CN114456392B - Benzoyl polysilazane and preparation method thereof - Google Patents
Benzoyl polysilazane and preparation method thereof Download PDFInfo
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- CN114456392B CN114456392B CN202210246706.0A CN202210246706A CN114456392B CN 114456392 B CN114456392 B CN 114456392B CN 202210246706 A CN202210246706 A CN 202210246706A CN 114456392 B CN114456392 B CN 114456392B
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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
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Abstract
The invention relates to benzoyl polysilazane and a preparation method thereof, in particular to a structure shown in a formula (I). The polysilazane of the invention designs and synthesizes a compound shown as a formula (I) with a novel structure, and the compound has benzoyl and monobenzeneCompared with the similar compounds, the compound has the characteristic of high porcelain yield, can be used for preparing high-performance materials such as ceramics, ceramic coatings, fibers and the like, and has wide application.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to benzoyl polysilazane and a preparation method of the benzoyl polysilazane.
Background
Polysilazane is a series of compounds whose main chain uses Si-N bond as repeating unit, on one hand, the Si-N bond has larger bond energy and higher thermal stability, on the other hand, the main chain of the molecule or the tail end of the molecule contains carbon-carbon triple bond, so that it can be cross-linked and solidified at a certain temperature to obtain thermosetting resin with good compactness, and further raise the heat resistance of the resin. Thus. Polysilazane as the ceramic precursor can be prepared into silicon nitride (Si 3N 4) and silicon carbon nitride (SixNyCz) ceramics, which have excellent properties of high temperature resistance, wear resistance, corrosion resistance, etc., and can be made into ceramic coatings, ceramic fibers, nanomaterials, magnetic ceramics, ceramic Matrix Composites (CMC), ultra-high temperature materials, bulk ceramics, catalysts, porous materials, lithium battery anodes, 3D printing materials, adhesives for ceramics, multilayer connection for computer chips, etc. Therefore, a reasonable design is required to realize a better performance of polysilazane.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides benzoyl polysilazane and a preparation method thereof.
To achieve the object of the present invention, in one aspect, the present invention provides a benzoylpolysilazane having a structure represented by the following formula (I),
wherein m and n are each independently a natural number; preferably m, n are each independently a natural number between 1 and 10.
In another aspect, the present invention provides a process for the preparation of a compound of formula (I) comprising the reaction steps of:
1) Under the protection of inert gas, mixing n-butyl lithium and an organic solvent according to the volume ratio of 1-1;
2) Under the protection of inert gas, slowly dripping the obtained mixed solution into organic solution of organosilane while stirring, and reacting to obtain chlorosilane oligomers;
3) Dissolving the obtained chlorosilane oligomer and an organic solvent according to the weight ratio of 1 to 1.
Preferably, the organic solvent is one or more selected from alkanes with 6-8 carbon atoms, aromatic hydrocarbons, tetrahydrofuran and diethyl ether.
Preferably, the inert gas is nitrogen or argon.
Preferably, the reaction of step 1) is carried out by stirring at-80 ℃ to-35 ℃ for 1-8 hours, and then continuing stirring at-10 ℃ to 60 ℃ for 1-36 hours.
Preferably, the reaction of step 2) is performed by stirring at-50 ℃ to 50 ℃ for 1 to 12 hours, and then continuing stirring at 0 ℃ to 80 ℃ for 2 to 30 hours.
Preferably, the reaction of step 3) is carried out by introducing ammonia gas under stirring at 10 ℃ to 50 ℃ for 1 to 15 hours.
Preferably, the reaction of step 3) is carried out by introducing ammonia gas under stirring at 10 ℃ to 50 ℃ for 1 to 15 hours, and then continuing the reaction under stirring at 20 ℃ to 100 ℃ for 1 to 12 hours.
The preparation method of benzoyl polysilazane is characterized by comprising the following reaction steps:
1) Under the protection of nitrogen, mixing n-butyllithium and tetrahydrofuran according to a volume ratio of 1-1;
2) Under the protection of nitrogen, slowly dripping the obtained mixed solution into tetrahydrofuran solution of organosilane under stirring at a temperature of between-5 and-18 ℃ to react to obtain chlorosilane oligomers;
3) Dissolving the obtained chlorosilane oligomer and tetrahydrofuran according to the weight ratio of 1-1.
Compared with the prior art, the invention has the beneficial effects that:
the inventor of the invention unexpectedly discovers that the modified polysilazane shown as the formula (I) has benzoyl, has the characteristic of high porcelain yield compared with similar monophenyl compounds, can be used for preparing high-performance materials such as ceramics, ceramic coatings, fibers and the like, and has wide application.
Detailed Description
The following representative examples are intended to better illustrate the present invention and are not intended to limit the scope of the present invention. The materials used in the following examples are all commercially available unless otherwise specified.
Example 1
170ml of tetrahydrofuran and 65ml of n-butyllithium (2.5 mol/L) were charged in a 500ml three-necked flask, and a mixed solution of 65ml of tetrahydrofuran and 49.3g of 2, 3-trichloro-1-phenylpropan-1-one was slowly dropped into the three-necked flask at-78 ℃ under a nitrogen blanket. After the dropwise addition, the mixture is kept at a low temperature and is continuously stirred for reaction for 1.5 hours, and the temperature is gradually increased to 30 ℃ and is continuously stirred for reaction for 7 hours to obtain a mixed solution.
Adding 125ml of tetrahydrofuran and 50.9g of dimethyldichlorosilane into a 500ml three-necked bottle, keeping the system at-5 ℃ by using a low-temperature bath, slowly dripping the mixed solution under the protection of nitrogen, continuously stirring for 4 hours at-5 ℃, heating to 30 ℃, continuously stirring for reaction for 6 hours, standing for layering, transferring the supernatant into another clean and dry 500ml three-necked bottle under the protection of nitrogen, washing the precipitate with tetrahydrofuran for three times, combining the filtrates, and spin-drying to obtain the brown red viscous liquid chlorosilane oligomer. By measuring the chlorine content, m in formula (I) averages 5.
And (3) dissolving 17.0g of chlorosilane oligomers prepared in the steps by using 300ml of toluene, stirring at the temperature of 30 ℃, introducing ammonia gas for reaction for 12 hours until the ammonia gas is not absorbed by the system, and then continuously introducing ammonia for 2 hours. Standing and settling, transferring the supernatant to another clean and dry 500ml three-neck flask, washing the precipitate with toluene for three times, combining the filtrates, and evaporating the solvent to obtain the brown viscous liquid polysilazane. In the formula (I), n is 5 on average.
The yield of the polysilazane prepared by the embodiment is as high as 93 percent; the strength of the SiCN fiber prepared by the method reaches 3.5GPa, and the modulus reaches 304GPa. After high-temperature oxidation at 1000 ℃ for 400 hours, the strength retention rate reaches 91 percent.
Example 2
170ml of tetrahydrofuran and 65ml of n-butyllithium (2.5 mol/L) were charged in a 500ml three-necked flask, and a mixed solution of 65ml of tetrahydrofuran and 46.3g of 2, 3-trichloro-1-phenylpropan-1-one was slowly dropped into the three-necked flask at-78 ℃ under a nitrogen blanket. Keeping the low temperature for continuously stirring and reacting for 2 hours after the dropwise adding is finished, gradually raising the temperature to 20 ℃, and continuously stirring and reacting for 8 hours to obtain a mixed solution.
Adding 125ml of tetrahydrofuran and 55.3g of dimethyldichlorosilane into a 500ml three-necked bottle, keeping the system at-15 ℃ by using a low-temperature bath, slowly dripping the mixed solution under the protection of nitrogen, continuously stirring for 3 hours at-5 ℃ after dripping is finished, heating to 20 ℃, continuously stirring for reaction for 10 hours, standing for layering, transferring the supernatant into another clean and dry 500ml three-necked bottle under the protection of nitrogen, washing the precipitate with tetrahydrofuran for three times, combining the filtrates, and spin-drying to obtain the chlorosilane oligomer of brownish red viscous liquid. By measuring the chlorine content, m in formula (I) averages 6.
And (3) dissolving 19.0g of chlorosilane oligomers prepared in the steps by using 300ml of toluene, stirring at the temperature of 30 ℃, introducing ammonia gas for reaction for 12 hours until the ammonia gas is not absorbed by the system, and then continuously introducing ammonia for 2 hours. Standing and settling, transferring the supernatant to another clean and dry 500ml three-neck bottle, washing the precipitate with toluene for three times, combining the filtrates, and evaporating the solvent to obtain the polysilazane as a brownish red viscous liquid. In the formula (I), n is 4 on average.
The polysilazane prepared by the embodiment has the ceramic yield as high as 91%; the strength of the SiCN fiber prepared by the method reaches 3.1GPa, and the modulus reaches 311GPa. After high-temperature oxidation at 1000 ℃ for 400 hours, the strength retention rate reaches 88 percent.
Example 3
170ml of tetrahydrofuran and 65ml of n-butyllithium (2.5 mol/L) were charged in a 500ml three-necked flask, and a mixed solution of 65ml of tetrahydrofuran and 47.1g of 2, 3-trichloro-1-phenylpropan-1-one was slowly dropped into the three-necked flask at-78 ℃ under nitrogen protection. Keeping the low temperature for continuously stirring and reacting for 2 hours after the dropwise adding is finished, gradually raising the temperature to 20 ℃, and continuously stirring and reacting for 8 hours to obtain a mixed solution.
Adding 125ml of tetrahydrofuran and 57.5g of dimethyldichlorosilane into a 500ml three-necked bottle, keeping the system at-10 ℃ by using a low-temperature bath, slowly dripping the mixed solution under the protection of nitrogen, continuously stirring for 3 hours at-5 ℃ after dripping is finished, heating to 20 ℃, continuously stirring for reaction for 10 hours, standing for layering, transferring the supernatant to another clean and dry 500ml three-necked bottle under the protection of nitrogen, washing the precipitate with tetrahydrofuran for three times, combining the filtrates, and spin-drying to obtain the brownish red viscous liquid chlorosilane oligomer. By measuring the chlorine content, m in formula (I) averages 7.
And (3) dissolving 23.0g of the chlorosilane oligomer prepared in the steps by using 300ml of toluene, stirring at the temperature of 30 ℃, introducing ammonia gas for reaction for 12 hours until the system does not absorb ammonia gas any more, and then continuously introducing ammonia for 2 hours. Standing and settling, transferring the supernatant to another clean and dry 500ml three-neck flask, washing the precipitate with toluene for three times, combining the filtrates, and evaporating the solvent to obtain the brown viscous liquid polysilazane. In the formula (I), n is 4 on average.
The yield of the polysilazane prepared by the embodiment is up to 91%; the strength of the SiCN fiber prepared by the method reaches 3.7GPa, and the modulus reaches 320GPa. After high-temperature oxidation at 1000 ℃ for 400 hours, the strength retention rate reaches 88 percent.
Comparative example 1
170ml of tetrahydrofuran and 65ml of n-butyllithium (2.5 mol/L) were charged in a 500ml three-necked flask, and a mixed solution of 65ml of tetrahydrofuran and 31.2g of (1, 2-trichloroethyl) benzene was slowly dropped into the three-necked flask at-78 ℃ under a nitrogen atmosphere. After the dropwise addition, the mixture is kept at a low temperature and is continuously stirred for reaction for 2 hours, and the temperature is gradually increased to 20 ℃ and is continuously stirred for reaction for 10 hours to obtain a mixed solution.
Adding 125ml of tetrahydrofuran and 49.9g of dimethyldichlorosilane into a 500ml three-necked bottle, keeping the system at-5 ℃ by using a low-temperature bath, slowly dripping the mixed solution under the protection of nitrogen, continuously stirring for 4 hours at-5 ℃, heating to 20 ℃, continuously stirring for reaction for 6 hours, standing for layering, transferring the supernatant into another clean and dry 500ml three-necked bottle under the protection of nitrogen, washing the precipitate with tetrahydrofuran for three times, combining the filtrates, and spin-drying to obtain the brown red viscous liquid chlorosilane oligomer. By measuring the chlorine content, m in formula (I) averages 5.
And (3) dissolving 17.0g of chlorosilane oligomers prepared in the steps by using 300ml of toluene, stirring at the temperature of 30 ℃, introducing ammonia gas for reaction for 12 hours until the ammonia gas is not absorbed by the system, and then continuously introducing ammonia for 2 hours. Standing and settling, transferring the supernatant to another clean and dry 500ml three-neck bottle, washing the precipitate with toluene for three times, combining the filtrates, and evaporating the solvent to obtain the polysilazane as a brownish red viscous liquid. In the formula (I), n is 3 on average.
Polysilazane prepared in this example gave a ceramic yield of 81%; the SiCN fiber prepared by the method has the strength of 2.1GPa and the modulus of 263GPa. After high-temperature oxidation at 1000 ℃ for 400 hours, the strength retention rate is 67%.
Although the present invention has been described in detail above, those skilled in the art will appreciate that various modifications and changes can be made to the present invention without departing from the spirit and scope of the invention. The scope of the invention is not to be limited by the above detailed description but is only limited by the claims.
Claims (10)
1. A benzoylpolysilazane characterized by having a structure represented by the following formula (I),
wherein m and n are each independently a natural number.
2. A benzoylpolysilazane according to claim 1, wherein m and n are each independently a natural number from 1 to 10.
3. A method of preparing a benzoylpolysilazane of claim 1, comprising the steps of:
1) Under the protection of inert gas, mixing n-butyl lithium and an organic solvent according to the volume ratio of 1-1;
2) Under the protection of inert gas, slowly dripping the obtained mixed solution into an organic solution of dimethyldichlorosilane under stirring to react to obtain chlorosilane oligomers;
3) Dissolving the obtained chlorosilane oligomer and an organic solvent according to the weight ratio of 1 to 1.
4. The method for preparing benzoylpolysilazane as claimed in claim 3, wherein the organic solvent is one or more selected from the group consisting of C6-C8 alkanes, aromatic hydrocarbons, tetrahydrofuran, and diethyl ether.
5. The method of claim 3, wherein the inert gas is nitrogen or argon.
6. The method of claim 3, wherein the reaction of step 1) is carried out by stirring at-80 to-35 ℃ for 1 to 8 hours, and then at-10 to 60 ℃ for 1 to 36 hours.
7. The method of claim 3, wherein the reaction in step 2) is performed by stirring at-50 ℃ to 50 ℃ for 1 to 12 hours, and then at 0 ℃ to 80 ℃ for 2 to 30 hours.
8. The method of claim 3, wherein the reaction of step 3) is performed by introducing ammonia gas at 10 to 50 ℃ for 1 to 15 hours while stirring.
9. The method of claim 3, wherein the reaction of step 3) is carried out by introducing ammonia gas at 10 to 50 ℃ under stirring for 1 to 15 hours, and then further reacting at 20 to 100 ℃ under stirring for 1 to 12 hours.
10. The method for preparing benzoylpolysilazane according to claim 3, comprising the following steps:
1) Under the protection of nitrogen, mixing n-butyllithium and tetrahydrofuran according to the volume ratio of 1-1;
2) Under the protection of nitrogen, slowly dripping the obtained mixed solution into tetrahydrofuran solution of dimethyldichlorosilane under stirring at a temperature of between 5 ℃ below zero and 18 ℃ below zero to react to obtain chlorosilane oligomers;
3) Dissolving the obtained chlorosilane oligomer and tetrahydrofuran according to the weight ratio of 1-1.
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| US5030702A (en) * | 1987-12-04 | 1991-07-09 | Hoechst Aktiengesellschaft | Polysilazanes, processes for their preparation, ceramic materials which contain silicon nitride and can be prepared from them, and preparation thereof |
| DE4217579A1 (en) * | 1992-05-27 | 1993-12-02 | Wacker Chemie Gmbh | Process for the production of polysilazanes |
| CN100408615C (en) * | 2005-05-20 | 2008-08-06 | 中国科学院化学研究所 | Diacetylene-containing poly-siloxane and method for preparing same |
| CN103724627B (en) * | 2013-11-19 | 2017-02-15 | 华东理工大学 | Polysilazane-aniline acetylene-terminated polysilazane and preparation method thereof |
| CN103881101A (en) * | 2014-03-18 | 2014-06-25 | 天津大学 | Polycarbosilazane precursor for silicon carbonitride ceramic and preparation method thereof |
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