CN109265687B - Preparation method of polycarbosilane containing heterogeneous elements - Google Patents
Preparation method of polycarbosilane containing heterogeneous elements Download PDFInfo
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/398—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing boron or metal atoms
Abstract
The invention discloses a preparation method of polycarbosilane containing heterogeneous elements. The method comprises the steps of taking liquid low-molecular-weight poly-silicon carbosilane and halide or organic complex containing heterogeneous elements as raw materials, placing the raw materials in a high-temperature high-pressure reaction device, vacuumizing and sealing the reaction device under the condition of an alkali metal silicon-aluminum compound catalyst, heating the reaction device to 350-450 ℃, carrying out closed reaction, cooling the reaction device to room temperature after the reaction is finished, and discharging gas in the reaction system to obtain a crude product containing the heterogeneous elements, namely the poly-silicon carbosilane. The method can shorten the reaction time and improve the preparation efficiency, and the prepared precursor has less branching and cyclic structure and higher Si-H content, thereby being beneficial to the improvement of the spinnability of the precursor and the control of the oxygen content and the structure in the ceramic process.
Description
Technical Field
The invention belongs to the technical field of silicon carbide precursor preparation, and particularly relates to a preparation method of carbosilane containing heterogeneous elements.
Background
Continuous silicon carbide fiber reinforced silicon carbide based composite material (SiC)fthe/SiC) has the characteristics of small density, high temperature resistance, corrosion resistance, high strength and the like, is widely applied to the fields of heat-resistant parts of aerospace engines, high-temperature gas filtration, heat exchangers and the like, and is considered as one candidate of a new-generation accident fault-tolerant nuclear fuel cladding material due to the characteristics of neutron irradiation resistance, high-temperature oxidation resistance and the like.
Since Yajima et al of northeast university of Japan began to prepare SiC fibers by using Polycarbosilane (PCS) as a precursor, the organic precursor conversion method gradually becomes an important method for preparing SiC fibers and ceramics. It is a method that uses organic polymer as precursor, uses its soluble characteristic to make it form, then makes it be converted into inorganic ceramic material by high-temp. heat treatment.
PCS is one of the important precursors for SiC fibers and ceramics. When PCS is used as a SiC fiber precursor, the SiC fiber precursor is generally required to be not melted by air, so that the final fiber contains excessive oxygen and is combined with carbon and silicon elements to form SiCxOyPhase, above 1400 ℃, decomposes, causing rapid degradation of fiber properties. When PCS is used as a ceramic precursor, the size of beta-SiC microcrystal can grow rapidly at the temperature of more than 1400 ℃, so that the interface stress between crystal grains is increased, and the mechanical property of SiC ceramic is reduced. Heterogeneous elements including aluminum, titanium, zirconium, iron, yttrium, lanthanum and the like are introduced into the PCS, some elements can increase densification and inhibit grains from growing rapidly in the high-temperature sintering process, so that the ultrahigh-resistant performance of a final product is improved, and some elements can endow electromagnetic and wave-absorbing performance and increase the functional attributes of the final product.
Taking polyaluminum carbosilane (PACS) as an example, the following methods are mainly used for preparing the polycarbosilane containing the foreign elements at present:
(1) solid Polydimethylsilane (PDMS) or Polycarbosilane (PCS) is reacted with an aluminum-containing compound. Ishikawa et al (Nature,1998,391:773-775) in Japan employ solid PCS and aluminum acetylacetonate (Al (AcAc)3) Reacting at 300 ℃ under normal pressure to generate PACS; chen Jiangxi et al (Ph. thesis of Xiamen university, 2007) prepared PACS in a closed reaction kettle by using solid PDMS; in CN201410675365.4, PCS and an oxygen-free monofunctional compound are used as raw materials to react at the temperature of 130-145 ℃, and then the temperature is raised to 380-450 ℃ and the temperature is preserved for 1-5 hours to obtain the PACS.
(2) Liquid Polycarbosilane (PSCS) or polycarbosilane (LPCS) with Al (AcAc)3The reaction is carried out under normal pressure. CN200910111053.X Liquid Polycarbosilane (LPCS) and Al (AcAc)3The PACS is prepared by reaction at the temperature of 420 ℃ and 300 ℃ as raw materials, and the PACS obtained by the method has low molecular weight and softening point and is not suitable for being used as a fiber precursor. In order to increase the molecular weight of PACS, a cracking column is usually added, and the cracking temperature is usually above 500 ℃ (Zhao gener, university of Beijing technology, 2007, 29: 130-.
In the various methods for preparing the PACS, when solid PDMS, PCS or PSCS with higher molecular weight reacts with an aluminum-containing compound, the problems of uneven heat conduction of solid materials and difficult control of the reaction often exist; the reaction is carried out under the normal pressure state, and the aluminum-containing compound is easy to volatilize, so that the aluminum content in the precursor is difficult to control; when liquid LPCS or PSCS is reacted with an aluminum-containing compound under normal pressure, the reaction time is often long (40 hours or more, particularly when prepared in large quantities), and the use of an ultra-high cracking temperature leads to an increase in branching and cyclic structures in the precursor, which is disadvantageous for spinning.
Similar problems to PACS also exist in the preparation of polycarbosilane precursors containing other foreign elements.
Disclosure of Invention
The technical purpose of the invention is to provide a preparation method of heterogeneous element-containing polycarbosilane, aiming at the problems in the preparation of heterogeneous element-containing polycarbosilane, the method has high preparation efficiency, and the prepared heterogeneous element-containing polycarbosilane has an excellent structure.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows: a preparation method of polycarbosilane containing heterogeneous elements is characterized by comprising the following steps: taking poly-silicon carbosilane and halide or organic complex containing heterogeneous elements as raw materials, wherein the poly-silicon carbosilane is a low molecular product of poly-dimethyl silane after pyrolysis, is in a liquid state at room temperature, and has a molecular weight of less than 1000 g/mol;
placing the raw materials in a high-temperature high-pressure reaction device, vacuumizing and sealing the high-temperature high-pressure reaction device in the presence of an alkali metal silicon-aluminum compound catalyst, and then heating the reaction device to 350-; after the reaction is finished, cooling to room temperature, and discharging gas in the reaction system to obtain a crude product containing heterogeneous element polycarbosilane.
Preferably, the reaction apparatus is sealed after replacing the reaction apparatus with nitrogen or an inert gas for 2 or more times and then evacuating.
Preferably, the obtained crude product containing the heterogeneous element polycarbosilane is added with an organic solvent for dissolving, then the crude product is filtered, and the filtered product is cooled to room temperature after vacuum distillation at the temperature of 200-350 ℃ to obtain the heterogeneous element-containing polycarbosilane. The organic solvent is not limited, and comprises one or more of benzene, toluene, xylene, tetrahydrofuran, chloroform, n-hexane and the like. In the vacuum distillation process, the vacuum state is preferably a pressure of less than 20 Pa.
The heterogeneous elements in the invention are elements except carbon, silicon, hydrogen and oxygen, and include but are not limited to one or more of aluminum, iron, zirconium, titanium, cobalt, nickel, niobium, yttrium, lanthanum and the like.
The heterogeneous element-containing organic complex comprises one or more of aluminum acetylacetonate, aluminum alkoxide, iron acetylacetonate, ferrocenium, zirconium acetylacetonate, titanium acetylacetonate, cobalt acetylacetonate, nickel acetylacetonate, niobium acetylacetonate, yttrium acetylacetonate, lanthanum acetylacetonate, and the like.
In the invention, the alkali metal aluminum silicon compound has a porous structure and high temperature resistance, and the structure is not changed below 600 ℃. Wherein the pore size is preferably less than 1 μm.
In the present invention, the heterogeneous element-containing halide or organic complex is collectively referred to as a heterogeneous element-containing compound, and the amount of the heterogeneous element-containing compound added is preferably 0.1% to 10%, more preferably 2% to 8%, based on the mass of the polysilanesilane.
Preferably, the addition amount of the alkali metal aluminum silicon compound accounts for 1-10% of the mass of the polysilanesilane.
Preferably, the high-temperature high-pressure reaction device is evacuated to a pressure of less than 5 Pa.
Preferably, the temperature of the reaction device is raised to 400-450 ℃.
Preferably, the reaction is carried out in a closed environment for 3 to 20 hours, more preferably for 5 to 15 hours.
Compared with the prior art, the invention takes low molecular liquid poly silicon carbosilane and halide or organic complex containing heterogeneous elements as raw materials, adopts a high-temperature and high-pressure device under the condition of the existence of an alkali metal silicon-aluminum compound catalyst, is sealed after vacuumizing, and heats up to react, the pressure in the device is increased in the reaction process, and can reach 5MPa-15MPa, and the invention has the following beneficial effects:
(1) the liquid low-molecular-weight silicon carbosilane is used as a raw material, so that the problem of uneven heat transfer of solid materials can be effectively avoided, the reaction process can be controlled, and the quality of a final product can be improved;
(2) the reaction time can be shortened and the preparation efficiency can be improved by adopting a high-temperature and high-pressure method and using a certain amount of alkali metal silicon-aluminum compound catalyst in a matching way;
(3) the temperature is increased to 350-450 ℃, the use of ultrahigh temperature is avoided, the molecular structure of the polycarbosilane containing the heterogeneous elements can be optimized, the prepared polycarbosilane containing the heterogeneous elements has less molecular branching and cyclic structure, and the improvement of the spinnability is facilitated; in addition, the sublimation of the compound containing the heterogeneous elements is avoided, and the control of the content of the heterogeneous elements in the polycarbosilane containing the heterogeneous elements is facilitated.
Drawings
FIG. 1 is an FTIR spectrum of PACS-1 prepared in example 1 of the present invention.
FIG. 2 is a photograph of PACS-1 obtained in example 1 of the present invention29And (3) a SiNMR spectrogram.
FIG. 3 is a photograph of PACS-1 obtained in example 1 of the present invention27AlNMR spectrum.
Detailed Description
The present invention is described in further detail below with reference to examples, which are intended to facilitate the understanding of the present invention without limiting it in any way.
Example 1:
the polydimethylsiloxane is subjected to pyrolysis to obtain the polysilacarbosilane, the molecular weight of which is less than 1000g/mol, and the polysilacarbosilane is liquid at room temperature. Adding 1000g of liquid silicon carbosilane, 30g of aluminum acetylacetonate and 20g of alkali metal silicon-aluminum compound into a high-temperature high-pressure device, replacing the kettle with high-purity nitrogen for three times, pumping to a vacuum state, and sealing the device; then, starting temperature rise, raising the temperature to 410 ℃ at a certain temperature rise rate, and stopping after reacting for 8 hours. And when the temperature is reduced to the room temperature state, taking out the crude product PACS-1 of the reactant polyaluminocarbosilane to be tested.
FIG. 1 is an FTIR spectrum of PACS-1. This spectrum is similar to the FTIR spectrum of common polycarbosilanes. In the drawing at 2100cm-1Intensity of the peak representing Si-H to 1250cm-1Wherein represents Si-CH3The ratio of the intensities of the peaks was taken as the relative Si-H content, and the ratio wasThe value was 0.79.
FIG. 2 is that of PACS-129And (3) a SiNMR spectrogram. In the figure, SiC4Peak and SiC3The area ratio of the H peaks is 1.56, which may represent the degree of branching of the molecular structure to some extent.
FIG. 3 is that of PACS-127AlNMR spectrum. AlO in the figure6、AlO5、AlO4The presence of various ligands indicates that the Al element is incorporated into the precursor molecule, which is polyaluminocarbosilane.
In addition, the weight average molecular weight of PACS-1 was determined by GPC to be 3210g/mol, and the molecular weight distribution coefficient was 3.1; the softening point of PACS-1 was 135 ℃ as measured by a melting point apparatus.
Comparative example 1:
this example is a comparative example to example 1 above.
In this comparative example, liquid polycarbosilane was used, which was obtained by pyrolysis of polydimethylsiloxane, having a molecular weight of less than 1000g/mol, and being liquid at room temperature, as in example 1.
1000g of liquid silicon carbosilane and 30g of aluminum acetylacetonate are added into a high-temperature normal-pressure reaction device, and the high-temperature normal-pressure reaction device comprises a reaction kettle and a pyrolysis column. And replacing the kettle with high-purity nitrogen for three times, starting the kettle to heat to 410 ℃ under normal pressure under the protection of nitrogen, starting the cracking column to heat to 500 ℃ at the same time, and stopping the reaction after 20 hours. And obtaining a crude polyaluminocarbosilane product PACS-2.
Partial test results for this PACS-2 are as follows:
the relative content of Si-H in an FTIR spectrogram is 0.71;29SiC in SiNMR spectrogram4Peak and SiC3The area ratio of the H peak is 2.48; the weight average molecular weight was 3120g/mol and the molecular weight distribution coefficient was 30 ℃ as determined by GPC; the softening point was determined to be 145 ℃ by a melting point apparatus.
Comparing PACS-1 with PACS-2, the high-temperature high-pressure method for preparing PACS does not need a high-temperature cracking column, has shorter time and greatly improves the preparation efficiency when compared with the high-temperature normal-pressure method; meanwhile, the molecular structure has lower branching degree and higher Si-H relative content, which is beneficial to the improvement of the spinnability of the precursor and the structural control of the subsequent ceramic formation.
Example 2:
in this example, liquid polycarbosilane is used, which is the same as the liquid polycarbosilane in example 1, and is obtained by pyrolysis of polydimethylsiloxane, and has a molecular weight of less than 1000g/mol, and is liquid at room temperature.
1000g of liquid silicon carbosilane, 40g of iron acetylacetonate and 20g of alkali metal silicon-aluminum compound are added into a high-temperature high-pressure device, the kettle is replaced by high-purity nitrogen for three times, and then the kettle is pumped to a vacuum state and sealed. Then, the temperature is raised to 420 ℃ at a certain heating rate, and the reaction is stopped after 6 hours. And taking out the product after the temperature is reduced to room temperature to obtain a crude product PFCS of the polyferric carbon silane.
Partial test results for this PFCS are as follows: the relative content of Si-H in an FTIR spectrogram is 0.73; the weight average molecular weight is 3310g/mol and the molecular weight distribution coefficient is 3.2 in GPC measurement; the softening point of the melt was measured by a melting point tester to be 156 ℃.
Example 3:
in this example, liquid polycarbosilane is used, which is the same as the liquid polycarbosilane in example 1, and is obtained by pyrolysis of polydimethylsiloxane, and has a molecular weight of less than 1000g/mol, and is liquid at room temperature.
1000g of liquid silicon carbosilane, 45g of zirconium acetylacetonate and 25g of alkali metal silicon aluminum compound are added into a high-temperature high-pressure device, the kettle is replaced by high-purity nitrogen for three times, and then the kettle is pumped to a vacuum state and sealed. Then, the temperature is raised to 425 ℃ at a certain temperature raising rate, and the reaction is stopped after 10 hours. And taking out the crude product PZCS after the temperature is reduced to room temperature.
Partial test results for this PZCS are as follows: the relative content of Si-H in an FTIR spectrogram is 0.75; the weight average molecular weight in GPC measurement was 3415g/mol, and the molecular weight distribution coefficient was 3.15; the softening point measured by a melting point tester is 160 ℃.
Example 4:
in this example, liquid polycarbosilane is used, which is the same as the liquid polycarbosilane in example 1, and is obtained by pyrolysis of polydimethylsiloxane, and has a molecular weight of less than 1000g/mol, and is liquid at room temperature.
1000g of liquid silicon carbon silane, 50g of lanthanum acetylacetonate and 15g of alkali metal silicon aluminum compound are added into a high-temperature and high-pressure device, the kettle is replaced by high-purity nitrogen for three times, and then the kettle is pumped to a vacuum state and sealed. Then, starting temperature rise, raising the temperature to 420 ℃ at a certain temperature rise rate, and stopping reaction after 12 hours. And taking out the mixture after the temperature is reduced to room temperature to obtain the poly lanthanum carbon silane PLCS.
Partial test results for this PLCS are as follows: the relative content of Si-H in an FTIR spectrogram is 0.72; the weight average molecular weight of the gel was 3230g/mol and the molecular weight distribution coefficient was 3.25 in terms of GPC measurement; the softening point of the melt point was determined to be 148 ℃.
Example 5:
in this example, liquid polycarbosilane is used, which is the same as the liquid polycarbosilane in example 1, and is obtained by pyrolysis of polydimethylsiloxane, and has a molecular weight of less than 1000g/mol, and is liquid at room temperature.
1000g of liquid silicon carbosilane, 45g of yttrium acetylacetonate and 25g of alkali metal silicon-aluminum compound are added into a high-temperature high-pressure device, the kettle is replaced by high-purity nitrogen for three times, and then the kettle is pumped to a vacuum state and sealed. Then, the temperature is raised to 430 ℃ at a certain temperature raising rate, and the reaction is stopped after 6 hours. And taking out the product after the temperature is reduced to room temperature to obtain a crude product PYCS of the poly yttrium carbon silane.
The results of a partial test of this PYCS are as follows: the relative content of Si-H in an FTIR spectrogram is 0.75; the weight average molecular weight is 3310g/mol and the molecular weight distribution coefficient is 3.4 by GPC measurement; the softening point measured by a melting point tester was 138 ℃.
The embodiments described above are intended to illustrate the technical solutions of the present invention in detail, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modification, supplement or similar substitution made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (13)
1. A preparation method of polycarbosilane containing heterogeneous elements is characterized by comprising the following steps: taking poly-silicon carbosilane and halide or organic complex containing heterogeneous elements as raw materials, wherein the poly-silicon carbosilane is a low molecular product of poly-dimethyl silane after pyrolysis, is in a liquid state at room temperature, and has a molecular weight of less than 1000 g/mol;
placing the raw materials in a high-temperature high-pressure reaction device, vacuumizing and sealing the high-temperature high-pressure reaction device in the presence of an alkali metal silicon-aluminum compound catalyst, and then heating the reaction device to 350-; after the reaction is finished, cooling to room temperature, and discharging gas in the reaction system to obtain a crude product containing heterogeneous element polycarbosilane.
2. The method of preparing polycarbosilane containing foreign elements as set forth in claim 1, wherein: the heterogeneous elements comprise one or more of aluminum, iron, zirconium, titanium, cobalt, nickel, niobium, yttrium and lanthanum.
3. The method of preparing polycarbosilane containing foreign elements as set forth in claim 1, wherein: the organic complex containing heterogeneous elements comprises one or more of aluminum acetylacetonate, aluminum alkoxide, ferric acetylacetonate, cyclopentadienyl iron, zirconium acetylacetonate, titanium acetylacetonate, cobalt acetylacetonate, nickel acetylacetonate, niobium acetylacetonate, yttrium acetylacetonate and lanthanum acetylacetonate.
4. The method of preparing polycarbosilane containing foreign elements as set forth in claim 1, wherein: the halide containing the heterogeneous elements and the organic complex are collectively called as heterogeneous element-containing compounds, and the addition amount of the heterogeneous element-containing compounds accounts for 0.1-10% of the mass of the polysilanesilane.
5. The method according to claim 4, wherein the heterogeneous element-containing polycarbosilane is prepared by the following steps: the addition amount of the compound containing the heterogeneous elements accounts for 2-8% of the mass of the polysilanesilane.
6. The method of preparing polycarbosilane containing foreign elements as set forth in claim 1, wherein: the addition amount of the alkali metal aluminum silicon compound accounts for 1-10% of the mass of the polysilanesosilane.
7. The method of preparing polycarbosilane containing foreign elements as set forth in claim 1, wherein: and vacuumizing the high-temperature high-pressure reaction device until the pressure is less than 5 Pa.
8. The method of preparing polycarbosilane containing foreign elements as set forth in claim 1, wherein: the temperature of the reaction device is raised to 400-450 ℃.
9. The method of preparing polycarbosilane containing foreign elements as set forth in claim 1, wherein: sealing and reacting for 3-20 h.
10. The method of preparing polycarbosilane containing foreign elements as set forth in claim 9, wherein: and sealing and reacting for 5-15 h.
11. The method of preparing polycarbosilane containing foreign elements as set forth in claim 1, wherein: and adding an organic solvent into the obtained crude product containing the heterogeneous element polycarbosilane for dissolving, then filtering, and cooling the filtered product to room temperature after vacuum distillation at 200-350 ℃ to obtain the heterogeneous element-containing polycarbosilane.
12. The method of preparing polycarbosilane containing foreign elements as set forth in claim 1, wherein: the organic solvent comprises one or more of benzene, toluene, xylene, tetrahydrofuran, chloroform and n-hexane.
13. The process for preparing a heteroelement-containing polycarbosilane as claimed in any one of claims 1 to 12, wherein: in the reaction process, the pressure in the high-temperature high-pressure reaction device reaches 5MPa-15 MPa.
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| CN110698678B (en) * | 2019-10-24 | 2022-06-24 | 中国科学院宁波材料技术与工程研究所 | Liquid curable boron-containing polycarbosilane and preparation method thereof |
| CN112266482B (en) * | 2020-10-23 | 2022-02-18 | 浙江华茂航天科技股份有限公司 | Polyaluminocarbosilane and preparation method thereof |
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| CN106278274A (en) * | 2016-08-03 | 2017-01-04 | 湖南博翔新材料有限公司 | A kind of preparation method containing composition metal phase ceramics precursor |
| CN108623812A (en) * | 2017-03-23 | 2018-10-09 | 中国科学院上海应用物理研究所 | Polycarbosilane and preparation method thereof containing heterogeneous element |
| CN107057071A (en) * | 2017-05-15 | 2017-08-18 | 中国人民解放军国防科学技术大学 | The preparation method of polycarbosilane precusor |
| CN107555997A (en) * | 2017-09-05 | 2018-01-09 | 湖南博翔新材料有限公司 | A kind of preparation method of the precursor body of poly carbon silane ceramics containing beryllium |
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