CN104177621B - A kind of liquid Polycarbosilane and preparation method and application - Google Patents
A kind of liquid Polycarbosilane and preparation method and application Download PDFInfo
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- CN104177621B CN104177621B CN201410398757.0A CN201410398757A CN104177621B CN 104177621 B CN104177621 B CN 104177621B CN 201410398757 A CN201410398757 A CN 201410398757A CN 104177621 B CN104177621 B CN 104177621B
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Abstract
The invention discloses crosslinkable liquid Polycarbosilane of a kind of new low viscosity, high storage stability and preparation method and application.The Polycarbosilane is obtained with chloromethyl alkoxy silane or its mixture as raw material by grignard coupling reaction and reduction reaction, shown in its structure such as formula (1).Contain the unsaturated bond such as Si H keys and C=C in the structure simultaneously, self-crosslinkable solidification under certain condition, with higher ceramic yield, can impregnate the silicon carbide precursor of pyrolysis (PIP) technique as polymer precursor.The Polycarbosilane, structure composition is adjustable, and storage stability is good, and viscosity is low, and boiling point is relatively low, with as chemical vapor deposition/chemical vapor infiltration (CVD/CVI) application potential of silicon carbide ceramics presoma.Additionally, the Polycarbosilane can also substitute the divinylbenzene that commonly uses as the cross-linking agent of solid-state Polycarbosilane (PCS).
Description
Technical field
The present invention relates to a kind of new liquid Polycarbosilane and preparation method thereof, belongs to silicon carbide ceramics presoma and carbon silicon
The Material Fields such as alkane fire resistant resin.
Background technology
Carborundum (SiC) ceramic matric composite has high temperature resistant, low-density, high intensity, high-moduluss, anti-thermal shock and resistance to spoke
The excellent properties such as penetrate, be strategic thermal structure material of new generation, be widely used in Aero-Space, space technology, the energy, change
The fields such as work, traffic.Its main preparation methods have polymer precursor dipping pyrolysis (PIP), reactive melt infiltration (RMI),
The method such as chemical vapor infiltration (CVI) and CVI+PIP, CVI+RMI.In CVI techniques, the presoma for generally adopting is methyl
Trichlorosilane.It can discharge HCl gas attack equipment, and use substantial amounts of hydrogen as reproducibility in process of production
Gas and carrier gas, the safe and stable operation and maintenance to equipment propose that very high requirement, equipment investment and maintenance cost are high.
Later, researchers have developed the partially hydrogenated carbon silane of liquid as CVI/CVD SiC ceramic presomas, solve
Etching problem, improves sedimentation rate, but still suffers from free carbon too high levels or need to be passed through a large amount of hydrogen to reduce carbon content
Problem.
Polymer carbonization silicon precursor is the key raw material that PIP methods prepare SiC ceramic based composites, and current technology is most
The poly- carbon of the ripe and most popular solid-state obtained by the rearrangement of polydimethylsiloxane Pintsch process for being Yajima inventions
Silane (PCS).Initially, PCS is mainly used in melt spinning and prepares continuous SiC fiber, and softening point is higher, passes through PIP techniques by which
When preparing SiC ceramic based composites, it is necessary to add more organic solvent to be dissolved and can just use, so cause dipping effect
Rate is low, and ceramic product richness carbon is more；Although reducing softening point can reduce solvent load, its ceramic yield can be also made
Reduce, cannot still improve pickling efficiency.Although adding the crosslinking coagents such as divinylbenzene (DVB) improve when PCS solidifies
Pickling efficiency, but the free carbon too high levels of ceramic product, are unfavorable for the lifting of substrate performance；And DVB itself is easily
Autohemagglutination and affect use.Additionally, existing PCS needs high temperature or the condition of High Temperature High Pressure to prepare, synthetic yield or inefficient,
Preparation cost is higher, also have impact on its more massive commercial applications.
In order to improve pickling efficiency, researchers have developed liquid Si C ceramic forerunner, such as polymethyl silicane (PMS),
Modified polymethyl silicane (such as CN103214675A) and hyperbranched polycarbosilanes etc..In US2007/0093587A1, US2007/
In the liquid hyperbranched polycarbosilanes of the patent reports such as 0167599A1, CN102675649A, it is to realize high ceramic yield, its
Reaction raw materials are the Chloromethyltrichlorosilane of part methanolizing, contain substantial amounts of SiH in actual molecules structure3End group.High activity
SiH3Although being conducive to improving ceramic yield, during storage easily from polycondensation or with air in reaction of moisture and produce
Hydrogen, viscosity can also increase, and be unfavorable for the storage of safety and stability, while bubble is also easy to produce during forming and hardening.In presoma main chain
Other groups such as vinyl, pi-allyl isoreactivity group and methyl, phenyl are introduced in molecular structure can improve that these are not enough, but
The Residual carbon of ceramic product will be improved.Although reactions such as PCS prepared by the Yajima methods for comparing classics, vinyl, pi-allyls
Property group modified perhydro Polycarbosilane due to low viscosity and high ceramic yield, impregnate when PIP methods prepare SiC based composites
Efficiency is significantly improved, but foams how further to improve its storage stability, suppression solidification, and all for PIP processing
Later stage phase, pickling efficiency is remarkably decreased etc., and aspect was still highly desirable innovation due to the porosity of composite and diminishing for aperture
The technological approaches of property are solving.
The content of the invention
It is an object of the invention to overcome the shortcomings of in prior art, there is provided a kind of novel more low viscosity of structure and Geng Gao
Crosslinkable liquid Polycarbosilane of storage stability and preparation method and application.
The present invention provides following technical scheme：
A kind of crosslinkable liquid Polycarbosilane, shown in its structural formula such as formula (1)：
Wherein R is the reactive group containing C=C, C ≡ C or cyclopropyl etc. independently of one another；M is positive integer, and m >=
3；0.05≤n≤2；
The Polycarbosilane is circulus or line ring structure, in the line ring structure ratio of ring body structurc account for 20% with
On.
In the present invention, the Polycarbosilane is preferably six-membered cyclic structure.
In the present invention, the R is R independently of one another1-(CR2 2)x-, wherein R1It is CR3 2=CR3-、R3C ≡ C- or (CH2)2CH-, R2And R3It is H or C1-C4 alkyl independently of one another (such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl or isobutyl group
Deng), x is 0,1,2 or 3.Preferably, the R is CH independently of one another2=CH-, CH2=CHCH2-, CH2=C (CH3)-, CH3CH
=CH-, HC ≡ C-, HC ≡ C-CH2- or (CH2)2CH-.Preferably CH2=CH-.
In the present invention, SiH3/SiH2Si-H integrations than much smaller than 1.35, preferably less than 0.9, even more preferably less than
0.7, still more preferably less than 0.5.
This new crosslinkable liquid Polycarbosilane is with single chloromethyl trialkoxy silane or chloromethyl three
Alkoxy silane is raw material with the mixture of chloromethyl dimethoxy chlorosilane, one methoxyl group dichlorosilane of chloromethyl, by lattice
Family name is coupled and reduction reaction is obtained, its molecule be circulus or line ring structure (wherein, the ratio of ring body structurc account for 20% with
On), preferably six-membered cyclic structure.The Polycarbosilane of this ring-type, molecular structure are symmetrical and stable, with good processing
The introducing of the unsaturated bond such as performance, especially Si -- H bond and C=C so as in the presence of platinum catalyst or peroxide, can
To be solidified under the conditions of relatively mild.
The present invention also provides following technical scheme：
The preparation method of above-mentioned crosslinkable liquid Polycarbosilane, which comprises the steps：
(1) magnesium chips or magnesium powder are added in dry ether solvent, thereto a small amount of chloromethyl tri-alkoxy silicon of Deca
Alkane or chloromethyl trialkoxy silane and chloromethyl dimethoxy chlorosilane, the mixture of one methoxyl group dichlorosilane of chloromethyl and
Ether solvent, after reaction causes, Deca chloromethyl trialkoxy silane or chloromethyl trialkoxy silane and chloromethyl under stirring
The mixed solution of dimethoxy chlorosilane, the mixture of one methoxyl group dichlorosilane of chloromethyl and ether solvent, 0～80 DEG C of reaction
1～12h；
(2) stir Grignard reagent of the lower Deca containing reactive group or can with magnesium be formed in situ Grignard reagent containing reactivity
The halogenated hydrocarbons or chloromethyl silane compound of group, 0～80 DEG C of 1～36h of reaction；
(3) lower addition reducing agent, 0～80 DEG C of 1～36h of reaction are stirred；
(4) it is sufficiently stirred for down, adds deionized water, concentrated hydrochloric acid and low boiling alkane, -20～30 DEG C of 0.5～5h of reaction is quiet
.5～5h is set to 0, upper organic phase drying after split-phase, is isolated, distillation obtains product.
In the preparation method of above-mentioned crosslinkable liquid Polycarbosilane, ether solvent is selected from ether, tetrahydrofuran, 2- first
Base tetrahydrofuran, glycol dimethyl ether, butyl cellosolve, diethylene glycol dimethyl ether, dibutyl ethylene glycol ether, methyl tertbutyl
One kind or its two or more mixture in ether, tert amyl methyl ether(TAME), cyclopentyl methyl ether etc., preferably tetrahydrofuran, 2- first
Base tetrahydrofuran, methyl tertiary butyl ether(MTBE) or tert amyl methyl ether(TAME).Low boiling alkane is selected from pentane, Pentamethylene., hexane and petroleum ether
One kind or its two or more mixture, preferably hexane and Pentamethylene. in (30-60 DEG C) etc..And when using methyl tertbutyl
When ether and cyclopentyl methyl ether, as their own can be with water split-phase well, therefore can be without separately adding when being acidified post processing
Low boiling alkane solvent, so as to be very beneficial for the recycling of solvent.
In the preparation method of above-mentioned crosslinkable liquid Polycarbosilane, the alkoxyl in chloromethyl trialkoxy silane is
C1-C4 alkoxyls, such as methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy etc..It is excellent
Selection of land, the chloromethyl trialkoxy silane are chloromethyl trimethoxy silane, chloromethyl triethoxysilane or chloromethyl
Three isopropoxy silane, more preferably chloromethyl triethoxysilane.
In the preparation method of above-mentioned crosslinkable liquid Polycarbosilane, chloromethyl tri-alkoxy silicon in described mixture
The molar content of alkane is more than 30%.
In the preparation method of above-mentioned crosslinkable liquid Polycarbosilane, chloromethyl trialkoxy silane monomer and ethers are molten
The volume ratio of agent is 1:1～1:5.
In the preparation method of above-mentioned crosslinkable liquid Polycarbosilane, the Grignard reagent containing reactive group is containing second
The unsaturated alkyl magnesium halide of alkenyl or alkynyl, selected from it is following any one：CH2=CH-MgBr, CH2=CH-MgCl, CH2
=CHCH2- MgBr, CH2=C (CH3)-MgBr, CH3CH=CH-MgBr, CH2=CHCH2- MgCl, CH3CH=CH-MgCl, HC
≡ C-MgBr, HC ≡ C-CH2MgBr, preferably CH2=CH-MgBr；Halogenated hydrocarbons containing reactive group include：CH2=
CHCH2Cl, CH2=CHBr, HC ≡ C-CH2Br, (CH2)2CHBr；Chloromethyl silane compound includes：ClCH2SiMeH2,
ClCH2SiH2(CH=CH2)。
In the preparation method of above-mentioned crosslinkable liquid Polycarbosilane, reducing agent is lithium aluminium hydride reduction, lithium hydride, hydrogenation
Magnesium, sodium hydride or calcium hydride, preferably lithium aluminium hydride reduction.
In the preparation method of above-mentioned crosslinkable liquid Polycarbosilane, deionized water, concentrated hydrochloric acid and low boiling alkane
Volume ratio is 2:1:0.5～11:1:5.
The present invention also provides following technical scheme：
A kind of method that SiC ceramic is prepared by above-mentioned crosslinkable liquid Polycarbosilane, wherein, above-mentioned cross-linking
Liquid Polycarbosilane structure in, Si-H and C=C, C ≡ C etc. unsaturation alkane group deposit in platinum catalyst or peroxide
Cross-linked structure is formed in lower generation Si―H addition reaction or Raolical polymerizable, so as to obtain the SiC ceramic of higher ceramic yield.
In the present invention, the platinum catalyst is chloroplatinic acid or Karstedt ' s catalyst, and consumption is Polycarbosilane quality
10-50ppm；Described peroxide is cumyl peroxide (DCP), and consumption is the 0.1-0.5wt% of Polycarbosilane quality.
The present invention also provides following technical scheme：
The preparation method of the ceramic sample of above-mentioned crosslinkable liquid Polycarbosilane, which comprises the steps：
Cured is carried out to the product that distillation in (4) the step of above-mentioned preparation method is obtained, cured product is again through height
Temperature sintering obtains ceramic sample.
In the present invention, the cured is carried out in inert atmosphere (nitrogen or argon).Typically program curing is：80
～150 DEG C of insulation 2h, 150～280 DEG C of insulation 4h.
In the present invention, the high temperature sintering be cured product under nitrogen or argon gas atmosphere, 800～1600 DEG C insulation 0.5-
10h obtains ceramic sample.
Above-mentioned crosslinkable liquid Polycarbosilane, can be used as the cross-linking agent of business Yajima method solid-state PCS, and its consumption is
5～the 50wt% of PCS, preferably 10～30wt%.Additionally, this Polycarbosilane can also prepare carbon fiber as PIP techniques
Or the presoma matrix resin of the enhanced SiC based composites of silicon carbide fibre.Further, this Polycarbosilane (molecular weight control
When relatively low) can also be used as CVD/CVI silicon carbide ceramics presomas.
It is an advantage of the current invention that：First, the key raw material used in the present invention is chloromethyl trialkoxy silane,
Corrosion-free to equipment, good stability is easy to storage, cheap and easy to get；Second, Polycarbosilane prepared by the present invention, ceramic yield are high,
Can be used as PIP high-performance silicon carbide ceramic forerunners；3rd, by feed change species and ratio, the present invention can also
Low-molecular-weight polycarbosilane is prepared, boiling point is relatively low, pyrolysis product environmentally safe can be made pottery with carborundum as CVD/CVI
Porcelain presoma；4th, Polycarbosilane prepared by the present invention, molecular weight is relatively low and contains circulus, with lower viscosity, especially
There is advantage in terms of the pickling efficiency for improving PIP later stages process-cycle, the porosity of the final composite of reduction and aperture, from
And improve the mechanical property and antioxygenic property of composite.5th, preferred, reduction of the present invention to reaction raw materials and condition
SiH in molecular structure3/SiH2Relative scale, improve storage stability.And unsaturated group Grignard reagent is adopted to ring
Shape compound is blocked, and on the one hand can further reduce SiH3Content, while ceramic yield can be improved and suppress solidification foaming
Phenomenon.Additionally, the low viscosity of the Polycarbosilane of the present invention and containing unsaturated active group so as to fit making as PCS cross-linking agent
With can be obviously improved the cure process of PCS, while improving its ceramic yield, not increase substantially its ceramic product
Free carbon content.
Description of the drawings
Thermal weight loss (TG) curves of the Fig. 1 for 1 product of embodiment；
Fig. 2 is 2 product of embodiment and suction heat release (DSC) curve for adding platinum catalyst；
Thermal weight loss (TG) curves of the Fig. 3 for 2 cured product of embodiment；
Thermal weight loss (TG) curves of the Fig. 4 for 5 cured product of PCS and embodiment；
Patterns of the Fig. 5 for 1000 DEG C of cracking ceramic samples of 5 solidified sample of embodiment, wherein after (a) is for PCS self-curings
Ceramic sample exterior appearance, (b) be ceramic sample after PCS and 5 product crosslinking curing of embodiment exterior appearance；
Fig. 6 is with ClCH2Si(OMe)1.75Cl1.25Highly -branched perhydro Polycarbosilane (HPCS) prepared for raw material and ethylene
Modified perhydro Polycarbosilane (VHPCS) of base1H-NMR；
Fig. 7 is with ClCH2Si(OEt)3The HPCS prepared for raw material and VHPCS1H-NMR。
Specific embodiment
With reference to embodiments the present invention is described further.It should be noted that following embodiments cannot function as it is right
The restriction of the scope of the present invention, any spirit improved all without prejudice to the present invention made on the basis of the present invention.
Comparative example
One dry 1L three neck round bottom flask, connects mechanical agitator, reflux condensing tube, constant pressure funnel and inducing QI
Device, then evacuation displacement nitrogen three times, while heat gun baking is except the steam of attachment removal.In a nitrogen atmosphere, to reaction
5.0g magnesium chips is added in bottle, 4mL tetrahydrofurans is added, is heated to 40 DEG C.Add 2.44g's in constant pressure funnel
ClCH2Si(OMe)1.75Cl1.25(i.e. ClCH2Si(OMe)2Cl:ClCH2Si(OMe)Cl2Mol ratio is 3：1 mixture) and 2mL
The mixed solution of tetrahydrofuran, is slowly dropped in reaction bulb to cause grignard reaction.49.0g is added in constant pressure funnel
ClCH2Si(OMe)1.75Cl1.25With the mixed solution of 150mL tetrahydrofurans, above reaction is added drop-wise to appropriate speed under stirring
In system, then insulation reaction 9h at 60 DEG C.Then the first of 60.32g vinyl magnesium bromides is added by constant pressure funnel
Base tetrahydrofuran solution, 50 DEG C of insulation reaction 3h.After reaction terminates, 7.45g lithium aluminium hydride reductions are added, continue 6h to be reacted at 50 DEG C.
368mL deionized waters, 130mL concentrated hydrochloric acid and 150mL hexanes are added, 0.5～2h is reacted at 0～5 DEG C, is stood and is divided
Layer, water are mutually extracted with 150mL hexanes, are merged organic faciess, and are washed with the dilute hydrochloric acid of the 1.2mol/L of 260mL three times, and separation has
Machine phase, adds 15g anhydrous magnesium sulfates to be dried, and filters revolving and obtains final product, is yellow liquid Polycarbosilane, and yield is
75%, ceramic yield is 75%.The product is-CH=CH corresponding to the R in formula (1)2, n=0.32, its molecular weight Mw=1683,
Mn=720.Product sealed storage 3 months at room temperature, viscosity increase to 100cP from 40cP.Fig. 6 is with ClCH2Si
(OMe)1.75Cl1.25Highly -branched perhydro Polycarbosilane (HPCS) prepared for raw material and vinyl modified perhydro Polycarbosilane
(VHPCS)1H-NMR, wherein 4.10ppm are the SiH in 6 yuan of rings2, SiHs of the 3.90ppm for linear structure2, and 3.61ppm is
SiH3.Should1H-NMR is composed and is shown, its SiH2(ring)/SiH2(line)/SiH3Si-H integrations than for 0.38/1.0/1.86, with linear
Based on structure, containing more SiH3。
Embodiment 1
One dry 1L three neck round bottom flask, connects mechanical agitator, reflux condensing tube, constant pressure funnel and inducing QI
Device, then evacuation displacement nitrogen three times, while heat gun baking is except the steam of attachment removal.In a nitrogen atmosphere, to reaction
5.0g magnesium chips is added in bottle, 4mL tetrahydrofurans is added, is heated to 30 DEG C.2.97g chloromethyls are added in constant pressure funnel
The mixed solution of triethoxysilane and 2mL tetrahydrofurans, is slowly dropped in reaction bulb to cause grignard reaction.Drip to constant pressure
The mixed solution of 59.17g chloromethyls triethoxysilane and 150mL tetrahydrofurans is added in liquid funnel, with appropriate under stirring
Speed is added drop-wise in above reaction system, insulation reaction 4h at 30 DEG C.Then 69.0g ethylene is added by constant pressure funnel
The methyltetrahydrofuran solution of base magnesium bromide (1.6mol/L), 30 DEG C of insulation reaction 6h.After reaction terminates, 7.45g hydrogenations are added
Aluminum lithium, continues to react 10h at 30 DEG C.
368mL deionized waters, 130mL concentrated hydrochloric acid and 150mL hexanes are added, 0.5～2h is reacted at 0～5 DEG C, is stood and is divided
Layer, water are mutually extracted with 150mL hexanes, are merged organic faciess, and are washed with the dilute hydrochloric acid of 260mL, 1.7mol/L three times, are separated organic
Phase, adds 15.0g anhydrous magnesium sulfates to be dried, and filters revolving and obtains final product, is light yellow liquid Polycarbosilane, and yield is
73%, the product is-CH=CH corresponding to the R in formula (1)2, n=0.32, its molecular weight Mw=1162, Mn=584.The product
Sealed storage 5 months at room temperature, viscosity have almost no change, about 41cP.Under nitrogen atmosphere, the Polycarbosilane is 1000
DEG C TGA ceramic yields be 30.7%；And solidify in 120～220 DEG C of catalytic crosslinkings through Karstedt catalyst (40ppm)
Afterwards, the TGA ceramic yields (1000 DEG C) of its cured product are 87.0%.
Embodiment 2
One dry 1L three neck round bottom flask, connects mechanical agitator, reflux condensing tube, constant pressure funnel and inducing QI
Device, then evacuation displacement nitrogen three times, while heat gun baking is except the steam of attachment removal.In a nitrogen atmosphere, to reaction
19.2g magnesium chips is added in bottle, the 2- methyltetrahydrofurans of 30mL is added, is heated to 50 DEG C.Add in constant pressure funnel
The mixed solution of 1.20g chloromethyls trimethoxy silane and 2- methyltetrahydrofurans (2mL), is slowly dropped in reaction bulb to draw
Send out grignard reaction.The 2- methyl of 67.1g chloromethyl trimethoxy silanes (0.4mol) and 170mL is added in constant pressure funnel
Tetrahydrofuran mixed solution, is added drop-wise in above reaction system with appropriate speed under stirring, insulation reaction 6h at 50 DEG C.So
40g allyl bromide, bromoallylenes (0.33mol), 50 DEG C of insulation reaction 5h are slowly added to by constant pressure funnel afterwards.After reaction terminates, add
5.45g lithium aluminium hydride reductions, continue to react 13h at 50 DEG C.
240mL deionized waters, 60mL concentrated hydrochloric acid and 60mL hexanes are added, 0.5～2h is reacted at 0～5 DEG C, is stood and is divided
Layer, separates organic faciess；Water is mutually extracted with 100mL hexanes, is merged organic faciess twice, and is washed with the dilute hydrochloric acid 120mL of 1.2mol/L
Wash three times, separate organic faciess, add 20.0g anhydrous magnesium sulfates to be dried, filter revolving and obtain final product, be the poly- carbon of yellow liquid
Silane, yield are 94%, and the product is-CH corresponding to the R in formula (1)2- CH=CH2, n=0.75, its molecular weight Mw=686,
Mn=410.Product sealed storage 5 months at room temperature, viscosity have almost no change, about 7cP.The Polycarbosilane is consolidated
Change sample is crocus solid, and under nitrogen atmosphere, 1200 DEG C of ceramic yield is 77.6%.
Embodiment 3
One dry 500mL three neck round bottom flask, connect mechanical agitator, reflux condensing tube, constant pressure funnel and
Gas operated device, then evacuation displacement nitrogen three times, while heat gun baking is except the steam of attachment removal.In a nitrogen atmosphere, to
12.9g magnesium chips is rapidly joined in reaction bulb, 15mL glycol dimethyl ethers and 1-2 grain iodine crystal is added, 70 DEG C are heated five minutes.
The mixing of 100g chloromethyl triethoxysilanes (0.47mol) and 200mL glycol dimethyl ethers is added in constant pressure funnel
Solution, is first slowly added dropwise 1-3% in reaction bulb to cause grignard reaction.It is determined that after causing, stirring, and by mixed liquor with suitable
When speed be added drop-wise in above reaction system, insulation reaction 8h at 70 DEG C.Then 250mL is added by constant pressure funnel
Vinylimidazolium chloride magnesium (2.0mol/L) tetrahydrofuran solution, 70 DEG C reaction 5h, be subsequently adding 5.45g lithium aluminium hydride reductions, 50
DEG C lower reaction 8h of stirring.
Under stirring, above-mentioned reaction solution is slowly added into by 180mL deionized waters, 80mL concentrated hydrochloric acid and 150mL hexanes
In the beaker that (is cooled to less than -5 DEG C in advance) in the mixed liquor of composition, then proceed to 0.5～1h is reacted at 0～5 DEG C.It is transferred to point
Stratification in liquid funnel, separates organic faciess；Water is mutually extracted with 90mL hexanes, merges organic faciess twice, and with dilute salt of 80mL
Sour (1.2mol/L) washing three times, separates organic faciess, adds 16.0g anhydrous magnesium sulfates to be dried, and filters, rotates and finally produced
Thing, is brown color liquid Polycarbosilane, and yield is 86%, and the product is-CH=CH corresponding to the R in formula (1)2, n=0.97,
Its molecular weight Mw=2393, Mn=806.Product sealed storage 6 months at room temperature, viscosity have almost no change, about
191cP, gel time was more than 2 years.The solidified sample of the Polycarbosilane is brown solid, under nitrogen atmosphere, 1300 DEG C of ceramics
Yield is 75.7%.
Embodiment 4
One dry 1L three neck round bottom flask, connects mechanical agitator, reflux condensing tube, constant pressure funnel and inducing QI
Device, then evacuation displacement nitrogen three times, while heat gun baking is except the steam of attachment removal.In a nitrogen atmosphere, to reaction
19g magnesium chips is rapidly joined in bottle, 25mL diethylene glycol dimethyl ethers is added, is heated to 40 DEG C.Add in constant pressure funnel
Three isopropoxy silane (0.5mol) of 127.4g chloromethyls, 4.5g allyl chlorides (0.06mol) and 200mL diethylene glycol dimethyl ethers
Mixed solution, be first slowly added dropwise the 1-3% of total amount in reaction bulb to cause grignard reaction.Then with appropriate speed under stirring
Degree is added drop-wise in above reaction system, insulation reaction 8h at 80 DEG C.Then cool at 50 DEG C, by constant pressure funnel elder generation
After adding one methoxyl group dichlorosilane (0.125mol) reaction 5h of 45g chloromethyls, the corundum pottery of 10g lithium hydrides and 1～3mm is added
Porcelain bead, in 60 DEG C of reduction reactions 12h under quick stirring.
300mL deionized waters, 120mL concentrated hydrochloric acid and 120mL hexanes are added, 0.5～2h is reacted at 0～5 DEG C, is stood and is divided
Layer, water are mutually extracted with 120mL hexanes, are merged organic faciess, and are washed three times with the dilute hydrochloric acid (1.5mol/L) of 100mL, and separation has
Machine phase, adds 20.0g anhydrous magnesium sulfates to be dried, and filters revolving and obtains final product, is yellow liquid Polycarbosilane, and yield is
85%, the product is-CH corresponding to the R in formula (1)2- CH=CH2, n=0.1, its molecular weight Mw=769, Mn=484.The product
Thing sealed storage 6 months at room temperature, viscosity have almost no change, about 11cP.The Polycarbosilane is solidified with the PCS of solid-state
It is white solid afterwards, under nitrogen atmosphere, 1000 DEG C of ceramic yield is 76.8%.
Embodiment 5
One dry 1L three neck round bottom flask, connects mechanical agitator, reflux condensing tube, constant pressure funnel and inducing QI
Device, then evacuation displacement nitrogen three times, while heat gun baking is except the steam of attachment removal.In a nitrogen atmosphere, to reaction
11.0g magnesium chips is rapidly joined in bottle, 20mL methyltetrahydrofurans is added, is heated to 78 DEG C.Add in constant pressure funnel
The mixed solution of 85g chloromethyl triethoxysilanes (0.4mol) and 150mL methyltetrahydrofurans, is first slowly added dropwise about 1-3%
To in reaction bulb causing grignard reaction.Under stirring, appropriate speed Deca, insulation reaction 12h at 80 DEG C are kept.Then lead to
Cross the methyltetrahydrofuran solution (1.6mol/L) that constant pressure funnel adds 180mL vinyl magnesium bromides, 65 DEG C of insulation reaction
4h.After reaction terminates, 5.85g lithium aluminium hydride reductions are added, continue 12h to be reacted at 60 DEG C.
250mL deionized waters, 100mL concentrated hydrochloric acid are added, 0.5～2h is reacted at 0～5 DEG C, stratification is separated organic
Phase；Water is mutually extracted with 120mL hexanes, is merged organic faciess, and is washed three times with the dilute hydrochloric acid (1.5mol/L) of 120mL, and separation has
Machine phase, adds 36.0g anhydrous magnesium sulfates to be dried, and filters revolving and obtains final product, is brown color liquid Polycarbosilane, and yield is
79%, the product is-CH=CH corresponding to the R in formula (1)2, n=0.66, its molecular weight Mw=1385, Mn=541.The product
Sealed storage 5 months at room temperature, viscosity have almost no change, about 87cP.The ceramic yield of solid-state PCS is 58%, nitrogen
Self-curing temperature in gas easily foams more than 450 DEG C；And after the Polycarbosilane of addition 20w% is as cross-linking agent, the PCS
Can solidify at 180-230 DEG C of nitrogen, its ceramic yield brings up to 80.7%, and its exterior appearance is as shown in Figure 5.
Embodiment 6
One dry 1L three neck round bottom flask, connects mechanical agitator, reflux condensing tube, constant pressure funnel and inducing QI
Device, then evacuation displacement nitrogen three times, while heat gun baking is except the steam of attachment removal.In a nitrogen atmosphere, to reaction
15.0g magnesium chips is rapidly joined in bottle, the 2- methyltetrahydrofurans of 20mL is added, is heated to 40 DEG C, and add 0.5ml dibromo second
Alkane activates magnesium chips.85g chloromethyl triethoxysilanes (0.4mol) and 170mL tetrahydrofurans are added in constant pressure funnel
Mixed solution, the 1-3% of first Deca total amount is in reaction bulb causing grignard reaction.Then with appropriate speed Deca under stirring
To in above reaction system, insulation reaction 6h at 40 DEG C.Then 17.0g Cyclopropyl Bromides are added by constant pressure funnel
(0.14mol), 40 DEG C of insulation reaction 9h.After reaction terminates, 7.63g lithium aluminium hydride reductions are added, continue 11h to be reacted at 40 DEG C.
300mL deionized waters, 100mL concentrated hydrochloric acid and 100mL hexanes are added, 0.5～2h is reacted at 0～5 DEG C, is stood and is divided
Layer, water are mutually extracted with 100mL hexanes, are merged organic faciess, and are washed three times with the dilute hydrochloric acid (1.5mol/L) of 90mL, are separated organic
Phase, adds 15.0g anhydrous magnesium sulfates to be dried, and filters revolving and obtains final product, is brown color liquid Polycarbosilane, and yield is
75%, the product is-CH (CH corresponding to the R in formula (1)2)2, n=0.31, its molecular weight Mw=1052, Mn=524.The product
Sealed storage 5 months at room temperature, viscosity have almost no change, about 36cP.The poly- carbon of 5w% is added in solid-state PCS
After silane is as cross-linking agent, PCS can solidify at 180-230 DEG C of nitrogen, and its ceramic yield brings up to 66.7%.
Embodiment 7
One dry 1L three neck round bottom flask, connects mechanical agitator, reflux condensing tube, constant pressure funnel and inducing QI
Device, then evacuation displacement nitrogen three times, while heat gun baking is except the steam of attachment removal.In a nitrogen atmosphere, to reaction
28.0g magnesium chips is rapidly joined in bottle, after vacuum stirring heat-activated 2h, 50 DEG C is cooled to, is added 40mL cyclopentyl methyl ethers.To
The mixed solution of 85.3g chloromethyl trimethoxy silanes (0.5mol) and 220mL cyclopentyl methyl ethers is added in constant pressure funnel,
First the 1-3% of total amount is added drop-wise in reaction bulb to cause grignard reaction, the above is added drop-wise to appropriate speed under then stirring
In reaction system, insulation reaction 2h at 55 DEG C.Then by constant pressure funnel add 42g allyl chlorides (0.55mol) and
40ml cyclopentyl methyl ether mixed solutions, 55 DEG C of insulation reaction 8h, are subsequently adding 4.74g lithium aluminium hydride reductions, in 55 DEG C of reduction reactions
12h。
240mL deionized waters, 80mL concentrated hydrochloric acid are added, 0.5～2h is reacted at 0～5 DEG C, stratification, water are mutually used
100mL cyclopentyl methyl ethers are extracted, and are merged organic faciess, and are washed three times with the dilute hydrochloric acid (1.2mol/L) of 130mL, are separated organic
Phase, adds 25g anhydrous magnesium sulfates to be dried, and filters revolving and obtains final product, is brown color liquid Polycarbosilane, and yield is
86%, the product is-CH corresponding to the R in formula (1)2- CH=CH2, n=0.94, its molecular weight Mw=824, Mn=421.The product
Thing sealed storage 5 months at room temperature, viscosity have almost no change, about 6cP.To in solid-state PCS add 15w% this gather
After carbon silane is as cross-linking agent, PCS can solidify at 180-230 DEG C of nitrogen, and its ceramic yield brings up to 70.5%.
Embodiment 8
One dry 1L three neck round bottom flask, connects mechanical agitator, reflux condensing tube, constant pressure funnel and inducing QI
Device, then evacuation displacement nitrogen three times, while heat gun baking is except the steam of attachment removal.In a nitrogen atmosphere, to reaction
5.08g magnesium chips is added in bottle, 5mL tetrahydrofurans is added, is heated to 30 DEG C.1.78g chloromethanes are added in constant pressure funnel
The mixed solution of ethyl triethoxy silicane alkane, one methoxyl group dichlorosilane of 1.18g chloromethyls and 3mL tetrahydrofurans, is slowly dropped to
Causing grignard reaction in reaction bulb.35.50g chloromethyl triethoxysilanes, 23.47g chlorine are added in constant pressure funnel
The mixed solution of one methoxyl group dichlorosilane of methyl and 160mL tetrahydrofurans, is added drop-wise to the above with appropriate speed under stirring anti-
In answering system, insulation reaction 3h at 30 DEG C.Then the methyl of 10.47g vinyl magnesium bromides is added by constant pressure funnel
Tetrahydrofuran solution, 30 DEG C of insulation reaction 3h.After reaction terminates, 5.83g lithium aluminium hydride reductions are added, continue 4h to be reacted at 30 DEG C.
218mL deionized waters, 64mL concentrated hydrochloric acid and 90mL hexanes are added, 0.5～2h is reacted at 0～5 DEG C, is stood and is divided
Layer, water are mutually extracted with 90mL hexanes, are merged organic faciess, and are washed with the dilute hydrochloric acid of the 1.2mol/L of 170mL three times, are separated organic
Phase, adds 9.0g anhydrous magnesium sulfates to be dried, and filters revolving and obtains final product, is light yellow liquid Polycarbosilane, and yield is
80%, the product is-CH=CH corresponding to the R in formula (1)2, n=0.05, its molecular weight Mw=462, Mn=384.The product exists
Sealed storage 5 months under room temperature, viscosity have almost no change.Under nitrogen atmosphere, the Polycarbosilane is in 1000 DEG C of ceramic yield
For 28%.
Embodiment 9
One dry 1L three neck round bottom flask, connects mechanical agitator, reflux condensing tube, constant pressure funnel and inducing QI
Device, then evacuation displacement nitrogen three times, while heat gun baking is except the steam of attachment removal.In a nitrogen atmosphere, to reaction
16.77g magnesium chips is rapidly joined in bottle, 20mL methyl tertiary butyl ether(MTBE)s and 0.5ml Bromofumes, 5 points of kinds of micro- backflow are added.Xiang Heng
In pressure Dropping funnel, the mixing of three isopropoxy silane (0.5mol) of addition 127.5g chloromethyls and 300mL methyl tertiary butyl ether(MTBE)s is molten
Liquid, is first slowly added dropwise the 1～3% of total amount in reaction bulb to cause grignard reaction.Then with appropriate speed Deca under stirring
To in above reaction system, insulation reaction 5h at 55 DEG C, then 18g chloromethyl vinyl base dichloros are added by constant pressure funnel
Silane, 55 DEG C are continued reaction 5h.After reaction terminates, 0.2g anhydrous zinc chlorides, 27g sodium hydrides and a diameter of 1-3mm are added
300g aluminium oxidies grind pearl, continue to react 24h at 55 DEG C, are cooled to room temperature.
In the dilute hydrochloric acid of the 3mol/L that above-mentioned addition solution is added to 350mL, 0.5～2h is reacted at 0～5 DEG C, it is quiet
Layering is put, water is mutually extracted with 150mL methyl tertiary butyl ether(MTBE)s, is merged organic faciess, and is washed with the dilute hydrochloric acid (1.2mol/L) of 150mL
Three times, organic faciess are separated, add 25.0g anhydrous magnesium sulfates to be dried, filtered revolving and obtain final product, be the poly- carbon of brown color liquid
Silane, yield are 83%, and the product is-CH=CH corresponding to the R in formula (1)2, n=0.17, its molecular weight Mw=763, Mn=
469.Product sealed storage 5 months at room temperature, viscosity have almost no change, about 14cP.10w% is added in PCS
The Polycarbosilane as cross-linking agent after, PCS can solidify at 180-230 DEG C of nitrogen, and its ceramic yield brings up to 66.2%.
Embodiment 10
One dry 1L three neck round bottom flask, connects mechanical agitator, reflux condensing tube, constant pressure funnel and inducing QI
Device, then evacuation displacement nitrogen three times, while heat gun baking is except the steam of attachment removal.In a nitrogen atmosphere, to reaction
16.0g magnesium chips is added in bottle, the 2- methyltetrahydrofurans of 20mL is added, is heated to 45 DEG C.Add in constant pressure funnel
63.8g chloromethyl triethoxysilanes (0.3mol), 35.0g chloromethyls dimethoxy chlorosilane (0.2mol), 18.0g chloromethyls
The mixed solution of one methoxyl group dichlorosilane (0.1mol) and 240mL methyltetrahydrofurans, the 1～4% of first Deca total amount arrives anti-
Answer in bottle to cause grignard reaction, be added drop-wise in above reaction system with appropriate speed under then stirring, be incubated at 45 DEG C
Reaction 8h.Then the methyltetrahydrofuran solution of 70mL vinyl magnesium bromides (1.6mol/L) is added by constant pressure funnel,
45 DEG C of insulation reaction 6h.After reaction terminates, 11.4g lithium aluminium hydride reductions are added, continue 12h to be reacted at 45 DEG C.
300mL deionized waters, 110mL concentrated hydrochloric acid and 60mL hexanes are added, 0.5～2h is reacted at 0～5 DEG C, is stood and is divided
Layer, water are mutually extracted with 60mL hexanes again, are merged organic faciess twice, and are washed with the dilute hydrochloric acid of the 1.2mol/L of 120mL three times,
Organic faciess are separated, adds 20.0 g anhydrous magnesium sulfates to be dried, filtered revolving and obtain final product, be the poly- carbon silicon of light yellow liquid
Alkane, yield are 77%, and the product is-CH=CH corresponding to the R in formula (1)2, n=0.15, its molecular weight Mw=5387, Mn=
1412.Product sealed storage 5 months at room temperature, viscosity have almost no change, about 120cP.Under nitrogen atmosphere, this gathers
Carbon silane is 78% in 1000 DEG C of ceramic yield.
Embodiment 11
One dry 1L three neck round bottom flask, connects mechanical agitator, reflux condensing tube, constant pressure funnel and inducing QI
Device, then evacuation displacement nitrogen three times, while heat gun baking is except the steam of attachment removal.In a nitrogen atmosphere, to reaction
15.6g magnesium chips is added in bottle, the tert amyl methyl ether(TAME) and 1mL Bromofumes of 20mL is added.Add in constant pressure funnel
The mixed solution of 106.4g chloromethyls triethoxysilane and 200mL tert amyl methyl ether(TAME)s, the 1～4% of first Deca total amount arrives anti-
Answer in bottle to cause grignard reaction, be added drop-wise in above reaction system with appropriate speed under then stirring, be incubated at 65 DEG C
Reaction 6h.5.4g chloromethyl vinyl base silane (ClCH are added by constant pressure funnel again2SiViH2) and 10mL methyl tert-amyls
The mixed liquor of ether, 65 DEG C of insulation reaction 4h.After reaction terminates, 9.8g lithium aluminium hydride reductions are added, continue 6h to be reacted at 55 DEG C.
300mL deionized waters, 100mL concentrated hydrochloric acid are added, 0.5～2h is reacted at 0～5 DEG C, stratification is separated organic
Phase；Water is mutually extracted with 120mL tert amyl methyl ether(TAME)s again, merges organic faciess twice, and the dilute hydrochloric acid with the 1.2mol/L of 120mL is washed
Wash three times, separate organic faciess, add 20.0g anhydrous magnesium sulfates to be dried, filter revolving and obtain final product, be that light yellow liquid is gathered
Carbon silane, yield are 77%, and the product is-CH=CH corresponding to the R in formula (1)2, n=0.1, its molecular weight Mw=4860, Mn
=1412.Product sealed storage 5 months at room temperature, viscosity have almost no change, about 120cP.Under nitrogen atmosphere, should
Polycarbosilane is 72% in 1000 DEG C of ceramic yield.
In the liquid Polycarbosilane of embodiments of the invention 1-11, it is and the SiH based on circulus3Content
It is relatively low, its SiH2(ring)/SiH2(line)/SiH3Si-H integrations than for (3.5～1.0)/1.0/ (1.2～1.84).It is concrete such as to scheme
Embodiment 3 shown in 71H-NMR is composed, wherein upper figure is reaction condition same as Example 3 but does not add the pure of vinyl modified
Polycarbosilane spectrogram, its SiH/SiH2(ring)/SiH2(line)/SiH3Si-H integrations than for 0.29/2.7/1.0/1.72, its point
In son based on ring structure；Figure below is the Polycarbosilane containing vinyl described in embodiment 3, its SiH/SiH2(ring)/SiH2(line)/
SiH3Integration compare for 1.62/3.43/1.0/1.19, as the introducing of vinyl not only increases crosslinking active group, and
As end-blocking is acted on, its SiH3Content is further reduced, and is conducive to improving its storage stability.
Claims (32)
1. a kind of crosslinkable liquid Polycarbosilane, shown in its structural formula such as formula (1)：
Wherein R is the reactive group containing C=C, C ≡ C or cyclopropyl independently of one another；M is positive integer, and m>3；0.05≤
n≤2；
The Polycarbosilane is circulus or line ring structure, and in the line ring structure, the ratio of ring body structurc accounts for more than 20%；
In the liquid Polycarbosilane, SiH3/SiH2Si-H integration than less than 0.9 and be more than 0.
2. crosslinkable liquid Polycarbosilane according to claim 1, it is characterised in that the R is R independently of one another1-
(CR2 2)x-, wherein R1It is CR3 2=CR3-、R3C ≡ C- orR2And R3It is H or C1-C4 alkane independently of one another
Base, x are 0,1,2 or 3.
3. crosslinkable liquid Polycarbosilane according to claim 2, it is characterised in that R2And R3Be independently of one another H,
Methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl or isobutyl group.
4. crosslinkable liquid Polycarbosilane according to claim 2, it is characterised in that the R is CH independently of one another2
=CH-, CH2=CHCH2-, CH2=C (CH3)-, CH3CH=CH-, HC ≡ C-, HC ≡ C-CH2- or
5. crosslinkable liquid Polycarbosilane according to claim 2, it is characterised in that the R is CH independently of one another2
=CH-.
6. crosslinkable liquid Polycarbosilane according to claim 1, it is characterised in that SiH3/SiH2Si-H integration ratio
Less than 0.7 and more than 0.
7. crosslinkable liquid Polycarbosilane according to claim 6, it is characterised in that SiH3/SiH2Si-H integration ratio
Less than 0.5 and more than 0.
8. the crosslinkable liquid Polycarbosilane according to any one of claim 1-7, it is characterised in that described crosslinkable
Liquid Polycarbosilane is with single chloromethyl trialkoxy silane or chloromethyl trialkoxy silane and chloromethyl dimethoxy
Chlorosilane, the mixture of one methoxyl group dichlorosilane of chloromethyl are raw material, are obtained by grignard coupling and reduction reaction.
9. the preparation method of the crosslinkable liquid Polycarbosilane any one of claim 1 to 8, which includes following step
Suddenly：
(1) magnesium chips or magnesium powder are added in dry ether solvent, thereto a small amount of chloromethyl trialkoxy silane of Deca or
Chloromethyl trialkoxy silane and chloromethyl dimethoxy chlorosilane, the mixture of one methoxyl group dichlorosilane of chloromethyl and ethers
Solvent, after reaction causes, Deca chloromethyl trialkoxy silane or chloromethyl trialkoxy silane and chloromethyl diformazan under stirring
The mixed solution of epoxide chlorosilane, the mixture of one methoxyl group dichlorosilane of chloromethyl and ether solvent, 0～80 DEG C reaction 1～
12h；
(2) stir Grignard reagent of the lower Deca containing reactive group or can with magnesium be formed in situ Grignard reagent containing reactive group
Halogenated hydrocarbons or chloromethyl silane compound, 0～80 DEG C reaction 1～36h；
(3) lower addition reducing agent, 0～80 DEG C of 1～36h of reaction are stirred；
(4) it is sufficiently stirred for down, adds deionized water, concentrated hydrochloric acid and low boiling alkane, -20～30 DEG C of 0.5～5h of reaction to stand
0.5～5h, isolates upper organic phase drying after split-phase, distillation obtains product.
10. preparation method according to claim 9, it is characterised in that ether solvent is selected from ether, tetrahydrofuran, 2- first
Base tetrahydrofuran, glycol dimethyl ether, butyl cellosolve, diethylene glycol dimethyl ether, methyl tertiary butyl ether(MTBE), methyl tert-amyl
One kind or its two or more mixture in ether, cyclopentyl methyl ether.
11. preparation methoies according to claim 10, it is characterised in that the ether solvent is tetrahydrofuran, 2- methyl
Tetrahydrofuran, methyl tertiary butyl ether(MTBE) or tert amyl methyl ether(TAME).
12. preparation methoies according to claim 9, it is characterised in that low boiling alkane is selected from pentane, Pentamethylene., hexane
With the one kind in petroleum ether or its two or more mixture.
13. preparation methoies according to claim 12, it is characterised in that low boiling alkane is selected from hexane and Pentamethylene., or
Person is selected from the petroleum ether that boiling point is 30-60 DEG C.
14. preparation methoies according to claim 9, it is characterised in that the alkoxyl in chloromethyl trialkoxy silane is
C1-C4 alkoxyls.
15. preparation methoies according to claim 14, it is characterised in that the alcoxyl in the chloromethyl trialkoxy silane
Base is methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy.
16. preparation methoies according to claim 15, it is characterised in that the chloromethyl trialkoxy silane is chloromethyl
Trimethoxy silane, three isopropoxy silane of chloromethyl triethoxysilane or chloromethyl.
17. preparation methoies according to claim 16, it is characterised in that the chloromethyl trialkoxy silane is chloromethyl
Triethoxysilane.
18. preparation methoies according to claim 9, it is characterised in that chloromethyl tri-alkoxy silicon in described mixture
The molar content of alkane is more than 30%.
19. preparation methoies according to claim 9, it is characterised in that chloromethyl trialkoxy silane monomer and ethers are molten
The volume ratio of agent is 1:1～1:5.
20. preparation methoies according to claim 9, it is characterised in that the Grignard reagent containing reactive group is containing second
The unsaturated alkyl magnesium halide of alkenyl or alkynyl, selected from it is following any one：CH2=CH-MgBr, CH2=CH-MgCl, CH2
=CHCH2- MgBr, CH2=C (CH3)-MgBr, CH3CH=CH-MgBr, CH2=CHCH2- MgCl, CH3CH=CH-MgCl, HC
≡ C-MgBr, HC ≡ C-CH2MgBr；Halogenated hydrocarbons containing reactive group include：CH2=CHCH2Cl, CH2=CHBr, HC ≡ C-
CH2Br,Chloromethyl silane compound includes：ClCH2SiMeH2,ClCH2SiH2(CH=CH2)。
21. preparation methoies according to claim 9, it is characterised in that reducing agent be lithium aluminium hydride reduction, lithium hydride, magnesium hydride,
Sodium hydride or calcium hydride.
22. preparation methoies according to claim 21, it is characterised in that reducing agent is lithium aluminium hydride reduction.
23. preparation methoies according to claim 9, it is characterised in that the body of deionized water, concentrated hydrochloric acid and low boiling alkane
Product is than being 2:1:0.5～11:1:5.
The method that a kind of 24. crosslinkable liquid Polycarbosilanes by any one of claim 1 to 8 prepare SiC ceramic,
Wherein, in above-mentioned crosslinkable liquid Polycarbosilane structure, Si-H and C=C, C ≡ C unsaturation alkane groups are urged in platinum
There is Si―H addition reaction or Raolical polymerizable in the presence of agent or peroxide and form cross-linked structure, so as to obtain compared with Gao Tao
The SiC ceramic of porcelain yield.
25. methods according to claim 24, it is characterised in that the platinum catalyst is that chloroplatinic acid or Karstedt ' s are urged
Agent, 10-50ppm of the consumption for Polycarbosilane quality；Described peroxide is cumyl peroxide (DCP), and consumption is
The 0.1-0.5wt% of Polycarbosilane quality.
The preparation method of the ceramic sample of the crosslinkable liquid Polycarbosilane any one of 26. claim 1 to 8,
Which comprises the steps：
Cured is carried out to product that distillation in (4) the step of preparation method described in any one of claim 9-23 is obtained,
Cured product obtains ceramic sample through high temperature sintering again.
27. preparation methoies according to claim 26, it is characterised in that the cured is carried out in an inert atmosphere.
28. preparation methoies according to claim 27, it is characterised in that the inert atmosphere is nitrogen or argon.
29. preparation methoies according to claim 27, it is characterised in that typically program curing is：80～150 DEG C of insulations
2h, 150～280 DEG C of insulation 4h.
30. preparation methoies according to claim 26, it is characterised in that the high temperature sintering be cured product in nitrogen or
Under argon gas atmosphere, 800～1600 DEG C of insulation 0.5-10h obtain ceramic sample.
The application of the crosslinkable liquid Polycarbosilane any one of 31. claim 1 to 8, it is characterised in that this poly-
Cross-linking agent of the carbon silane as business Yajima method solid-state PCS, 5～50wt% of its consumption for PCS；Or, this poly- carbon silicon
Alkane prepares the presoma matrix resin of carbon fiber or the enhanced SiC based composites of silicon carbide fibre as PIP techniques；Or,
This Polycarbosilane is used as CVD/CVI silicon carbide ceramics presomas.
32. applications according to claim 31, it is characterised in that this Polycarbosilane is used as business Yajima method solid-state
The cross-linking agent of PCS, its consumption are 10～30wt%.
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| CN116143534B (en) * | 2023-02-14 | 2024-06-21 | 福建立亚新材有限公司 | Preparation method of mixed polycarbosilane reinforced silicon carbide ceramic matrix composite |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07233259A (en) * | 1994-02-24 | 1995-09-05 | Dow Corning Kk | Production of polycarbosilane |
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2014
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07233259A (en) * | 1994-02-24 | 1995-09-05 | Dow Corning Kk | Production of polycarbosilane |
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