CN102585235A - Catalytic synthesis method of polycarbosilane precursor - Google Patents
Catalytic synthesis method of polycarbosilane precursor Download PDFInfo
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Abstract
The invention discloses a catalytic synthesis method of a polycarbosilane precursor. The method comprises the following steps: (1) vacuumizing a normal-pressure high-temperature cracking transformation synthesis device, and filling nitrogen in the device till the pressure in the device is normal; (2) introducing polycarbosilane into the normal-pressure high-temperature cracking transformation synthesis device; (3) placing catalyst metal oxide or composite oxide of silicon oxide and metal oxide in the normal-pressure high-temperature cracking transformation synthesis device; (4) heating to 420 DEG C-460 DEG C, reacting for 10 hours-16 hours, and cooling to room temperature; and (5) dissolving the crude product obtained in the step (4) with dimethylbenzene, filtering, carrying out rotary distillation on filtrate, and cooling to room temperature so as to obtain the polycarbosilane precursor. The method disclosed by the invention is short in reaction time and high in synthesis yield; the linearity of the product molecule structure is high; equipment is simple; catalyst cost is low; and operation is safe. The synthesized polycarbosilane precursor is suitable for preparation of SiC fiber and a SiC ceramic-based composite material.
Description
Technical field
The present invention relates to a kind of compound method of polycarbosilane precusor, especially relate to a kind of process for catalytic synthesis of polycarbosilane precusor.
Background technology
Development along with hi-techs such as Aeronautics and Astronautics, weapons, the energy has proposed increasingly high requirement to the elevated temperature heat structured material.Traditional metallic substance and macromolecular material have been difficult to satisfy these application requiring.High temperature resistant, low-density ceramic matric composite has become the development trend of high temperature material.Developed country drops into huge fund research refractory ceramics based composites invariably, and wherein continuous fibre enhanced ceramic matric composite becomes the emphasis of research and development because of its excellent comprehensive performance.
High-temperature fibre (at high temperature can keep HS and high-modulus continuous ceramic fiber) is the prerequisite and the basis of making the refractory ceramics based composites.The SiC fiber is as a kind of new ceramics fiber; Have that density is little, specific tenacity is big, specific modulus is high, linear expansivity is little, characteristics such as high temperature resistant, corrosion-resistant, HS; Having good compound consistency with metal, pottery, polymkeric substance, is the desirable fortifying fibre of high performance composite.Structure set-stealthy-solar heat protection is multi-functional for the SiC fiber simultaneously, is a kind of very ideal inorganic reinforcing fiber, is with a wide range of applications in some high-tech sectors such as space flight, aviation, weapons, boats and ships and nuclear industry.
The SiC based composites can at high temperature keep HS, high-modulus characteristic; Density is used widely in fields such as Aeronautics and Astronautics, nuclear energy, high speed brake, high temperature air filtration and heat exchangers with carbon (C) fiber, SiC fiber reinforcement SiC based composites much smaller than metal and alloy material at present simultaneously.
The organic precursor method conversion method is to be raw material with organic polymer (being mostly organometallic polymer), utilize its characteristic such as solvable, fusible to realize moulding after, through the elevated temperature heat disaggregating treatment, make it to change into the method for inorganic ceramic material from organism.This organometallic polymer just is called organic precursor method or ceramic precursor.The precursor conversion method have good manufacturability (being easy to prepare the complicated abnormal shape member), preparation temperature low, be easy to advantages such as industriallization and receive extensive concern.The organic precursor method conversion method is one of main method of preparation SiC fiber, SiC based composites.Organic precursor method then is that precursor transforms one of critical materials for preparing ceramic matric composite.
Polycarbosilane (polycarbosilane, be called for short PCS) be a kind of be the polymkeric substance of main chain with Si-C: [(SiR
1R
2-CH
2)
x(SiR
3H-CH
2)
1-x-]
nGathering silicon-carbon silane (Polysilacarbosilane, be called for short PSCS) and be a kind of is the low-molecular weight polymer of main chain, wherein block Si-C with Si-Si: [(SiR
1R
2-SiR
3R
4)
x(SiR
5R
6-CH
2)
1-x-].
It under the PCS room temperature solid; Good stability dissolves in organic solvents such as THF, YLENE, the heating melting; Having good processability, is that the organic precursor method conversion method prepares SiC fiber, most important, the most frequently used organic precursor method of SiC based composites.
The compound method of existing PCS has multiple.Common has: (1) pyrolysis-rearrangement conversion method; (2) ring-opening polymerization method; (3) hydrosilation method; (4) polymer metal method; (5) blending method.Also have pyrolysis method, sol-gel method, electrochemical process, photochemical method, polycondensation method, copolymerization method etc. in addition.But the realization industrialization, have only pyrolysis-rearrangement conversion method at present.
Research shows that reaction pressure has material impact to the physicochemical property of pyrolysis-rearrangement conversion method synthetic PCS precursor.Therefore, this method comprises high temperature and high pressure method and constant-pressure and high-temperature cracking conversion method again.This is at present domestic and international two kinds of typical PCS precursor compound methods.High temperature and high pressure method is more sophisticated method; Synthesis yield is generally 45%-55%; But this method need be used high-temperature high-pressure reaction kettle, needs the special safety issue of considering, owing to the volume restrictions of high-temperature high-pressure reaction kettle; Be difficult to realize the in enormous quantities synthetic of PCS precursor, cause the production cost of PCS precursor higher; Constant-pressure and high-temperature cracking conversion method synthesizer is simple, and security is good, realizes the in enormous quantities synthetic of PCS precursor easily; But; Though production cost is lower with respect to high temperature and high pressure method, because synthesis yield lower (generally between 35%-40%), production cost is still higher.
Improving structure, the physicochemical property of PCS precursor, improve the synthesis yield of PCS precursor, reduce cost, is one of main direction of studying of present PCS precursor.Existing research shows, is the synthetic PCS precursor of raw material constant-pressure and high-temperature cracking conversion method with liquid polysilane (LPS), and when not adding catalyzer, the reaction times is generally 24h-36h, and synthesis yield is generally 35%-40%.In addition, be raw material with LPS, when not adding catalyst reaction, adopt in the constant-pressure and high-temperature cracking conversion method synthetic PCS precursor Si-H content is on the low side (SiH/SiCH among the FT IR
3The ratio of absorbancy is generally less than 1.0), the degree of branching higher (
29SiC among the Si NMR
3H/SiC
4The ratio of peak area is generally 0.80-0.95), this causes disadvantageous effect to melt-spinning, preparation SiC fiber.
Existing research shows, is raw material with LPS, through adding the yield that certain organic catalyst can improve the synthetic PCS precursor of constant-pressure and high-temperature cracking conversion method.For example, the polyborosiloxane of processing with diphenyl dichlorosilane and acid reaction is as catalyzer, and the yield of PCS precursor can bring up to 48%.This method has been introduced assorted elements such as B and O in the structure of final product PCS.With butyl borate (B (OBu)
3) as catalyzer, the yield of PCS precursor can bring up to 50%.This method has been introduced assorted elements such as B and O equally in the structure of final product PCS.As catalyzer, the yield of PCS precursor can bring up to 50% with Vinylstyrene.This method is also introduced other assorted element in the structure of PCS precursor---and introduced new group or structures such as phenyl and vinyl, this SiC fiber, SiC based composites to preparation causes disadvantageous effect.
In LPS, add the synthetic PCS precursor of polydimethyl silane (PDMS) constant-pressure and high-temperature cracking conversion method, can improve the synthetic yield, but contain Na owing to removing among the PDMS
+, Cl
-Outside detrimental impurity, oxygen level is also high, causes synthetic PCS precursor oxygen level also higher (generally greater than 1.0wt%).This causes disadvantageous effect to SiC fiber, the SiC based composites of preparation equally.
In brief, there is following defective in existing PCS precursor constant-pressure and high-temperature cracking conversion synthesis method: synthesis yield is lower, and production cost is still higher; Synthetic PCS, Si-H content is lower, and the degree of branching is higher.
Summary of the invention
The objective of the invention is to overcome the defective of above-mentioned prior art, provide a kind of synthesis yield high, the synthetic product degree of branching is low, and required equipment is simple, the polycarbosilane precusor process for catalytic synthesis that security is good.
The objective of the invention is to realize through following technical scheme: to gather silicon-carbon silane is raw material, adds the certain proportion metal oxide catalyst therein, or composite oxide catalysts, adopts the synthetic PCS precursor of constant-pressure and high-temperature cracking conversion method.
The present invention specifically may further comprise the steps: (1) vacuumizes constant-pressure and high-temperature cracking conversion synthesizer and replaces gas reactor to normal pressure with high pure nitrogen, repeats 2-4 time (preferred 3 times); (2) will gather silicon-carbon silane is incorporated in the constant-pressure and high-temperature cracking conversion synthesizer; (3) with the composite oxides of catalyst metal oxide compound or silicon oxide and MOX, be incorporated into the constant-pressure and high-temperature cracking and transform in the synthesizer, catalyst consumption is to gather 0.1%～5% of silicon-carbon silane quality, continues to stir; (4) temperature programming to 400 ℃～460 ℃, reaction 10h～16h is cooled to room temperature; (5) go on foot the thick product of gained through xylene soluble, filtration with (4), filtrating is rotated distillation at 150 ℃～210 ℃, is cooled to room temperature.
Preferred aluminum oxide (the Al of said MOX
2O
3) or titanium oxide (TiO
2).
The preferred oxidation sial of the composite oxides of said silicon oxide and MOX (Al
2O
3SiO
2), silicon oxide titanium (TiO
2SiO
2) or oxidation sial titanium (Al
2O
3TiO
2SiO
2).
The specific surface area of each catalyzer, preferred>=600g/m
2
Compare with the method for the synthetic PCS precursor of existing atmospheric cracking conversion method, the present invention is through adding special catalyst MOX such as aluminum oxide, titanium oxide, or the composite oxides of silicon oxide and MOX such as oxidation sial, silicon oxide titanium or silicon oxide titanium aluminium; On the one hand; Because the mechanism of catalytic reaction when their mechanism of catalytic reaction is catalyzer with polyborosiloxane, butyl borate, Vinylstyrene etc. is different fully, therefore, the present invention can react under lower temperature; And improve speed of reaction greatly; Thereby improve the polyreaction degree, improve reaction efficiency, improve the synthesis yield of PCS precursor; On the other hand, catalyzer makes polyreaction show certain orientation, and the degree of branching of synthetic PCS precursor molecular structure is reduced, and the linear lag increases, and but can in PCS precursor structure, not introduce harmful assorted element or group.
Compare with the method for the synthetic PCS precursor of existing high temperature and high pressure method, equipment required for the present invention is simple, operational safety.
In brief, the present invention has following advantage: the reaction times is shortened in (1), improves reaction efficiency, improves the synthetic yield of PCS precursor; (2) in PCS precursor structure, do not introduce harmful assorted element or group; (3) linear lag of raising PCS precursor molecular structure; (4) equipment is simple, does not need that existing constant-pressure and high-temperature cracking conversion method PCS precursor synthesis system is done any equipment and changes; (5) the catalyzer cost that uses is lower; (6) operational safety.
Synthetic PCS precursor of the present invention is applicable to preparation SiC fiber and SiC ceramic matric composite.
Description of drawings
Fig. 1 gathers the infrared spectrum (FT IR) of silicon-carbon silane for raw material;
The X-photoelectron spectrum figure (XPS) of the PCS precursor that Fig. 2 makes for embodiment 1;
The infrared spectrum of the PCS precursor that Fig. 3 makes for embodiment 1 (FT IR);
The PCS precursor that Fig. 4 makes for embodiment 1
1The H nmr spectrum (
1H NMR);
The PCS precursor that Fig. 5 makes for embodiment 1
29The Si nmr spectrum (
29Si NMR).
Embodiment
Below in conjunction with embodiment the present invention is done further explain.
(1) the constant-pressure and high-temperature cracking is transformed synthesis system and vacuumize, the displacement high pure nitrogen repeats 3 times; (2) under the protection of high pure nitrogen, 500g is gathered silicon-carbon silane introduce in the constant-pressure and high-temperature cracking conversion synthesis system; (3) (its specific surface area is 610g/m with alumina catalyst
2) 2.5g is incorporated into the constant-pressure and high-temperature cracking and transforms in the synthesizer, continue to stir; (4) be warming up to 420 ℃ of reaction 10h, be warming up to 460 ℃ of reaction 2h again; (5) be cooled to room temperature, get the thick product of 319g PCS precursor; Thick product is through xylene soluble, filtration, and filtrating is rotated distillation at 200 ℃, gets the smart product of the light yellow arborescens PCS precursor of 308.5g after the cooling.
The thick product synthetic yield of present embodiment PCS precursor is 63.8%; Can be dissolved in organic solvents such as THF, YLENE.By the smart product of PCS precursor, yield is 61.7%.Through test, oxygen element content is 0.38wt%, and the oxygen element content that transforms synthetic PCS precursor with existing constant-pressure and high-temperature cracking is suitable.
The X-photoelectron spectrum figure (XPS) of the PCS precursor product that Fig. 2 makes for embodiment 1.Can know by Fig. 2, transform the XPS spectrum figure basically identical of synthetic PCS precursor, explain in the molecular structure of catalysis synthetic PCS precursor of the present invention and do not introduce harmful element or group with existing constant-pressure and high-temperature cracking.
The FT IR spectrogram of the PCS precursor that Fig. 3 makes for embodiment 1.Can know by Fig. 3, transform the FT IR spectrogram basically identical of synthetic PCS precursor, explain in the molecular structure of catalysis synthetic PCS precursor of the present invention and do not introduce new group or structure with existing constant-pressure and high-temperature cracking.SiH/SiCH among the FT IR
3The ratio of absorbancy is 1.04, explains that catalysis synthetic PCS precursor of the present invention has higher SiH content.
The PCS precursor that Fig. 4 makes for embodiment 1
1H NMR spectrogram.Can know by Fig. 4, transform synthetic PCS precursor with existing constant-pressure and high-temperature cracking
1H NMR spectrogram basically identical.The Si-H peak area is 0.13 with the ratio of C-H peak area, explains that catalysis synthetic PCS precursor of the present invention has higher SiH content.
The PCS precursor that Fig. 5 makes for embodiment 1
29Si NMR spectrogram.Can know by Fig. 5, transform synthetic PCS precursor with existing constant-pressure and high-temperature cracking
29Si NMR spectrogram basically identical.SiC
3H/SiC
4The ratio of peak area is 1.26, explains that catalysis synthetic PCS precursor of the present invention has higher linearity.
(1) the constant-pressure and high-temperature cracking is transformed synthesis system and vacuumize, replace high pure nitrogen, repeat 3 times; (2) under the protection of high pure nitrogen, 500g is gathered silicon-carbon silane introduce in the constant-pressure and high-temperature cracking conversion synthesis system; (3) (its specific surface area is 820g/m with catalyzer titanium oxide
2) 3.0g is incorporated into the constant-pressure and high-temperature cracking and transforms in the synthesizer, continue to stir; (4) be warming up to 430 ℃ of reaction 12h, be warming up to 460 ℃ of reaction 2h again; (5) be cooled to room temperature, promptly get the thick product of 301g PCS precursor; Thick product is through xylene soluble, filtration, and filtrating is rotated distillation at 160 ℃, is cooled to room temperature and gets the smart product of the light yellow arborescens PCS precursor of 281.5g.
The thick product synthetic yield of present embodiment PCS precursor is 60.2%, dissolves in organic solvents such as THF, YLENE; By the smart product of PCS precursor, yield is 56.3%.The XPS spectrum figure of PCS precursor, FT IR spectrogram,
1H NMR spectrogram,
29Si NMR spectrogram respectively with Fig. 2-5 basically identical, only each peak intensity is slightly different.
(1) the constant-pressure and high-temperature cracking is transformed synthesis system and vacuumize, replace high pure nitrogen, triplicate; (2) under the protection of high pure nitrogen, 500g is gathered silicon-carbon silane introduce in the constant-pressure and high-temperature cracking conversion synthesis system; (3) (its specific surface area is 730g/m with the catalyst oxidation sial
2) 4.0g is incorporated into the constant-pressure and high-temperature cracking and transforms in the synthesizer, continue to stir; (4) be warming up to 410 ℃ of reaction 2h, be warming up to 420 ℃ of reaction 10h again, be warming up to 460 ℃ of reaction 2h again; (5) be cooled to room temperature, promptly get the thick product of 356g PCS precursor; Thick product is through xylene soluble, filtration, and filtrating is rotated distillation at 200 ℃, is cooled to room temperature, gets the smart product of the light yellow arborescens PCS precursor of 340.5g.
The thick product synthetic yield of present embodiment PCS precursor is 71.2%, can be dissolved in organic solvents such as THF, YLENE.By the smart product of PCS precursor, yield is 68.1%.PCS precursor XPS spectrum figure, FT IR spectrogram,
1H NMR spectrogram,
29Si NMR spectrogram respectively with Fig. 2-Fig. 5 basically identical, only each peak intensity is slightly different.
(1) the constant-pressure and high-temperature cracking is transformed synthesis system and vacuumize, the displacement high pure nitrogen repeats 3 times; (2) under the protection of high pure nitrogen, 500g is gathered silicon-carbon silane introduce in the constant-pressure and high-temperature cracking conversion synthesis system; (3) (its specific surface area is 760g/m with catalyst oxidation silicon titanium
2) 4.0g is incorporated into the constant-pressure and high-temperature cracking and transforms in the synthesizer, continue to stir; (4) be warming up to 430 ℃ of reaction 12h, be warming up to 460 ℃ of reaction 3h again; (5) be cooled to room temperature, get the thick product of 326.5g PCS precursor; Thick product is through xylene soluble, filtration, and filtrating is rotated distillation at 160 ℃, is cooled to room temperature, gets the smart product of the light yellow arborescens PCS precursor of 311g.
The thick product synthetic yield of present embodiment PCS precursor is 65.3%, can be dissolved in organic solvents such as THF, YLENE.By the smart product of PCS precursor, yield is 62.2%.The XPS spectrum figure of PCS precursor, FT IR spectrogram,
1H NMR spectrogram,
29Si NMR spectrogram respectively with Fig. 2-Fig. 5 basically identical, only each peak intensity is slightly different.
(1) the constant-pressure and high-temperature cracking is transformed synthesis system and vacuumize, replace high pure nitrogen, repeat 3 times; (2) under the protection of high pure nitrogen, 500g is gathered silicon-carbon silane introduce in the constant-pressure and high-temperature cracking conversion synthesis system; (3) (its specific surface area is 830g/m with catalyst oxidation silicon titanium aluminium
2) 5.0g is incorporated into the constant-pressure and high-temperature cracking and transforms in the synthesizer, continue to stir; (4) be warming up to 420 ℃ of reaction 10h, be warming up to 460 ℃ of reaction 4h again; (5) be cooled to room temperature, promptly get the thick product of 378g PCS precursor, thick product is through xylene soluble, filtration, and filtrating is rotated distillation at 180 ℃, is cooled to room temperature, gets the smart product of the light yellow arborescens PCS precursor of 361.5g.
The thick product synthetic yield of present embodiment PCS precursor is 75.6%, can be dissolved in organic solvents such as THF, YLENE.By the smart product of PCS precursor, yield is 72.3%.The XPS spectrum figure of PCS precursor, FT IR spectrogram,
1H NMR spectrogram,
29Si NMR spectrogram respectively with Fig. 2-Fig. 5 basically identical, only each peak intensity is slightly different.
Visible from the above embodiment, be raw material to gather silicon-carbon silane, with MOXs such as aluminum oxide, titanium oxide; Or be catalyzer with composite oxides such as oxidation sial, silicon oxide titanium, silicon oxide titanium aluminium, through control certain reaction condition, can shorten the reaction times; Improve reaction efficiency; Improve the synthetic yield of polycarbosilane precusor, in the polycarbosilane precusor structure, do not introduce harmful assorted element or group, improve the linear lag of polycarbosilane precusor molecular structure.The synthetic polycarbosilane precusor is suitable for preparing SiC fiber and SiC ceramic matric composite.
Claims (4)
1. the process for catalytic synthesis of a polycarbosilane precusor is characterized in that, may further comprise the steps: (1) transforms synthesizer to the constant-pressure and high-temperature cracking and vacuumizes, and, repeats 2-4 time to normal pressure with the nitrogen replacement gas reactor; (2) will gather silicon-carbon silane is incorporated in the constant-pressure and high-temperature cracking conversion synthesizer; (3) with the composite oxides of catalyst metal oxide compound or silicon oxide and MOX, to introduce the constant-pressure and high-temperature cracking and transform in the synthesizer, catalyst consumption is to gather 0.1%～5% of silicon-carbon silane quality; (4) temperature programming to 400 ℃～460 ℃, reaction 10h～16h is cooled to room temperature; (5) go on foot the thick product of gained through xylene soluble, filtration with (4), filtrating is rotated distillation at 150 ℃～210 ℃, is cooled to room temperature.
2. the process for catalytic synthesis of polycarbosilane precusor according to claim 1 is characterized in that, said MOX is aluminum oxide or titanium oxide.
3. the process for catalytic synthesis of polycarbosilane precusor according to claim 1 is characterized in that, the composite oxides of said silicon oxide and MOX are oxidation sial, silicon oxide titanium or oxidation sial titanium.
4. according to the process for catalytic synthesis of one of claim 1-3 described polycarbosilane precusor, it is characterized in that, in the step (3), the specific surface area>=600g/m of catalyzer
2
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772710A (en) * | 2014-02-26 | 2014-05-07 | 中国人民解放军国防科学技术大学 | Synthesis method of spinning-grade polycarbosilane with high softening point |
| CN106045549A (en) * | 2016-05-30 | 2016-10-26 | 西北工业大学 | Method using sol-gel method to synthesize spiral ZrC whiskers in in-situ manner |
| CN109824905A (en) * | 2019-01-28 | 2019-05-31 | 江西嘉捷信达新材料科技有限公司 | High temperature resistant polycarbosilane precusor and preparation method thereof |
| CN112280049A (en) * | 2020-11-05 | 2021-01-29 | 江西信达航科新材料科技有限公司 | High-strength polycarbosilane and preparation method thereof |
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| CN103772710A (en) * | 2014-02-26 | 2014-05-07 | 中国人民解放军国防科学技术大学 | Synthesis method of spinning-grade polycarbosilane with high softening point |
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| CN106045549A (en) * | 2016-05-30 | 2016-10-26 | 西北工业大学 | Method using sol-gel method to synthesize spiral ZrC whiskers in in-situ manner |
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| CN109824905A (en) * | 2019-01-28 | 2019-05-31 | 江西嘉捷信达新材料科技有限公司 | High temperature resistant polycarbosilane precusor and preparation method thereof |
| CN109824905B (en) * | 2019-01-28 | 2021-06-29 | 江西嘉捷信达新材料科技有限公司 | High-temperature-resistant polycarbosilane precursor and preparation method thereof |
| CN112280049A (en) * | 2020-11-05 | 2021-01-29 | 江西信达航科新材料科技有限公司 | High-strength polycarbosilane and preparation method thereof |
| CN112280049B (en) * | 2020-11-05 | 2022-04-22 | 江西信达航科新材料科技有限公司 | High-strength polycarbosilane and preparation method thereof |
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| CN102585235B (en) | 2013-08-28 |
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