CN110078926A - A kind of high-volume high pressure synthesis method of Polycarbosilane - Google Patents
A kind of high-volume high pressure synthesis method of Polycarbosilane Download PDFInfo
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Abstract
Provide a kind of high-volume high pressure synthesis method of Polycarbosilane, comprising the following steps: (1) silicon-containing material and catalyst are placed in stainless steel autoclave, with high pure nitrogen displacement hot pressing gas reactor, sealing；(2) by temperature in the kettle temperature programming to reaction temperature, after the reaction time, Polycarbosilane crude product is obtained after cooling；(3) by Polycarbosilane crude product through xylene soluble, filtering, filtrate is evaporated under reduced pressure, up to Polycarbosilane after cooling；Catalyst is one of boracic, aluminium, titanium, zirconium, hafnium or a variety of organo-metallic compounds, the including but not limited to compound of boron alkyl, boron alkoxide, alkyl aluminum, aluminum alkoxide, alkyl titanium, alkoxytitanium, the cyclopentadienyl compounds of titanium, alkyl zirconium, zirconium alkoxide, the cyclopentadienyl compounds of zirconium, alkyl hafnium, alkoxy hafnium, hafnium；Reaction temperature is 400-450 DEG C, pressure 4-10MPa, reaction time are 2~12 hours；Autoclave volume is 50 liters -10000 liters.
Description
Technical field
The present invention generally belongs to Polycarbosilane synthesis technical field, is especially to be related to a kind of high-volume of Polycarbosilane
High pressure synthesis method.
Background technique
Polycarbosilane (Polycarbosilane, PCS) is the converting method preparation SiC fiber of precursor and precursor leaching
It is multiple that stain cracking process (Precursor infiltration and pyrolysis, PIP) prepares the SiC bases such as C/SiC, SiC/SiC
The important source material of condensation material has important application in fields such as aerospace, high-performance weaponry and derived energy chemicals.
There are many kinds of the synthetic methods of Polycarbosilane, mainly includes following four method.
(1) direct synthesis technique: for example, using organic silicon monomer, being reacted by Grignard Reagent, can be obtained structure and be compared rule
Whole carbon silane and Polycarbosilane.J P Wesson et al. is by the organic silicon monomer containing chlorine, in solvent appropriate (THF or diformazan
Benzene, toluene etc.) in acted on metallic potassium or sodium, directly generate Polycarbosilane (AD-AO-99030)；Or it is adopted in US 5153295
Reacted with Chloromethyltrichlorosilane and Grignard Reagent, and by LiAlH4 reduction, obtain Polycarbosilane, molecular weight distribution from
300 to 3000, yield 85%, 1000 DEG C of cracking ceramic yield 30-60% (yield is related to molecular weight).
(2) high temperature and pressure is pyrolyzed rearrangement method: for example, arrow island et al. is by dimethyldichlorosilane and metallic sodium in dimethylbenzene
It synthesizes polydimethylsiloxane (PS), uses argon gas in 100 kilograms per centimeters in autoclave by PS2Under in 450-470 DEG C of reaction 14-
48 hours, obtain the polymer for dissolving in n-hexane, referred to as Mark I type Polycarbosilane (J Am Ceram Soc, 59 (7-8)
324-77,1976).Another method be in US 4100233 by PS with a small amount of catalyst polyborosiloxane in nitrogen in normal
Pressure is heated to 350 DEG C of polymerizations and obtains a kind of polymer, referred to as Mark type III Polycarbosilane；CN1569926A, which is disclosed, to be adopted
With the method for autoclave synthesis Polycarbosilane, used temperature is 450 DEG C, and pressure reaches 15-20MPa, synthetic yield 45%；
It is reacted using 470 DEG C, pressure is more than 20MPa, and yield can be close to 60%, but high-pressure process synthesis is relatively high to equipment requirement, peace
Full property is poor, and synthesis temperature is more than 470 DEG C, and pressure is more than 10MPa, and laboratory lab scale is feasible, but amplification is synthetically produced, volume
Increase, then the materials such as general stainless steel (the highest pressure resistance if more than 10 liters of 450 DEG C of highest heatproof, big volume is no more than 10MPa)
Matter is all difficult to meet the requirements, it is necessary to use expensive niobium alloy, cost is caused to rise violently.
(3) constant-pressure and high-temperature synthetic method, for example, PS and a small amount of catalyst polyborosiloxane exist in 4100233 patent of US
350 DEG C of polymerizations are heated in nitrogen under normal pressure and obtain a kind of polymer, referred to as Mark type III Polycarbosilane；US
The method that two legal systems make Polycarbosilane is disclosed in 4377677: polysilane is heated steaming by the first step under 50~600 DEG C of normal pressures
It evaporates to obtain the Polycarbosilane for the low molecular weight that several divided doses are 300-600, the Polycarbosilane of harmonic component is then heated to 250-
500 DEG C obtain the Polycarbosilane of high molecular weight.CN85108006 discloses constant-pressure and high-temperature synthesis technology, that is, heats polysilane
To 150~500 DEG C, by 400 DEG C of hot-zone, Polycarbosilane crude product was obtained under inert atmosphere through 30 minutes to 10 hours, is passed through
Dissolution, filtering, distillation, can be obtained Polycarbosilane；Constant-pressure and high-temperature synthesis technology is current domestic main Polycarbosilane batch
Production technology, it is simple to equipment requirement, but synthetic yield is not high (generally 35-40%), and generated time is long, a batch
Generated time be up to 3-5 days, combined coefficient is very low.So low PCS synthetic yield, necessarily causes its production cost substantially
(domestic existing about 5000 yuan/kilogram of price) is improved, the cost for also further resulting in SiC fiber and SiC based composites occupies height
Under not, the popularization of related application is limited.
(4) yield can be improved by adding catalyst due to very long the time required to rearrangement reaction in catalysis synthesis process；?
Some researches show that by catalyzing and synthesizing the yield that non-pressure process can be improved and synthesize PCS；It is added in PDMS on a small quantity by diphenyl two
Polyborosiloxane made of chlorosilane and acid reaction makees catalyst, and 350 DEG C of reaction certain times can be obtained under normal pressure
PCS, yield can be improved to 48%；But the method introduces the miscellaneous element such as B and O in the structure of final product PCS.US
Disclose in 7202376: silicate (Si/Al=30) compound that similar zeolite on a small quantity is added in PDMS is catalyst, normal
It depresses 400 DEG C of reaction certain times and obtains the PCS with certain viscosity, yield can be improved to 50%；But by stickum
Actual yield is only 45% after removal；US9815944 is reported using triphenyl borine as catalyst, polysilane or small molecule
Polycarbosilane is raw material, has synthesized Polycarbosilane.But triphenyl borine is not common raw material, it is expensive.
As can be seen that the yield of non-pressure process synthesis PCS be also far from reaching high-pressure process synthetic yield (generally 60% with
On) level, and high-pressure process synthesis PCS is because reaction temperature is high, lead to that reaction pressure is poly- to be risen, the reaction vessel of general material without
Method meets temperature and pressure demand, therefore current high-pressure synthesis fado is suitable for laboratory research, raw in industrial mass
Aspect is produced because equipment requirement causes PCS preparation cost high.
Summary of the invention
It is an object of the invention to overcome the above-mentioned PSC of high-pressure synthesis in the prior art temperature is high, pressure is high to lead to equipment
Defect at high cost provides a kind of high-volume high pressure synthesis method of Polycarbosilane, by adding catalyst, by reaction temperature control
System is no more than 450 DEG C, so that reacting kettle inner pressure control be made to be no more than 10MPa, that is, the autoclave of stainless steel material can be used,
Autoclave volume can be raised to 10000 liters from 50, while the synthesis yield of Polycarbosilane can achieve 50% or more, significant to shorten
Manufacturing cycle, reduces the cost of mass production.
The technical scheme is that a kind of high-volume high pressure synthesis method of Polycarbosilane, it uses stainless steel hot pressing
Kettle is reactor, using silicon-containing material and catalyst as start material；The catalyst is boracic, in aluminium, titanium, zirconium, hafnium
One or more organo-metallic compounds, including but not limited to boron alkyl, boron alkoxide, alkyl aluminum, aluminum alkoxide, alkyl
Titanium, alkoxytitanium, the cyclopentadienyl compounds of titanium, alkyl zirconium, zirconium alkoxide, the cyclopentadienyl compounds of zirconium, alkyl hafnium, alkoxy hafnium, hafnium compound；
Autoclave interior reaction temperature is 400-450 DEG C in synthesis process, pressure 4-10MPa, reaction time are 2~12 hours；Hot pressing
Kettle volume is 50 liters -10000 liters.
Because the amount that normal pressure the preparation method is once prepared can be more, but the period is long in the PSC synthesis of the prior art, general one
Week goes out a defective material；Although prepared by high pressure can go out a defective material for hair method one day, equipment is the small kettle in laboratory, restricted volume.
The method of the present invention can reduce reaction temperature, the reduction of reaction temperature by the use of above-mentioned catalyst first
The pressure in reaction kettle is reduced simultaneously, thus carry out reaction can under conditions of 400-450 DEG C, pressure 4-10MPa,
The reaction condition can be realized by common stainless steel autoclave as reaction kettle；And the prior art need to be higher than 450 DEG C, it is obvious
Condition of high voltage higher than 10MPa, this is that the stainless steel material reactor of the resistance to 450 DEG C of high temperature of highest is unable to satisfy the anti-of preparation demand
Condition is answered, the reactor of higher costs is needed；Secondly, the use of catalyst also accelerates reaction speed, synthesis cycle is shortened,
Compared to the situation that catalyst is not added in high pressure the preparation method, the reaction time shortens 1/3-1/2；In addition, the application is because using stainless
As reactor, volume can be done greatly steel material autoclave, in addition manufacturing cycle shortens, production capacity is easy to do big, significant corresponding drop
Low cost.
Further, synthetic method of the present invention the following steps are included:
(1) silicon-containing material and catalyst are placed in stainless steel autoclave, it is close with high pure nitrogen displacement hot pressing gas reactor
Envelope；
(2) by temperature in the kettle temperature programming to reaction temperature, after the reaction time, Polycarbosilane crude product is obtained after cooling；
(3) by Polycarbosilane crude product through xylene soluble, filtering, filtrate is evaporated under reduced pressure, up to poly- carbon after cooling
Silane.
Further, catalyst of the present invention accounts for the ratio by mass 0.005%-10% of silicon-containing material.Catalyst
Content is high, can shorten the reaction time, improves molecular weight and softening point (general molecular weight is higher, and softening point is higher), can also be with
Improve the yield of synthetic product；But it is easy to cause product to be crosslinked when too high levels, the behaviour such as subsequent dissolution, melting can not be carried out
Make.When the content of catalyst is lower, the time of reaction is longer, and molecular weight and softening point are lower, and the yield of synthetic product is also therewith
It reduces；Pressure when too low in reaction kettle can be more than that design uses pressure.Control the techniques such as catalyst content, reaction time ginseng
Number, can adjust the molecular weight and softening point of Polycarbosilane, extensively to meet different application demands.
Further, above-mentioned silicon-containing material is the substance containing Si element and alkyl, including but not limited to small point simultaneously
Sub- silane, polysilane, small molecule carbon silane.
When silicon-containing material is small molecule silane or small molecule carbon silane, by temperature in the kettle program in the step (2)
Be warming up to before reaction temperature, further include first by temperature in the kettle temperature programming to predetermined temperature, heat preservation the predetermined time, cooling, put
The operation of gas pressure release；Wherein predetermined temperature is 350 DEG C, and the predetermined time is 1~2 hour.
Further, above-mentioned small molecule silane refers to linear and/or cricoid disilane, three silane containing alkyl, four
One of silane is a variety of, and molecular weight is no more than 300；The polysilane refer to containing alkyl using Si-Si bond as main chain
Polymer, molecular weight are greater than 3000；The small molecule carbon silane refers to the compound containing Si-C key and/or Si-Si bond, molecule
Amount is no more than 1000.
When silicon-containing material is polysilane, going back for autoclave is added in the step (1) and silicon-containing material and catalyst simultaneously
Including solvent, the solvent accounts for the amount by weight 1~80% of silicon-containing material；Solvent includes but is not limited to n-hexane, toluene,
Dimethylbenzene, gasoline, one of diesel oil or a variety of.
Further, above-mentioned steps 3) in vacuum distillation temperature are as follows: 330~380 DEG C；Vacuum degree is 3-5kPa, is adopted
Vacuum level requirements can be met with water ring pump.
The advanced point of the present invention compared with the prior art is:
1) compared with conventional high temperature and high pressure method, on the one hand the method for the present invention reduces synthesis temperature by addition catalyst
Degree, correspondingly reduces synthesis pressure, meet the requirements stainless steel material autoclave can, drops in terms of energy conservation and equipment cost
Low cost and equipment requirement；On the other hand, it catalyzes and synthesizes and also improves synthesis yield, pass through control catalyst content, synthesis
The technological parameters such as time can adjust the molecular weight and softening point of Polycarbosilane extensively, and the softening point of Polycarbosilane can be 60
DEG C~250 DEG C between adjust, meet the requirement of different application.
2) technological parameter significantly reduces equipment requirement, such as 420-450 DEG C of temperature, pressure 6- in the method for the present invention
The condition of 10MPa is the high temperature and pressure requirement that stainless steel material autoclave can be resistant to, and can satisfy industrialized production (volume
10000 liters can be raised to from 50), method is easier to implement and significantly improves synthesis yield simultaneously.
3) the method for the present invention is comprehensive is avoided using catalyzing and synthesizing and stainless steel autoclave using expensive materials such as niobium alloys,
Greatly reduce the cost of equipment, the synthesis cost of Polycarbosilane can be greatly reduced, for example, make the synthesis of Polycarbosilane at
Originally it can drop to 2500 yuan/kg from 5000 yuan/kg.
4) using small molecule silane, polysilane or small molecule PCS as raw material catalyst is added, in high pressure height in the method for the present invention
The lower reaction of temperature, can obtain the Polycarbosilane of yield 50.1%-71.5%.
Therefore, reaction temperature control is no more than 450 DEG C, by reaction kettle internal pressure by addition catalyst by the method for the present invention
Power control is being no more than 10MPa, that is, the autoclave of stainless steel material can be used, and autoclave volume can be raised to 10000 liters from 50,
The synthesis yield of Polycarbosilane can achieve 50% or more simultaneously, significantly shortens manufacturing cycle, reduces mass production
Cost.
Specific embodiment
In order to make those skilled in the art more fully understand the present invention, With reference to embodiment to the present invention make into
One step is described in detail.
Comparative example 1: catalyst is not added as raw material using polysilane and synthesizes Polycarbosilane
In 50L stainless steel autoclave, the commercially available polydimethylsiloxane of 35kg is added, with high pure nitrogen displacement gas reactor
After seal.Temperature programming reacts 1h to 450 DEG C, and maximum pressure continues to extend close to 10MPa according to small kettle experimental result in kettle
Reaction time, pressure also will continue to increase, and more than the design pressure of reaction kettle, therefore test and stop.
Solid and liquid product are obtained after cooling simultaneously.It is separated by filtration liquid and solid product, solid product is through diformazan
Benzene dissolution, filtering, filtrate are evaporated under reduced pressure at 350 DEG C, obtain 3.6kg solid Polycarbosilane, yield 10.3%.After tested,
Softening point is 55-58 DEG C.
Comparative example 2: catalyst is not added as raw material using polysilane and synthesizes Polycarbosilane
In 50L stainless steel autoclave, the commercially available polydimethylsiloxane of 35kg is added, with high pure nitrogen displacement gas reactor
After seal.Temperature programming reacts 22h, maximum pressure 9.76MPa in kettle to 415 DEG C.
Liquid product is obtained after cooling.It is evaporated under reduced pressure by 350 DEG C, fails to obtain solid Polycarbosilane.
Embodiment 1: using polysilane as Material synthesis Polycarbosilane
In 50L stainless steel autoclave, the commercially available polydimethylsiloxane of 35kg is added as silicon-containing material, 15kg dimethylbenzene
Solvent and 35g butyl borate catalyst, with being sealed after high pure nitrogen displacement gas reactor.Temperature programming is to 450 DEG C, reaction
8h, maximum pressure is 9.8MPa in kettle.Product is evaporated under reduced pressure at 350 DEG C, is obtained by filtering, filtrate after cooling
22.12kg Polycarbosilane, yield 63.2%.
By test, the softening point of Polycarbosilane is 182~203 DEG C, and IR analyzes to obtain ASi-H/ASi-CH3=0.91, and text
It offers report autoclave and synthesizes resulting ASi-H/ASi-CH3Value is close, and 1000 DEG C of inert atmosphere cracking ceramic yields are 57.3%.
Embodiment 2: using polysilane as Material synthesis Polycarbosilane
In 50L stainless steel autoclave, the commercially available polydimethylsiloxane of 35kg is added as silicon-containing material, 15kg dimethylbenzene
As solvent and 70g butyl borate catalyst, with being sealed after high pure nitrogen displacement gas reactor.Temperature programming to 420 DEG C,
10h is reacted, maximum pressure is 9.1MPa in kettle, and product is evaporated under reduced pressure at 350 DEG C, is obtained by filtering, filtrate after cooling
20.70kg Polycarbosilane, yield 59.1%.
By test, the softening point of Polycarbosilane is 155~176 DEG C, and IR analyzes to obtain ASi-H/ASi-CH3=0.91,1000
DEG C inert atmosphere cracking ceramic yield is 55.6%.
Embodiment 3: using polysilane as Material synthesis Polycarbosilane
In 50L stainless steel autoclave, the commercially available polydimethylsiloxane of 35kg is added as silicon-containing material, 15kg dimethylbenzene
For solvent and 70g butyl borate catalyst, with being sealed after high pure nitrogen displacement gas reactor.Temperature programming is to 450 DEG C, instead
10h is answered, maximum pressure is 9.8MPa in kettle, and product is evaporated under reduced pressure at 350 DEG C, is obtained by filtering, filtrate after cooling
25kg Polycarbosilane, yield 71.5%.
By test, the softening point of Polycarbosilane is 205~235 DEG C, and IR analyzes to obtain ASi-H/ASi-CH3=0.9,1000
DEG C inert atmosphere cracking ceramic yield is 61.6%.
Embodiment 4: using polysilane as Material synthesis Polycarbosilane
In 50L stainless steel autoclave, the commercially available polydimethylsiloxane of 35kg is added as silicon-containing material, 15kg dimethylbenzene
For solvent, 45g tetrabutyl titanate is as catalyst, with sealing after high pure nitrogen displacement gas reactor.Temperature programming to 450 DEG C,
8h is reacted, maximum pressure is 9.5MPa in kettle, and product is evaporated under reduced pressure at 350 DEG C, is obtained by filtering, filtrate after cooling
23.1kg Polycarbosilane, yield 66%.
By test, the softening point of Polycarbosilane is 206~217 DEG C, and IR analyzes to obtain ASi-H/ASi-CH3=0.88,1000
DEG C inert atmosphere cracking ceramic yield is 64.3%.
Embodiment 5: using small molecule Polycarbosilane as Material synthesis Polycarbosilane
In 50L stainless steel autoclave, 30kg small molecule Polycarbosilane is added as silicon-containing material, 35g butyl borate
As catalyst, with being sealed after high pure nitrogen displacement gas reactor.Temperature programming reacts 10h, maximum pressure in kettle to 450 DEG C
For 9.6MPa, it is cooling after up to Polycarbosilane crude product.The crude product is subtracted through xylene soluble, filtering, filtrate at 350 DEG C
Pressure distillation, obtains 25kg Polycarbosilane, yield 71.5%.
By test, the softening point of Polycarbosilane is 195~225 DEG C, and IR analyzes to obtain ASi-H/ASi-CH3=0.9,1000
DEG C inert atmosphere cracking ceramic yield is 59.4%.
In summary example, by controlling the amount in reaction time and catalyst, adjustable softening point, higher softening point pair
Answer higher molecular weight.
Embodiment 6: using small molecule silane as Material synthesis Polycarbosilane
In 50L stainless steel autoclave, 30kg hexamethyldisilane is added as silicon-containing material, 60g butyl borate is made
For catalyst, with being sealed after high pure nitrogen displacement gas reactor.Then temperature programming is cooled down to 350 DEG C, release gas reactor,
Temperature programming reacts 12h to 450 DEG C again, and maximum pressure is 9.8MPa in kettle, up to Polycarbosilane crude product after cooling.This is thick
Product is evaporated under reduced pressure through xylene soluble, filtering, filtrate at 350 DEG C, and 15.4kg Polycarbosilane, yield 50.1% are obtained.
By test, the softening point of Polycarbosilane is 126~148 DEG C, and IR analyzes to obtain ASi-H/ASi-CH3=0.94,1000
DEG C inert atmosphere cracking ceramic yield is 46.5%.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes are obvious for the those of ordinary skill in art field.Therefore, protection scope of the present invention is answered
This is subject to the protection scope in claims.
Claims (9)
1. a kind of high-volume high pressure synthesis method of Polycarbosilane, which is characterized in that it uses stainless steel autoclave for reactor,
Using silicon-containing material and catalyst as start material；
The catalyst is one of boracic, aluminium, titanium, zirconium, hafnium or a variety of organo-metallic compounds, the organometallic
Closing object includes but is not limited to boron alkyl, boron alkoxide, alkyl aluminum, aluminum alkoxide, alkyl titanium, alkoxytitanium, the cyclopentadienyl compounds of titanium, alkane
Base zirconium, zirconium alkoxide, the cyclopentadienyl compounds of zirconium, alkyl hafnium, alkoxy hafnium, hafnium compound；
Autoclave interior reaction temperature is 400-450 DEG C in synthesis process, pressure 4-10MPa, reaction time are 2~12 hours；
Autoclave volume is 50 liters -10000 liters.
2. the high-volume high pressure synthesis method of Polycarbosilane according to claim 1, which is characterized in that it includes following step
It is rapid:
(1) silicon-containing material and catalyst are placed in stainless steel autoclave, with high pure nitrogen displacement hot pressing gas reactor, sealing；
(2) by temperature in the kettle temperature programming to the reaction temperature, after the reaction time, Polycarbosilane is obtained after cooling and is slightly produced
Product；
(3) by Polycarbosilane crude product through xylene soluble, filtering, filtrate is evaporated under reduced pressure, up to Polycarbosilane after cooling.
3. the high-volume high pressure synthesis method of Polycarbosilane according to claim 2, which is characterized in that the catalyst accounts for
The ratio of silicon-containing material is 0.005%-10% by weight.
4. the high-volume high pressure synthesis method of Polycarbosilane according to claim 3, which is characterized in that the silicon-containing material
For the substance simultaneously containing Si element and alkyl, including but not limited to small molecule silane, polysilane, small molecule carbon silane.
5. the high-volume high pressure synthesis method of Polycarbosilane according to claim 4, which is characterized in that when silicon-containing material is
When small molecule silane or small molecule carbon silane, in the step (2) before by temperature in the kettle temperature programming to reaction temperature, also
Including first by temperature in the kettle temperature programming to predetermined temperature, heat preservation the predetermined time, cooling, deflation pressure release operation.
6. the high-volume high pressure synthesis method of Polycarbosilane according to claim 5, which is characterized in that the predetermined temperature
It is 350 DEG C, the predetermined time is 1~2 hour.
7. the high-volume high pressure synthesis method of Polycarbosilane according to claim 4, which is characterized in that the small molecule silicon
Alkane refers to linear and/or cricoid disilane, three silane containing alkyl, and one of tetrasilane or a variety of, molecular weight is no more than
300；The polysilane refer to containing alkyl using Si-Si bond as the polymer of main chain, molecular weight be greater than 3000；The small molecule
Carbon silane refers to that the compound containing Si-C key and/or Si-Si bond, molecular weight are no more than 1000.
8. the high yield synthetic method of Polycarbosilane according to claim 4, which is characterized in that when silicon-containing material is poly- silicon
When alkane, autoclave is added simultaneously with silicon-containing material and catalyst in the step (1) further includes solvent, and the solvent accounts for siliceous
The amount of raw material by weight 1~80%；Solvent includes but is not limited to n-hexane, toluene, dimethylbenzene, gasoline, one in diesel oil
Kind is a variety of.
9. the high yield synthetic method of Polycarbosilane according to claim 2, which is characterized in that subtracting in the step 3)
Press the temperature of distillation are as follows: 330~380 DEG C；Vacuum degree is 3-5kPa.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111019141A (en) * | 2019-12-10 | 2020-04-17 | 江苏赛菲新材料有限公司 | Novel method for synthesizing polycarbosilane |
| CN116284801A (en) * | 2023-02-14 | 2023-06-23 | 湖南远辉复合材料有限公司 | Synthesis method of polycarbosilane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111019141A (en) * | 2019-12-10 | 2020-04-17 | 江苏赛菲新材料有限公司 | Novel method for synthesizing polycarbosilane |
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| CN116284801A (en) * | 2023-02-14 | 2023-06-23 | 湖南远辉复合材料有限公司 | Synthesis method of polycarbosilane |
| CN116284801B (en) * | 2023-02-14 | 2023-10-20 | 湖南远辉复合材料有限公司 | Synthesis method of polycarbosilane |
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