high temperature air filtration and heat exchanger of aerospace engine Domain, simultaneously because it has the characteristics that resistance to neutron irradiation ability, high-temperature oxidation resistant, it is considered to be accident error-tolerance type core combustion of new generation Expect one of the candidate of cladding materials.
It is precursor for SiC fiber since the Yajima et al. of northeastern Japan university has been started with Polycarbosilane (PCS) The beginning, organic precursor method conversion method be increasingly becoming prepares SiC fiber and ceramics important method.It is to be with organic polymer Precursor makes its molding using its fusible soluble characteristic, then is allowed to be changed into the side of inorganic ceramic material through high-temperature heat treatment Method.
PCS is one of SiC fiber and the important precursor of ceramics.PCS is as SiC fiber precursor in use, usually needing Air curing is carried out to it, so that final fiber contains excessive oxygen, form SiC in conjunction with carbon, element siliconxOyPhase, 1400 DEG C or more can decompose, and fibre property is caused to decline rapidly.PCS as ceramic precursor in use, at 1400 DEG C or more, β-SiC crystallite dimension can grow up rapidly, cause interfacial stress between crystal grain to increase, cause SiC ceramic mechanical properties decrease.? Heterogeneous element, including aluminium, titanium, zirconium, iron, yttrium, lanthanum etc. are introduced in PCS, what is had can increase densification together in high-temperature sintering process When inhibit crystal grain to grow up rapidly so that the resistance to very-high performance of final products improves, what is had can assign electromagnetism and absorbing property, increase most Finished product functional attributes.
By taking polyaluminocarbosilane (PACS) as an example, preparing Polycarbosilane containing heterogeneous element at present mainly has following methods:
(1) solid-state polydimethylsiloxane (PDMS) or Polycarbosilane (PCS) are reacted with aluminum contained compound.Japanese Ishikawa Et al. (Nature, 1998,391:773-775) using solid-state PCS and aluminium acetylacetonate (Al (AcAc)3) 300 DEG C under normal pressure It reacts and generates PACS；Chen Jiang small stream et al. (Chen Jiangxi, Xiamen University's doctoral thesis, 2007) is using solid-state PDMS in confined reaction PACS is prepared in kettle；It using PCS and anaerobic mono-functional compounds is raw material first in 130-145 in CN201410675365.4 It is reacted at DEG C, then heats to 380-450 DEG C of heat preservation and obtain PACS in 1-5 hours.
(2) the poly- silicon-carbon silane (PSCS) of liquid or Polycarbosilane (LPCS) and Al (AcAc)3It reacts under normal pressure. With liquid Polycarbosilane (LPCS) and Al (AcAc) in CN200910111053.X3For raw material, reacted at 300-420 DEG C PACS is prepared, and the PACS molecular weight obtained in this way is relatively low, softening point is relatively low, is not suitable as fiber precursor It uses.To improve PACS molecular weight, it usually needs be added cracking column, cracking temperature be generally 500 DEG C or more (Zhao great Fang etc., University of Science & Technology, Beijing's journal, 2007,29:130-134).
In the above-mentioned various methods for preparing PACS, with solid-state PDMS, PCS or the PSCS and aluminum contained compound of higher molecular weight When reaction, often there is a problem of that solid material conduction inequality, reaction are difficult to control；It reacts under normal pressure state, is closed containing calorize Object is volatile, causes aluminium content in precursor not easy to control；It is anti-with aluminum contained compound under normal pressure with the LPCS of liquid or PSCS At once, often the reaction time is very long (when 40h or more, especially a large amount of preparations), and due to the use of superelevation cracking temperature, leads to elder generation Branching and cyclic structure in body is driven to increase, it is unfavorable to spinning.
When preparation is containing other heterogeneous element polycarbosilane precusors, there is also the problems similar with PACS.
Summary of the invention
The problem of technical purpose of the invention is for above-mentioned preparation Polycarbosilane containing heterogeneous element, provides one kind The preparation method of the Polycarbosilane containing heterogeneous element, this method preparation efficiency is high, and the structure of Polycarbosilane containing heterogeneous element obtained is excellent It is good.
To realize the above-mentioned technical purpose, the technical scheme adopted by the invention is as follows: a kind of Polycarbosilane containing heterogeneous element Preparation method, it is characterized in that: using poly- silicon-carbon silane and the halide containing heterogeneous element or organic complex as raw material, the poly- silicon Carbon silane is low molecule product of the polydimethylsiloxane after Pintsch process, and room temperature is in a liquid state, and molecular weight is less than 1000g/mol；
Raw material is placed in high-temperature high-voltage reaction device, it, will under the conditions of existing for the alkali metal silicoaluminate catalyst High-temperature high-voltage reaction device sealed after being vacuumized, is then warming up to 350-450 DEG C of confined reaction for reaction unit；After reaction It is cooled to room temperature, releases gas in reaction system, obtain the crude product of the Polycarbosilane containing heterogeneous element.
Preferably, then being vacuumized with nitrogen or inert gas replacement 2 times or more, the closed reaction unit.
Preferably, being dissolved organic solvent is added in the crude product of the obtained Polycarbosilane containing heterogeneous element, so After filter, by filtration product 200 DEG C -350 DEG C vacuum distillation after be cooled to room temperature, obtain Polycarbosilane containing heterogeneous element.Institute It is unlimited to state organic solvent, including one or more of benzene,toluene,xylene, tetrahydrofuran, chloroform, n-hexane equal solvent.Institute It states in vacuum distillation process, vacuum state is preferably that pressure is less than 20Pa.
Heretofore described heterogeneous element is the element in addition to carbon, silicon, hydrogen, oxygen, including but not limited to aluminium, iron, zirconium, One or more of elements such as titanium, cobalt, nickel, niobium, yttrium, lanthanum.
The organic complex containing heterogeneous element includes but is not limited to aluminium acetylacetonate, aluminium-alcohol salt, ferric acetyl acetonade, cyclopentadienyl Iron, acetylacetone,2,4-pentanedione zirconium, titanium acetylacetone, acetylacetone cobalt, nickel acetylacetonate, acetylacetone,2,4-pentanedione niobium, acetylacetone,2,4-pentanedione yttrium, acetylacetone,2,4-pentanedione One or more of lanthanum etc..
In the present invention, the composite alkali aluminum silicon compound has cavernous structure and high temperature resistant property, at 600 DEG C with flowering structure It does not change.Wherein, the size in hole is preferably smaller than 1 μm.
In the present invention, the halide or organic complex containing heterogeneous element is referred to as compound containing heterogeneous element, makees To be preferred, which accounts for the 0.1%-10% of poly- silicon-carbon silane quality, further preferably 2%-8%.
Preferably, the additive amount of the composite alkali aluminum silicon compound accounts for the 1%-10% of poly- silicon-carbon silane quality.
Preferably, high-temperature high-voltage reaction device is evacuated to pressure less than 5Pa.
Preferably, reaction unit is warming up to 400-450 DEG C.
Preferably, confined reaction 3h-20h, more preferably 5h-15h.
Compared with prior art, the present invention with the poly- silicon-carbon silane of low molecule liquid and the halide containing heterogeneous element or has Machine complex compound is raw material, under the conditions of existing for the alkali metal silicoaluminate catalyst, using high temperature high pressure device, after vacuumizing Closed, heating reacts, and pressure increases in device in reaction process, can reach 5Mpa-15MPa, has the following beneficial effects:
(1) using the low molecular weight polycaprolactone silicon-carbon silane of liquid as raw material, the problem that can effectively avoid solid material heat transfer uneven has Conducive to the quality of control reaction process and promotion final products；
(2) method for using high temperature and pressure, is used cooperatively a certain amount of alkali metal silicoaluminate catalyst, can shorten Reaction time improves preparation efficiency；
(3) it is warming up to 350-450 DEG C, avoids the use of superhigh temperature, the molecule of Polycarbosilane containing heterogeneous element can be optimized Structure, the branchign of molecule of Polycarbosilane containing heterogeneous element and cyclic structure obtained are less, are conducive to the raising of its spinnability；This Outside, the distillation for also avoiding the compound containing heterogeneous element is more advantageous to heterogeneous element in control Polycarbosilane containing heterogeneous element and contains Amount.
Detailed description of the invention
Fig. 1 is the FTIR spectrogram of PACS-1 obtained in the embodiment of the present invention 1.
Fig. 2 is PACS-1 obtained in the embodiment of the present invention 129SiNMR spectrogram.
Fig. 3 is PACS-1 obtained in the embodiment of the present invention 127AlNMR spectrogram.
Specific embodiment
Below with reference to embodiment, present invention is further described in detail, it should be pointed out that embodiment described below purport It is being convenient for the understanding of the present invention, and is not playing any restriction effect to it.
Embodiment 1:
Polydimethylsiloxane obtains poly- silicon-carbon silane after Pintsch process, and molecular weight is less than 1000g/mol, and room temperature is in liquid State.The poly- silicon-carbon silane of 1000g liquid, 30g aluminium acetylacetonate, 20g alkali metal silicoaluminate are added to high temperature high pressure device It is interior, vacuum state, sealing device are evacuated to afterwards three times with high pure nitrogen displacement kettle；Then, heating is opened, with certain heating rate liter Temperature stops after reacting 8h to 410 DEG C.When being down to room temperature state, reactant polyaluminocarbosilane crude product PACS-1 is taken out, to It surveys.
Fig. 1 is the FTIR spectrogram of PACS-1.This spectrogram is similar with the FTIR spectrogram of common Polycarbosilane.In scheming 2100cm-1Place represents the intensity and 1250cm at the peak Si-H-1Place represents Si-CH3The ratio of the intensity at peak as Si-H relative amount, The ratio is 0.79.
Fig. 2 is PACS-129SiNMR spectrogram.SiC in figure4Peak and SiC3The area ratio at the peak H is 1.56, can be certain The degree of branching of molecular structure is represented in degree.
Fig. 3 is PACS-127AlNMR spectrogram.AlO in figure6、AlO5、AlO4The appearance of various ligands illustrates that Al element combines Into precursor molecule, precursor is polyaluminocarbosilane.
In addition, the weight average molecular weight through GPC method measurement PACS-1 is 3210g/mol, molecular weight distribution index 3.1；Through The softening point that melting point apparatus measures PACS-1 is 135 DEG C.
Comparative example 1:
The present embodiment is the comparative example of above-described embodiment 1.
In this comparative example, using the poly- silicon-carbon silane of liquid, the liquid in the poly- silicon-carbon silane of the liquid and embodiment 1 is poly- Silicon-carbon silane is identical, is that polydimethylsiloxane obtains after Pintsch process, and molecular weight is less than 1000g/mol, and room temperature is in a liquid state.
The poly- silicon-carbon silane of 1000g liquid, 30g aluminium acetylacetonate are added to high-temperature pressure reaction unit, the high temperature is normal Pressure device both includes reaction kettle, also includes Pintsch process column.With high pure nitrogen displacement kettle three times after under nitrogen protection, under normal pressure Unlatching is warming up to 410 DEG C, while also opening cracking column and being warming up to 500 DEG C, stops after reacting 20h.Polyaluminocarbosilane is obtained slightly to produce Product PACS-2.
The partial test result of the PACS-2 is as follows:
Si-H relative amount is 0.71 in FTIR spectrogram；29SiC in SiNMR spectrogram4Peak and SiC3The area ratio at the peak H is 2.48；It is 3120g/mol, molecular weight distribution index 30. through GPC method measurement weight average molecular weight；Softening point is measured through melting point apparatus It is 145 DEG C.
PACS-1 is compared with PACS-2 it is found that not needing high temperature compared with high temperature and high pressure method preparation PACS when high-temperature pressure method Column is cracked, the time is shorter, and preparation efficiency greatly improves；There is lower degree of branching and higher Si-H phase with molecular configurational To content, be conducive to the raising and the structure control of subsequent ceramic of precursor spinnability.
Embodiment 2:
The poly- silicon-carbon of liquid in the present embodiment, using the poly- silicon-carbon silane of liquid, in the poly- silicon-carbon silane of the liquid and embodiment 1 Silane is identical, is that polydimethylsiloxane obtains after Pintsch process, and molecular weight is less than 1000g/mol, and room temperature is in a liquid state.
The poly- silicon-carbon silane of 1000g liquid, 40g ferric acetyl acetonade, 20g alkali metal silicoaluminate are added to high temperature and pressure In device, vacuum state, sealing device are evacuated to afterwards three times with high pure nitrogen displacement kettle.Then, heating is opened, with the speed that centainly heats up Rate is warming up to 420 DEG C, stops after reacting 6h.Room temperature to be down to is taken out, and Polyferrocarbosilane crude product PFCS is obtained.
The partial test result of the PFCS is as follows: Si-H relative amount is 0.73 in FTIR spectrogram；GPC measures Weight-average molecular Amount is 3310g/mol, molecular weight distribution index 3.2；It is 156 DEG C that melting point apparatus, which measures softening point,.
Embodiment 3:
The poly- silicon-carbon of liquid in the present embodiment, using the poly- silicon-carbon silane of liquid, in the poly- silicon-carbon silane of the liquid and embodiment 1 Silane is identical, is that polydimethylsiloxane obtains after Pintsch process, and molecular weight is less than 1000g/mol, and room temperature is in a liquid state.
The poly- silicon-carbon silane of 1000g liquid, 45g acetylacetone,2,4-pentanedione zirconium, 25g alkali metal silicoaluminate are added to high temperature and pressure In device, vacuum state, sealing device are evacuated to afterwards three times with high pure nitrogen displacement kettle.Then, heating is opened, with the speed that centainly heats up Rate is warming up to 425 DEG C, stops after reacting 10h.Room temperature to be down to is taken out, and poly- zirconium carbon silane crude product PZCS is obtained.
The partial test result of the PZCS is as follows: Si-H relative amount is 0.75 in FTIR spectrogram；GPC measures Weight-average molecular Amount is 3415g/mol, molecular weight distribution index 3.15；It is 160 DEG C that melting point apparatus, which measures softening point,.
Embodiment 4:
The poly- silicon-carbon of liquid in the present embodiment, using the poly- silicon-carbon silane of liquid, in the poly- silicon-carbon silane of the liquid and embodiment 1 Silane is identical, is that polydimethylsiloxane obtains after Pintsch process, and molecular weight is less than 1000g/mol, and room temperature is in a liquid state.
The poly- silicon-carbon silane of 1000g liquid, 50g lanthanum acetylacetone, 15g alkali metal silicoaluminate are added to high temperature and pressure In device, vacuum state, sealing device are evacuated to afterwards three times with high pure nitrogen displacement kettle.Then, heating is opened, with the speed that centainly heats up Rate is warming up to 420 DEG C, stops after reacting 12h.Room temperature to be down to is taken out, and poly- lanthanum carbon silane PLCS is obtained.
The partial test result of the PLCS is as follows: Si-H relative amount is 0.72 in FTIR spectrogram；GPC measures Weight-average molecular Amount is 3230g/mol, molecular weight distribution index 3.25；It is 148 DEG C that melting point apparatus, which measures softening point,.
Embodiment 5:
The poly- silicon-carbon of liquid in the present embodiment, using the poly- silicon-carbon silane of liquid, in the poly- silicon-carbon silane of the liquid and embodiment 1 Silane is identical, is that polydimethylsiloxane obtains after Pintsch process, and molecular weight is less than 1000g/mol, and room temperature is in a liquid state.
The poly- silicon-carbon silane of 1000g liquid, 45g acetylacetone,2,4-pentanedione yttrium, 25g alkali metal silicoaluminate are added to high temperature and pressure In device, vacuum state, sealing device are evacuated to afterwards three times with high pure nitrogen displacement kettle.Then, heating is opened, with the speed that centainly heats up Rate is warming up to 430 DEG C, stops after reacting 6h.Room temperature to be down to is taken out, and poly- yttrium carbon silane crude product PYCS is obtained.
The partial test result of the PYCS is as follows: Si-H relative amount is 0.75 in FTIR spectrogram；GPC measures Weight-average molecular Amount is 3310g/mol, molecular weight distribution index 3.4；It is 138 DEG C that melting point apparatus, which measures softening point,.
Technical solution of the present invention is described in detail in embodiment described above, it should be understood that the above is only For specific embodiments of the present invention, it is not intended to restrict the invention, all any modifications made in spirit of the invention, Supplement or similar fashion substitution etc., should all be included in the protection scope of the present invention.

Claims (10)

1.一种含异质元素聚碳硅烷的制备方法，其特征是：以聚硅碳硅烷和含异质元素的卤化物或有机络合物为原料，所述聚硅碳硅烷是聚二甲基硅烷经高温裂解后的低分子产物，室温呈液态，分子量小于1000g/mol；A method for preparing a polycarbosilane containing a heterogeneous element, characterized in that a polysilylcarbosilane and a heterogene-containing halide or an organic complex are used as a raw material, and the polysilylcarbosilane is a polydimethylene The low molecular product of the silane after pyrolysis, liquid at room temperature, molecular weight less than 1000g / mol; 将原料置于高温高压反应装置中，在碱金属硅铝化合物催化剂存在的条件下，将高温高压反应装置抽真空后密封，然后将反应装置升温至350-450℃密闭反应；反应结束后冷却至室温，放出反应体系内气体，得到含异质元素聚碳硅烷的粗产物。The raw material is placed in a high temperature and high pressure reaction device, and the high temperature and high pressure reaction device is vacuumed and sealed in the presence of an alkali metal silicoalumino compound catalyst, and then the reaction device is heated to 350-450 ° C to close the reaction; after the reaction is completed, it is cooled to At room temperature, the gas in the reaction system was evolved to obtain a crude product containing a heterojunction polycarbosilane. 2.如权利要求1所述的含异质元素聚碳硅烷的制备方法，其特征是：所述异质元素包括铝、铁、锆、钛、钴、镍、铌、钇、镧元素中的一种或几种。2 . The method according to claim 1 , wherein the heterogeneous element comprises aluminum, iron, zirconium, titanium, cobalt, nickel, lanthanum, cerium and lanthanum. One or several. 3.如权利要求1所述的含异质元素聚碳硅烷的制备方法，其特征是：所述含异质元素的有机络合物包括乙酰丙酮铝、铝醇盐、乙酰丙酮铁、茂铁、乙酰丙酮锆、乙酰丙酮钛、乙酰丙酮钴、乙酰丙酮镍、乙酰丙酮铌、乙酰丙酮钇、乙酰丙酮镧中的一种或几种。The method for preparing a heterogeneous element-containing polycarbosilane according to claim 1, wherein the heterogeneous element-containing organic complex comprises aluminum acetylacetonate, aluminum alkoxide, iron acetylacetonate, and ferrocene And one or more of zirconium acetylacetonate, titanium acetylacetonate, cobalt acetylacetonate, nickel acetylacetonate, acetylacetonate oxime, acetylacetonate oxime, and acetylacetonate oxime. 4.如权利要求1所述的含异质元素聚碳硅烷的制备方法，其特征是：所述含异质元素的卤化物与有机络合物统称为含异质元素化合物，所述含异质元素化合物的添加量占聚硅碳硅烷质量的0.1％-10％，进一步优选为2％-8％。The method for preparing a heterogeneous element-containing polycarbosilane according to claim 1, wherein the hetero-element-containing halide and the organic complex are collectively referred to as a heterogeneous element-containing compound, and the The amount of the elemental compound added is from 0.1% to 10% by mass based on the mass of the polysilylcarbosilane, and more preferably from 2% to 8%. 5.如权利要求1所述的含异质元素聚碳硅烷的制备方法，其特征是：所述碱金属铝硅化合物的添加量占聚硅碳硅烷质量的1％-10％。The method for preparing a heterogeneous element-containing polycarbosilane according to claim 1, wherein the alkali metal aluminum silicon compound is added in an amount of from 1% to 10% by mass based on the mass of the polysilylcarbosilane. 6.如权利要求1所述的含异质元素聚碳硅烷的制备方法，其特征是：将高温高压反应装置抽真空至压力小于5Pa。The method for preparing a heterogeneous element-containing polycarbosilane according to claim 1, wherein the high temperature and high pressure reaction device is evacuated to a pressure of less than 5 Pa. 7.如权利要求1所述的含异质元素聚碳硅烷的制备方法，其特征是：反应装置升温至400-450℃。The method according to claim 1, wherein the reaction device is heated to 400-450 °C. 8.如权利要求1所述的含异质元素聚碳硅烷的制备方法，其特征是：密闭反应3h-20h，优选为5h-15h。The method for preparing a heterogeneous element-containing polycarbosilane according to claim 1, wherein the sealing reaction is carried out for 3 to 20 hours, preferably for 5 to 15 hours. 9.如权利要求1所述的含异质元素聚碳硅烷的制备方法，其特征是：将得到的含异质元素聚碳硅烷的粗产物中加入有机溶剂进行溶解，然后过滤，将过滤产物在200℃-350℃真空蒸馏后冷却至室温，得到含异质元素聚碳硅烷；The method for preparing a heterogeneous element-containing polycarbosilane according to claim 1, wherein the obtained crude product containing a heterogeneous polycarbosilane is added to an organic solvent to be dissolved, and then filtered to filter the product. After vacuum distillation at 200 ° C -350 ° C, and then cooled to room temperature, to obtain a hetero-element containing polycarbosilane; 作为优选，所述有机溶剂包括苯、甲苯、二甲苯、四氢呋喃、氯仿、正己烷中的一种或几种。Preferably, the organic solvent includes one or more of benzene, toluene, xylene, tetrahydrofuran, chloroform, and n-hexane. 10.如权利要求1至9中任一权利要求所述的含异质元素聚碳硅烷的制备方法，其特征是：反应过程中，所述高温高压反应装置内的压力达到5Mpa-15MPa。The method for preparing a heterogeneous element-containing polycarbosilane according to any one of claims 1 to 9, wherein during the reaction, the pressure in the high-temperature and high-pressure reaction device reaches 5 MPa to 15 MPa.
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CN109797460A (en) * 2019-01-28 2019-05-24 江西嘉捷信达新材料科技有限公司 Preparation method under the SiC fiber of boron containing aluminium and its supercritical fluid
CN109824905A (en) * 2019-01-28 2019-05-31 江西嘉捷信达新材料科技有限公司 High temperature resistant polycarbosilane precursor and preparation method thereof
CN110003476A (en) * 2019-04-12 2019-07-12 苏州赛力菲陶纤有限公司 A kind of preparation method of the Polycarbosilane containing zirconium
CN110563955A (en) * 2019-10-24 2019-12-13 中国科学院宁波材料技术与工程研究所 Liquid curable metal-based polycarbosilane and preparation method thereof
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