CN109485858A - One kind Polycarbosilane containing metallic element and the preparation method and application thereof - Google Patents
One kind Polycarbosilane containing metallic element and the preparation method and application thereof Download PDFInfo
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Abstract
The present invention relates to a kind of Polycarbosilanes containing metallic element and the preparation method and application thereof, belong to ceramic forerunner technical field.Be different from traditional high temperature, high pressure vapor reaction process, the present invention at normal pressure, lower temperature can liquid phase directly synthesize Polycarbosilane.According to the difference of transition metal used (Ti, Zr, Hf) series catalysts type, corresponding metallic element, and the content controllable precise of metallic element are contained in gained Polycarbosilane.Products therefrom of the present invention can obtain the complex phase ceramic of silicon carbide Yu respective metal carbide after 1000 DEG C of refractory ceramics, which has good high-temperature oxidation resistance and Burning corrosion resistance energy.
Description
Technical field
The present invention relates to a kind of Polycarbosilanes containing metallic element and the preparation method and application thereof, belong to ceramics precursor body technique
Field.
Background technique
There is silicon carbide (SiC) ceramic material high intensity, high-modulus, anti-oxidant, high temperature resistant, resistance to ablation, low-density, height to lead
Many excellent properties such as hot coefficient, low-expansion coefficient are the thermal structure materials that current aerospace, space industry fall over each other research and development.
However, SiC can sharply decline in the at a temperature of mechanical strength higher than 1600 DEG C, while with the quick generation of actively oxidation.To
Introduce in SiC ceramic fusing point is higher, the better metal carbides of heat-resisting quantity mutually can an effective step improve whole resistance to of material
High-temperature behavior, therefore the concern by numerous studies personnel.
The preparation method of SiC ceramic based composites generally comprises melting osmosis (RM), chemical vapour deposition technique
(CVD), chemical vapor infiltration (CVI) and polymer infiltration and pyrolysis method (PIP) etc., wherein PIP method is good using mobility
Good high molecular polymer, i.e. presoma after impregnated material precast body, are impregnated, repeatedly more wheels again using solidification cracking
It can be prepared by SiC ceramic based composites after secondary, cracking temperature is low, short preparation period and easily prepared since this method has
The advantages such as complicated large-size components and more applied.
Polycarbosilane (PCS) is to prepare the most common presoma of SiC ceramic material, and PCS traditional preparation method is by day
The high temperature and pressure vapour phase rearrangement method of this scientist S.Yajima invention, prepared polydimethylsiloxane using sodium contracting method before this
(PDMS), then 450 DEG C~470 DEG C, 8~10MPa under conditions of so that PDMS is decomposed vaporization, while methyl intramolecular weight occurs
Row's reaction ultimately generates PCS, and this method mainly has the disadvantages of severe reaction conditions, energy consumption is high, and yield is low, and process flow is long.
Metal carbides are introduced into SiC ceramic mutually generally to realize by the method for introducing respective metal element into PCS,
Common method is to react that Polycarbosilane containing metal is made with PCS using metal alkoxide or metal oxa- alkane, and this method can draw
Enter oxygen element, causes to contain great amount of hydroxy group and acetyl group in the Polycarbosilane containing metal of preparation, lead to after ceramic that there are oxygen
Compound phase influences the mechanical behavior under high temperature of precursor ceramic yield (generally 35%) and ceramic material.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of completely new synthetic method of Polycarbosilane containing metal, the conjunctions
It can be completed in atmospheric low-temperature liquid phase at method, mild condition, product yield high.
The method of preparation Polycarbosilane containing metal according to the present invention, comprising steps of
A kind of Polycarbosilane containing metallic element, structural formula are as follows:
Wherein, R1 be methyl, ethyl, vinyl or phenyl, R2 be cyclopentadiene or cyclopentadiene alkyl-substituted derivative,
It is 0~30, m be 1~30, n is 0~30, M Ti, Zr or Hf that x, which is 1~10, y,.
In an alternative embodiment, x is 1~3；Y is 3~10；M is 5~15；N is 5~15.
A kind of preparation method of the Polycarbosilane containing metal, comprising the following steps:
(1) first metallocene and alkali metal are added in organic solvent 1, obtain mixed system 1, then by chloromethane ylmethyl two
Chlorosilane instills in the mixed system 1, carries out rearrangement polymerization reaction；
(2) alkaline-earth metal is added in the system that step (1) obtains, obtains mixed system 2, then by chloromethyl dichloro silicon
Alkane, which instills, carries out coupling polymerization reaction in mixed system 2；
(3) hydride is added in the system that step (2) obtains, carries out reduction reaction, is cooled to room after fully reacting
Temperature；
(4) reaction system obtained by step (3) is added dropwise in acid solution, adds organic solvent 2, at one section of sufficient standing
Between after obtain layered system；
(5) upper organic phase is collected, finally obtains Polycarbosilane containing metal after removing the organic solvent 2.
In an alternative embodiment, the metallocene is that two cyclopentadienyl M of dichloro or dichloro two replace luxuriant M, wherein M for Ti, Zr or
Hf。
In an alternative embodiment, the chloromethyl dichlorosilane is chloromethylmethyldichlorsilane, chloromethyl ethyl two
At least one of chlorosilane, chloromethyl phenyl dichlorosilane or chloromethyl vinyl base dichlorosilane.
In an alternative embodiment, the hydride is at least one of lithium aluminium hydride reduction, calcium hydride or sodium borohydride.
In an alternative embodiment, the organic solvent 1 be tetrahydrofuran, n-hexane, petroleum ether or dry ether at least
It is a kind of.
In an alternative embodiment, the organic solvent 2 is at least one of petroleum ether, acetone or chloroform.
In an alternative embodiment, in step (1), the mass ratio of the metallocene and chloromethylmethyldichlorsilane is
(0.1~1.8): 1, the quality of the alkali metal be the metallocene and chloromethylmethyldichlorsilane gross mass 0.3~
0.35 times.
In an alternative embodiment, step carries out rearrangement polymerization reaction in (1) at 60-110 DEG C.
In an alternative embodiment, chloromethyl described in chloromethyl dichlorosilane described in step (2) and step (1)
The mass ratio of dimethyl dichlorosilane (DMCS) is (1~10): 1.
In an alternative embodiment, in step (2), the mass ratio of the alkaline-earth metal and chloromethyl dichlorosilane is
(0.3~0.4): 1.
In an alternative embodiment, step (2) carries out coupling polymerization reaction at 0-70 DEG C.
In an alternative embodiment, the quality of hydride described in step (3) is chloromethane ylmethyl two described in step (1)
0.1~0.2 times of the gross mass of chloromethyl dichlorosilane described in chlorosilane and step (2).
In an alternative embodiment, step (3) carries out reduction reaction at 0-70 DEG C.
Application of the above-mentioned Polycarbosilane containing metal in preparation SiC ceramic material and ceramic matric composite.
The invention has the following beneficial effects:
(1) Polycarbosilane containing metallic element provided in an embodiment of the present invention can introduce vinyl and Si -- H bond isoreactivity base
Self-crosslinking solidification occurs under proper condition, improves precursor ceramic yield and craftsmanship for group；In addition hydroxyl is not contained in structure
The oxygen-containing groups such as base and acetyl group, can make presoma be converted to target ceramic phase under lower cracking temperature；
(2) ceramic yield is after Polycarbosilane containing metal provided by the invention cracks under the conditions of 1000 DEG C of argon atmosphere
52% or more, gained pyrolysis product is the wherein nanoscale MC by SiC phase and the complex phase ceramic of MC phase composition (M=Ti, Zr, Hf)
Even particulate dispersion is in continuous SiC phase.
Detailed description of the invention
Fig. 1 is the infared spectrum of products therefrom C1 in embodiment 1；
Fig. 2 is the XRD diagram of the pyrolysis product of products therefrom C1 in embodiment 1；
Fig. 3 is the TG curve graph of products therefrom C1 in embodiment 1.
Specific embodiment
Invention further progress is stated below by specific embodiment and in conjunction with attached drawing.Those skilled in the art should manage
Solution is described below and is only used for explaining that invention makes any restrictions not for it.
The embodiment of the invention provides a kind of Polycarbosilanes containing metallic element, shown in structural formula such as following formula (1):
Wherein, R1 is methyl, ethyl, vinyl or phenyl, and preferred vinyl, R2 is cyclopentadiene or cyclopentadiene alkyl
Substitutive derivative, preferably cyclopentadiene, it be 0~30, m be 1~30, n is 0~30 that x, which is 1~10, y,.
Polycarbosilane containing metallic element provided in an embodiment of the present invention can introduce vinyl and Si -- H bond isoreactivity group,
Self-crosslinking solidification can occur under proper condition, improve precursor ceramic yield (up to 50% or more) and craftsmanship；In addition
Without containing oxygen-containing groups such as hydroxyl and acetyl group in structure, presoma can be made to be converted to target ceramics under lower cracking temperature
Phase.
In an alternative embodiment, x is 1~3；Y is 3~10；M is 5~15；N is 5~15.
The embodiment of the invention also provides a kind of preparation methods of Polycarbosilane containing metal, comprising the following steps:
Metallocene and alkali metal: being first added in organic solvent 1 by step (1), obtains mixed system 1, then by chloromethyl
Dimethyl dichlorosilane (DMCS) instills in the mixed system 1, carries out rearrangement polymerization reaction；
Wherein, the preferred two cyclopentadienyl M of dichloro of the metallocene or dichloro two replace luxuriant M, and wherein M is Ti, Zr or Hf；The alkali gold
Belong to preferred sodium, potassium or Na-K alloy, more preferable sodium；The preferred tetrahydrofuran of the organic solvent 1, n-hexane, petroleum ether or dry ether
At least one of equal organic solvents, more preferable tetrahydrofuran；
In an alternative embodiment, in step (1), the mass ratio of the metallocene and chloromethylmethyldichlorsilane is
(0.1~1.8): 1, the quality of the alkali metal be the metallocene and chloromethylmethyldichlorsilane gross mass 0.3~
0.35 times, to reduce byproduct of reaction, improve yield；
In an alternative embodiment, rearrangement polymerization reaction is carried out at 60-110 DEG C, is carried out preferably at 60~70 DEG C anti-
It answers, carries out and improve reaction rate to ensure to react safety, save preparation time, reaction time preferably 9~11h.
Step (2): alkaline-earth metal being added in the system that step (1) obtains, and obtains mixed system 2, then by chloromethyl
Dichlorosilane, which instills, carries out coupling polymerization reaction in mixed system 2；
Wherein, the preferred lithium of the alkaline-earth metal or magnesium；The chloromethyl dichlorosilane can be chloromethyl methyl dichloro
At least one of silane, chloromethyl ethyl dichlorosilane, chloromethyl phenyl dichlorosilane or chloromethyl vinyl base dichlorosilane；
In an alternative embodiment, chloromethyl described in chloromethyl dichlorosilane described in step (2) and step (1)
The mass ratio of dimethyl dichlorosilane (DMCS) is (1~10): 1；Chloromethane described in alkaline-earth metal described in step (2) and step (2)
The mass ratio of base dichlorosilane is (0.3~0.4): 1；Activity group content in product can be improved in the proportional region, is ensuring
Under the premise of product stability, ceramic yield is further improved；
In an alternative embodiment, step (2) carries out coupling polymerization reaction at 0-70 DEG C, preferably anti-at 40~65 DEG C
It answers, implode, reaction time preferably 9~11h is prevented while guaranteeing that polymerization reaction is gone on smoothly.
Step (3): hydride being added in the system that step (2) obtains, and carries out reduction reaction, cooling after fully reacting
To room temperature；
Specifically, at least one of the preferred lithium aluminium hydride reduction of the hydride, calcium hydride or sodium borohydride；Step (3)
Chloromethyl first described in chloromethylmethyldichlorsilane described in the quality preferred steps (1) of the hydride and step (2)
0.1~0.2 times of the gross mass of base dichlorosilane；
In an alternative embodiment, step (3) carries out reduction reaction at 0-70 DEG C, preferably reacts at 30~50 DEG C,
Guarantee to prevent product implode while reduction reaction is gone on smoothly, reaction time preferably 4~6h.
Step (4): reaction system obtained by step (3) is added dropwise in acid solution, organic solvent 2, sufficient standing are added
Layered system is obtained after a period of time；
Specifically, in the embodiment of the present invention, the acid solution can make the olefin(e) acids solution such as hydrochloric acid, sulfuric acid and phosphoric acid, preferably
The hydrochloric acid solution that mass concentration is 10%；At least one of the preferred petroleum ether of the organic solvent 2, chloroform or acetone, it is more excellent
Select petroleum ether.
Step (5): collecting upper organic phase, finally obtains Polycarbosilane containing metal after removing the organic solvent 2.
Wherein, reaction need to carry out under the conditions of anhydrous and oxygen-free in step (1), (2) and (3).
Shown in product structure such as formula (1) made from the preparation method of the Polycarbosilane provided by the invention containing metal, specifically retouch
Effect is addressed referring to the said goods embodiment, details are not described herein.In addition, the preparation method is at normal pressure, lower temperature
Can liquid phase directly synthesize Polycarbosilane.According to the difference of transition metal used (Ti, Zr, Hf) series catalysts type, the poly- carbon of gained
Contain corresponding metallic element, and the content controllable precise of metallic element in silane.
Present invention implementation additionally provides above-mentioned Polycarbosilane containing metal in preparation SiC ceramic material and ceramic matric composite
In application.
Ceramic yield is 52% or more after above-mentioned Polycarbosilane containing metal cracks under the conditions of 1000 DEG C of argon atmosphere, gained
Pyrolysis product be by SiC phase and the complex phase ceramic of MC phase composition (M=Ti, Zr, Hf), wherein nanoscale MC even particulate dispersion in
In continuous SiC phase, the mechanical behavior under high temperature of ceramic material can be effectively improved.
The following are specific embodiments of the present invention:
Raw materials used various embodiments of the present invention are commercial product.
Embodiment 1
Dry toluene 200ml is added in the three-necked flask of 500ml, is heated to after being put into the sodium block of 10g scale removal
It 100 DEG C, is quickly stirred after the fusing of sodium block using magneton and sodium block is broken into fine particle, finally stop stirring and being down to room temperature,
Sodium sand is obtained after removal toluene；
It separately takes a 500ml three-necked flask and 100ml anhydrous tetrahydro furan and above-mentioned sodium sand 3.5g is added, then weigh dichloro
Zirconocene 3g is added flask and starts to warm up, and starts that 8.2g chloromethylmethyldichlorsilane is slowly added dropwise after being warming up to 65 DEG C, drips
65 DEG C insulated and stirred 10 hours under protection of argon gas after complete；
System temperature is down to 40 DEG C, magnesium chips 3g is added into flask, then chloromethyl vinyl base two is slowly added dropwise into flask
Temperature is risen to 65 DEG C after dripping off and starts insulation reaction 10 hours by chlorosilane 8.2g；
System temperature is down to 40 DEG C, and lithium aluminium hydride reduction 3g is added by several times into flask, is then warming up to 65 DEG C again and starts
Insulated and stirred is reacted 5 hours, and room temperature is naturally cooling to after heat preservation, finally obtains Solution H 1；
It takes the beaker of a 2L to be packed into the hydrochloric acid and 300ml petroleum ether of 1L mass concentration 10%, beaker is cooled to 10 DEG C
Hereinafter, starting that Solution H 1 is slowly added dropwise to the inside of beaker, dropwise addition process need to remain temperature at 10 DEG C hereinafter, completing after being added dropwise
It is thoroughly mixed liquid with glass bar, is then allowed to stand and is layered completely to it, finally take upper organic phase with separatory funnel point, obtain
Solvent removal is finally obtained final product C1 with Rotary Evaporators by crude product in solution W1.
Product C1 is tested using infared spectrum, the result is shown in Figure 1., it is apparent that 2100cm-1(Si-H
Stretching), 880cm-1(Si-H deformation), 1020cm-1(Si-CH2- Si stretching) and 1355cm-1(Si-CH2- Si bending) etc. absorption peaks be both present in the infared spectrum of C1；In addition, there is also belong in map
The 3090cm of cyclopentadiene-1、1450cm-1、1041cm-1And 805cm-1Characteristic absorption peak, and belong to vinyl
1592cm-1Characteristic absorption peak, it is a kind of poly- carbon silicon of structural formula as shown in formula (1) containing zr element that these, which demonstrate C1,
Alkane, wherein R1 is vinyl, and R2 is cyclopentadienyl group, x 1；Y is 4；M is 5；N is 5.
Ceramic yield with TG-DTA with the heating rate detection product C1 of 10 DEG C/min at 1000 DEG C, as a result such as Fig. 2
It is shown.It can be seen that product C1 quick weight loss since 350 DEG C in Fig. 2, and basic holding weight no longer becomes after 850 DEG C
Change, at 1000 DEG C, its ceramic yield is 62.0%.
1000 DEG C of high-temperature process are carried out to product C1 with the heating rate of 5 DEG C/min with tube furnace, the ceramics for measuring C1 produce
Rate is 58.6%.
By product C1, the rate of 2 DEG C/min is warming up to 1500 DEG C under argon atmosphere protection, and keeps the temperature 2 hours, obtains ash
Black cellular solid, pulverize it is last tested with XRD, as a result see Fig. 3.In Fig. 3 it can be seen that 33.074 °,
There is diffraction maximum at 38.386 °, 55.377 °, 66.049 °, 69.337 °, 82.208 °, the characteristic peak kissing with face-centered cubic ZrC
It closes；Diffraction maximum is had also appeared at 35.744 °, 60.026 °, 72.033 °, is matched with the characteristic peak of face-centred cubic SiC, is schemed
In do not occur other obvious diffraction maximums, it was demonstrated that the high-temperature split product of C1 be SiC phase and ZrC phase compound.
Embodiment 2
Tetrahydrofuran 100ml is added in the three-necked flask of 500ml, is heated to 65 after being put into the potassium block of 4g scale removal
DEG C, it is quickly stirred after the fusing of potassium block using magneton and is broken into fine particle, then stop stirring, support potassium sand；
It weighs bis cyclopentadienyl zirconium dichloride 3g flask is added and restarts to stir, starts that 8.2g chloromethyl is slowly added dropwise after ten minutes
Dimethyl dichlorosilane (DMCS), 65 DEG C insulated and stirred 10 hours under protection of argon gas after dripping off；System temperature is down to 40 DEG C, adds into flask
Enter magnesium chips 3g, then chloromethylmethyldichlorsilane 8.2g is slowly added dropwise into flask, temperature is risen to 65 DEG C after dripping off and starts
Insulation reaction 10 hours；System temperature is down to 40 DEG C, and lithium aluminium hydride reduction 3g is added by several times into flask, is then warming up to 65 DEG C again
And start insulated and stirred and react 5 hours, it is naturally cooling to room temperature after heat preservation, finally obtains Solution H 2；Take the burning of a 2L
Cup enters the hydrochloric acid and 300ml petroleum ether of 1L concentration 10%, and beaker is cooled to 10 DEG C hereinafter, starting slowly to drip to the inside of beaker
Solubilization liquid H2, dropwise addition process need to remain temperature at 10 DEG C hereinafter, completing to be thoroughly mixed liquid with glass bar after being added dropwise, so
After stand and be layered completely to it, then point take upper organic phase with separatory funnel, obtain crude product in solution W2, finally steamed with rotation
It sends out instrument and solvent removal is obtained into final product C2.
It carries out test to product C2 using infared spectrum to obtain, 2100cm-1(Si-H stretching), 880cm-1(Si-
H deformation), 1020cm-1(Si-CH2- Si stretching) and 1355cm-1(Si-CH2- Si bending) etc.
Absorption peak has been both present in the infared spectrum of C2；In addition, there is also the 3090cm for belonging to cyclopentadiene in map-1、
1450cm-1、1041cm-1And 805cm-1Characteristic absorption peak, it is a kind of structural formula as shown in formula (1) that these, which demonstrate C2,
Polycarbosilane containing zr element, wherein R1 is methyl, and R2 is cyclopentadienyl group, x 1；Y is 4；M is 5；N is 5.
Ceramic yield of the product C2 at 1000 DEG C is detected as 59.3% with the heating rate of 10 DEG C/min with TG-DTA.With
Tube furnace carries out 1000 DEG C of high-temperature process to product C2 with the heating rate of 5 DEG C/min, and the ceramic yield for measuring C2 is 57.4%.
By product C2, the rate of 2 DEG C/min is warming up to 1500 DEG C under argon atmosphere protection, and keeps the temperature 2 hours, obtains ash
Black cellular solid, pulverize it is last tested with XRD, as the result is shown 33.074 °, 38.386 °, 55.377 °,
There is diffraction maximum at 66.049 °, 69.337 °, 82.208 °, matches with the characteristic peak of face-centered cubic ZrC；35.744 °,
Diffraction maximum is had also appeared at 60.026 °, 72.033 °, is matched with the characteristic peak of face-centred cubic SiC, does not find that other are obvious
Diffraction maximum, it was demonstrated that the high-temperature split product of C2 is the compound of SiC phase and ZrC phase.
Embodiment 3
Dry toluene 200ml is added in the three-necked flask of 500ml, is heated to after being put into the sodium block of 10g scale removal
It 100 DEG C, is quickly stirred after the fusing of sodium block using magneton and sodium block is broken into fine particle, finally stop stirring and being down to room temperature,
Sodium sand is obtained after removal toluene；
It separately takes a 500ml three-necked flask and 100ml anhydrous tetrahydro furan and above-mentioned sodium sand 3.5g is added, then weigh dichloro
Titanocenes 2.5g is added flask and starts to warm up, and starts that 8.2g chloromethylmethyldichlorsilane is slowly added dropwise after being warming up to 65 DEG C,
65 DEG C insulated and stirred 10 hours under protection of argon gas after dripping off；System temperature is down to 40 DEG C, the addition magnesium chips 3g into flask, then to
Chloromethylmethyldichlorsilane 8.2g is slowly added dropwise in flask, temperature is risen to 65 DEG C after dripping off and to start insulation reaction 10 small
When；System temperature is down to 40 DEG C, and lithium aluminium hydride reduction 3g is added by several times into flask, is then warming up to 65 DEG C again and starts heat preservation and stirs
Reaction 5 hours is mixed, room temperature is naturally cooling to after heat preservation, finally obtains Solution H 3；The beaker of a 2L is taken to be packed into 1L concentration
Beaker is cooled to 10 DEG C hereinafter, starting that Solution H 3 is slowly added dropwise to the inside of beaker, drop by 10% hydrochloric acid and 300ml petroleum ether
Add process that need to remain that temperature hereinafter, complete with glass bar to be thoroughly mixed liquid after being added dropwise, is then allowed to stand to it at 10 DEG C
Layering completely finally point takes upper organic phase with separatory funnel, obtains crude product in solution W3, finally with Rotary Evaporators by solvent
Removing obtains final product C3.
It carries out test to product C3 using infared spectrum to obtain, 2100cm-1(Si-H stretching), 880cm-1(Si-
H deformation), 1020cm-1(Si-CH2- Si stretching) and 1355cm-1(Si-CH2- Si bending) etc.
Absorption peak has been both present in the infared spectrum of C3；In addition, there is also the 3090cm for belonging to cyclopentadiene in map-1、
1450cm-1、1041cm-1And 805cm-1Characteristic absorption peak, it is a kind of structural formula as shown in formula (1) that these, which demonstrate C3,
Polycarbosilane containing titanium elements, wherein R1 is methyl, and R2 is cyclopentadienyl group, x 1；Y is 4；M is 5；N is 5.
Ceramic yield of the product C3 at 1000 DEG C is detected as 56.3% with the heating rate of 10 DEG C/min with TG-DTA.With
Tube furnace carries out 1000 DEG C of high-temperature process to product C3 with the heating rate of 5 DEG C/min, and the ceramic yield for measuring C3 is 54.6%.
By product C3, the rate of 2 DEG C/min is warming up to 1500 DEG C under argon atmosphere protection, and keeps the temperature 2 hours, obtains ash
Black cellular solid, pulverize it is last tested with XRD, as the result is shown 36.040 °, 41.987 °, 60.899 °,
There is diffraction maximum at 72.673 °, matches with the characteristic peak of face-centered cubic TiC；At 35.744 °, 60.026 °, 72.033 ° also
There is diffraction maximum, match with the characteristic peak of face-centred cubic SiC, does not find other obvious diffraction maximums, it was demonstrated that the high temperature of C3
Pyrolysis product is the compound of SiC phase and TiC phase.
The above, a specific embodiment only of the invention, but scope of protection of the present invention is not limited thereto, appoints
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of, all by what those familiar with the art
It is covered by the protection scope of the present invention.
Unspecified part of the present invention belongs to common sense well known to those skilled in the art.
Claims (16)
1. a kind of Polycarbosilane containing metallic element, which is characterized in that its structural formula is as follows:
Wherein, R1 is methyl, ethyl, vinyl or phenyl, and R2 is cyclopentadiene or cyclopentadiene alkyl-substituted derivative, x 1
It is 1~30, n is 0~30, M Ti, Zr or Hf that~10, y, which are 0~30, m,.
2. Polycarbosilane containing metallic element according to claim 1, which is characterized in that x is 1~3；Y is 3~10；M is 5
~15；N is 5~15.
3. a kind of preparation method of Polycarbosilane containing metal, which comprises the following steps:
(1) first metallocene and alkali metal are added in organic solvent 1, obtain mixed system 1, then by chloromethyl methyl dichloro silicon
Alkane instills in the mixed system 1, carries out rearrangement polymerization reaction；
(2) alkaline-earth metal is added in the system that step (1) obtains, obtains mixed system 2, then chloromethyl dichlorosilane is dripped
Enter progress coupling polymerization reaction in mixed system 2；
(3) hydride is added in the system that step (2) obtains, carries out reduction reaction, is cooled to room temperature after fully reacting；
(4) reaction system obtained by step (3) is added dropwise in acid solution, adds organic solvent 2, sufficient standing for a period of time after
Obtain layered system；
(5) upper organic phase is collected, finally obtains Polycarbosilane containing metal after removing the organic solvent 2.
4. the preparation method of the Polycarbosilane according to claim 3 containing metal, which is characterized in that the metallocene is dichloro
Two cyclopentadienyl M or dichloro two replace luxuriant M, and wherein M is Ti, Zr or Hf.
5. the preparation method of the Polycarbosilane according to claim 3 containing metal, which is characterized in that the chloromethyl dichloro silicon
Alkane is chloromethylmethyldichlorsilane, chloromethyl ethyl dichlorosilane, chloromethyl phenyl dichlorosilane or chloromethyl vinyl base two
At least one of chlorosilane.
6. the preparation method of the Polycarbosilane according to claim 3 containing metal, which is characterized in that the hydride is hydrogen
Change at least one of aluminium lithium, calcium hydride or sodium borohydride.
7. the preparation method of the Polycarbosilane according to claim 3 containing metal, which is characterized in that the organic solvent 1 is
At least one of tetrahydrofuran, n-hexane, petroleum ether or dry ether.
8. the preparation method of the Polycarbosilane according to claim 3 containing metal, which is characterized in that the organic solvent 2 is
At least one of petroleum ether, acetone or chloroform.
9. the preparation method of the Polycarbosilane according to claim 3 containing metal, which is characterized in that in step (1), the cyclopentadienyl
The mass ratio of metal and chloromethylmethyldichlorsilane is (0.1~1.8): 1, the quality of the alkali metal be the metallocene and
0.3~0.35 times of chloromethylmethyldichlorsilane gross mass.
10. the preparation method of the Polycarbosilane according to claim 3 containing metal, which is characterized in that in 60- in step (1)
Rearrangement polymerization reaction is carried out at 110 DEG C.
11. the preparation method of the Polycarbosilane according to claim 3 containing metal, which is characterized in that described in step (2)
The mass ratio of chloromethylmethyldichlorsilane described in chloromethyl dichlorosilane and step (1) is (1~10): 1.
12. the preparation method of the Polycarbosilane according to claim 3 containing metal, which is characterized in that described in step (2)
Alkaline-earth metal and chloromethyl dichlorosilane mass ratio be (0.3~0.4): 1.
13. the preparation method of the Polycarbosilane according to claim 3 containing metal, which is characterized in that step (2) is at 0-70 DEG C
Lower progress coupling polymerization reaction.
14. the preparation method of the Polycarbosilane according to claim 3 containing metal, which is characterized in that hydrogen described in step (3)
The quality of compound is the total of chloromethyl dichlorosilane described in chloromethylmethyldichlorsilane described in step (1) and step (2)
0.1~0.2 times of quality.
15. the preparation method of the Polycarbosilane according to claim 3 containing metal, which is characterized in that step (3) is at 0-70 DEG C
Lower carry out reduction reaction.
16. Polycarbosilane containing metal as claimed in claim 1 or 2 answering in preparation SiC ceramic material and ceramic matric composite
With.
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| CN110776320A (en) * | 2019-10-12 | 2020-02-11 | 航天材料及工艺研究所 | C/SiC-ZrC complex phase ceramic matrix composite and preparation method thereof |
| CN112321835A (en) * | 2020-10-30 | 2021-02-05 | 宁波众兴新材料科技有限公司 | Boron-containing polymetallic carbosilane and preparation method thereof |
| CN114106339A (en) * | 2021-12-06 | 2022-03-01 | 长沙达菲新材料科技有限公司 | Preparation method of polymetallic carbosilane precursor |
| CN115746307A (en) * | 2022-12-01 | 2023-03-07 | 长沙达菲新材料科技有限公司 | Preparation method of polymetallic carbosilane precursor |
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| CN112321835A (en) * | 2020-10-30 | 2021-02-05 | 宁波众兴新材料科技有限公司 | Boron-containing polymetallic carbosilane and preparation method thereof |
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