CN114015059A - High boron content carborane polymer and synthetic method thereof - Google Patents
High boron content carborane polymer and synthetic method thereof Download PDFInfo
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Abstract
The invention belongs to the field of high molecular materials, and relates to a synthesis method of a carborane polymer with high boron content, which comprises the following steps: and reacting the alkynyl-containing polysilazane, decaborane complex and reaction solvent in an inert atmosphere at 60-120 ℃ for 7-15 h, and carrying out suction drying and sublimation to obtain the carborane polymer with high boron content. The invention successfully synthesizes the carborane polymer with high boron content and controllable boron content, and provides new possibility for the production and application of the carborane polymer.
Description
Technical Field
The invention belongs to the field of high molecular materials, and relates to a carborane polymer with high boron content and a synthesis method thereof.
Background
Carborane is an icosahedral boron hydride formed by replacing two BH units with equal charges by two CH-units, each vertex atom in carborane is hexa-coordinated, a three-center two-electron chemical bond exists, and belongs to a highly electron-deficient structure, and adjacent bond positions can be shortened, so that the closed cage-shaped structure has a highly symmetrical framework structure and a large volume, and simultaneously shows typical properties, thermal stability and chemical stability of a plurality of aromatic structures. Therefore, the unique properties of carborane make the research of the potential application of carborane attach importance to the field of polymer materials. The molecular structure with high boron content is beneficial to further application and expansion of related materials in the high-temperature ablation-resistant field such as aerospace and the like, and can greatly improve the high-temperature carbon residue rate of a resin structure and the ceramic yield of an embedded structure, so that the carborane-containing polymer with high boron content has important value in the fields of ablation-resistant materials and coatings.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a synthesis method, and successfully synthesizes a carborane polymer with high boron content and controllable boron content.
In a first aspect, the present invention provides a high boron content carborane polymer having the formula:
wherein x is any integer of 1-10000, and y is any integer of 0-10000; r1、R3、R4、R6Is independently selected from-CzH2z+1、-COOCzH2z+1、-COCzH2z+1、-Ph、-NHCzH2z+1、-OCzH2z+1、-OH-NH2Wherein z is more than or equal to 0.
In another aspect, the invention provides a method for synthesizing a carborane polymer with high boron content, which comprises the following steps:
and reacting the alkynyl-containing polysilazane, decaborane complex and reaction solvent in an inert atmosphere at 60-120 ℃ for 7-15 h, and carrying out suction drying and sublimation to obtain the carborane polymer with high boron content.
Preferably, the decaborane complex is (CH)3CN)2B10H12(abbreviated as (MeCN)2B10H12) And/or ((CH)3CH2)2S)2B10H12(abbreviated to (Et)2S)2B10H12)。
Preferably, the alkynyl-containing polysilazane has the following structural formula:
wherein n is any integer of 1-10000; r1、R3、R4、R6Is independently selected from-CzH2z+1、-COOCzH2z+1、-COCzH2z+1、-Ph、-NHCzH2z+1、-OCzH2z+1、-OH-NH2Wherein z is more than or equal to 0.
Preferably, the alkynyl-containing polysilazane is prepared by a process comprising the steps of:
(1) reacting silazane, dichlorosilane and aluminum trichloride at 40-60 ℃ for 60-80 h in an inert atmosphere, drying, and carrying out reduced pressure distillation to obtain dichlorosilazane;
(2) under the inert atmosphere, dissolving trichloroethylene in a reaction solvent, slowly dropping the trichloroethylene into a reaction bottle containing n-butyl lithium, placing the reaction bottle in a low-temperature reactor at the temperature of-60 to-80 ℃, heating to 15 to 37 ℃ after dropping, and reacting for 10 to 18 hours;
(3) and dissolving dichlorosilazane in a reaction solvent under an inert atmosphere, dripping the dichlorosilazane into the reaction system (2) at 15-37 ℃, heating to 70-90 ℃ after dripping, reacting for 10-18 h, draining, extracting, concentrating, recrystallizing, filtering, and draining to obtain the alkynyl-containing polysilazane.
Preferably, the silazane has the following structural formula:
wherein R is1、R2、R3、R4、R5、R6Is independently selected from-CzH2z+1、-COOCzH2z+1、-COCzH2z+1、-Ph、-NHCzH2z+1、-OCzH2z+1、-OH-NH2Wherein z is more than or equal to 0.
Preferably, the dichlorosilane has the following structural formula:
wherein R is7、R8Is independently selected from-CzH2z+1、-COOCzH2z+1、-COCzH2z+1、-Ph、-NHCzH2z+1、-OCzH2z+1、-OH-NH2Wherein z is more than or equal to 0.
Preferably, the molar ratio of silazane to dichlorosilane is 1: (2-3).
Preferably, the molar ratio of n-butyllithium to trichloroethylene is (2.5-3.5): 1.
preferably, the reaction solvent is one or more of xylene, benzene, dimethylether, tetrahydrofuran, toluene, and dimethylformamide.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the carborane polymer with high boron content and controllable boron content is successfully synthesized through the reaction of alkynyl-containing polysilazane and decaborane complex;
2. the invention successfully prepares dichlorosilazane through silazane, dichlorosilane and aluminum trichloride, and then the dichlorosilazane reacts with acetylene lithium under certain conditions to prepare alkynyl-containing polysilazane;
3. the carborane polymer with controllable boron content is liquid to powder solid, is easy to dissolve in various organic solvents, and can be used for preparing high-temperature-resistant composite materials, ceramic precursors, high-temperature-resistant coatings and the like;
4. the carborane polymer with high boron content obtained by the invention has excellent performance, expands the application field of carborane polymers, and provides new possibility for production and application of carborane polymers.
Drawings
FIG. 1 is a FT-IR plot of a carborane-containing polymer with high boron content in SiBCN (1:1) in example 1 of the present invention.
FIG. 2 is a nuclear magnetic hydrogen spectrum of a high boron content carborane-containing polymer in deuterated DMSO solvent in SiBCN (1:1) in example 1 of the present invention.
FIG. 3 is a nuclear magnetic boron spectrum of a high boron content carborane-containing polymer in deuterated DMSO solvent in SiBCN (1:1) in example 1 of the present invention.
FIG. 4 is a graph of argon TG for a high boron content carborane-containing polymer in SiBCN (1:1) of example 1 of the present invention.
FIG. 5 is a FT-IR plot of a carborane-containing polymer with high boron content in SiBCN (1:0.75) in example 2 of the present invention.
FIG. 6 is a nuclear magnetic hydrogen spectrum of a high boron content carborane-containing polymer in deuterated DMSO solvent in SiBCN (1:0.75) in example 2 of the present invention.
FIG. 7 is a nuclear magnetic boron spectrum of a high boron content carborane-containing polymer in deuterated DMSO solvent in SiBCN (1:0.75) in example 2 of the present invention.
FIG. 8 is a graph of argon TG for a high boron content carborane-containing polymer in SiBCN (1:0.75) in example 2 of the present invention.
FIG. 9 is a FT-IR plot of carborane-containing polymers with high boron content in SiBCN (1:0.5) in example 3 of the present invention.
FIG. 10 is a nuclear magnetic hydrogen spectrum of a high boron content carborane-containing polymer in deuterated DMSO solvent in SiBCN (1:0.5) in example 3 of the present invention.
FIG. 11 is a nuclear magnetic boron spectrum of a high boron content carborane-containing polymer in deuterated DMSO solvent in SiBCN (1:0.5) in example 3 of the present invention.
FIG. 12 is a graph of argon TG for a high boron content carborane-containing polymer of SiBCN (1:0.5) in example 3 of the present invention.
FIG. 13 is a FT-IR plot of carborane-containing polymers with high boron content in SiBCN (1:0.25) in example 4 of the present invention.
FIG. 14 is a nuclear magnetic hydrogen spectrum of a high boron content carborane-containing polymer in deuterated DMSO solvent in SiBCN (1:0.25) in example 4 of the present invention.
FIG. 15 NMR spectra of high boron content carborane-containing polymers in deuterated DMSO solvents in SiBCN (1:0.25) in example 4 of the invention.
FIG. 16 is a graph of argon TG for a high boron content carborane-containing polymer in SiBCN (1:0.25) in example 4 of the present invention.
Detailed Description
Hereinafter, embodiments will be described in detail with respect to the method of synthesizing a high boron content carborane polymer of the present invention, however, these embodiments are exemplary and the present disclosure is not limited thereto.
In some embodiments of the invention, a method of synthesizing a high boron content carborane polymer comprises the steps of:
(1) and reacting silazane, dichlorosilane and aluminum trichloride at 40-60 ℃ for 60-80 h in an inert atmosphere, drying, and distilling under reduced pressure to obtain the dichlorosilazane.
(2) Under the inert atmosphere, trichloroethylene is dissolved in a reaction solvent, and then the trichloroethylene is slowly dripped into a reaction bottle containing n-butyl lithium, the reaction bottle is placed in a low-temperature reactor at minus 60 to minus 80 ℃, the temperature is increased to 15 to 37 ℃ after the dripping is finished, and the reaction is carried out for 10 to 18 hours.
(3) And dissolving dichlorosilazane in a reaction solvent under an inert atmosphere, dripping the dichlorosilazane into the reaction system (2) at 15-37 ℃, heating to 70-90 ℃ after dripping, reacting for 10-18 h, draining, extracting, concentrating, recrystallizing, filtering, and draining to obtain the alkynyl-containing polysilazane.
(4) Reacting the alkynyl-containing polysilazane, decaborane complex and reaction solvent at 60-120 ℃ for 7-15 h in an inert atmosphere, and carrying out pumping drying and sublimation to obtain the carborane polymer with high boron content.
The whole reaction scheme is as follows:
(1)
(2)
(3)
(4)
in the reaction process, n is any integer of 1-10000, x is any integer of 1-10000, and y is any integer of 0-10000; r1、R2、R3、R4、R5、R6、R7、R8Is independently selected from-CzH2z+1、-COOCzH2z+1、-COCzH2z+1、-Ph、-NHCzH2z+1、-OCzH2z+1、-OH-NH2Wherein z.gtoreq.0, preferably, 50.gtoreq.z.gtoreq.0.
In the above step (1), the molar ratio of silazane to dichlorosilane is preferably 1: (2-3), wherein the total mass ratio of the aluminum trichloride to the silazane to the dichlorosilane is 1: (20-1000).
In the above step (2), the trichloroethylene is dissolved in the reaction solvent, and the volume ratio of the trichloroethylene to the reaction solvent is not limited, for example, the volume ratio of the trichloroethylene to the reaction solvent is 1: (10-50), slowly dropping a solution formed by dissolving trichloroethylene in a reaction solvent (the dropping speed is preferably 1-2 seconds per drop) into a reaction bottle containing n-butyl lithium, placing the reaction bottle in a low-temperature reactor at-60 to-80 ℃, heating the reaction bottle to 15-37 ℃ after the dropping is finished, and reacting for 10-18 hours. The mol ratio of n-butyllithium to trichloroethylene is preferably (2.5-3.5): 1.
in the above step (3), dichlorosilazane is dissolved in the reaction solvent, and the ratio of dichlorosilazane to reaction solvent is not limited, and for example, the ratio of the mass (g) of dichlorosilazane to the volume (ml) of reaction solvent is 1: (5-50). And (3) dripping a solution formed by dissolving dichlorosilazane in a reaction solvent into the reaction system in the step (2) at the temperature of 15-37 ℃, heating to 70-90 ℃ after dripping, reacting for 10-18 h, drying, extracting, concentrating, recrystallizing, filtering, and drying to obtain the alkynyl-containing polysilazane.
In the step (4), the alkynyl-containing polysilazane and decaborane complex are dissolved in a reaction solvent, the mass ratio of the alkynyl-containing polysilazane to the decaborane complex is not limited, and carborane polymers with different boron contents can be obtained by different mass ratios of the alkynyl-containing polysilazane to the decaborane complex; the ratio of the alkynyl-containing polysilazane and decaborane complex to the reaction solvent is also not limited, and is exemplified by a ratio of the total mass (g) of the alkynyl-containing polysilazane and decaborane complex to the volume (ml) of the reaction solvent of 1: (5-50). Dissolving the alkynyl-containing polysilazane and decaborane complex in a reaction solvent, filling the reaction solvent into an inert atmosphere, reacting for 7-15 h at the temperature of 60-120 ℃, and removing the decaborane complex through pumping drying and sublimation to obtain the carborane polymer with high boron content.
In the above steps, the reaction solvent is preferably one or more of xylene, benzene, dimethylether, tetrahydrofuran, toluene, and dimethylformamide.
In the above steps (1) to (4), the reaction is carried out in an inert atmosphere, which is a gas such as nitrogen or argon.
The technical solutions of the present invention are further described and illustrated by the following specific embodiments and the accompanying drawings, it should be understood that the specific embodiments and the accompanying drawings described herein are only for better illustrating the present disclosure, and do not limit the scope of protection. The raw materials used in the examples of the present invention are those commonly used in the art, and the methods used in the examples are those conventional in the art, unless otherwise specified.
Example 1
This example prepares a high boron content carborane polymer by:
(1) adding 21ml hexamethyldisilazane, 0.1g aluminum trichloride and 25ml dimethyldichlorosilane into a 100ml reaction eggplant bottle filled with nitrogen, raising the temperature to 60 ℃, reacting for 72 hours, vacuumizing, and distilling under reduced pressure at 40 ℃ to obtain the product, namely the tetramethyldichlorosilazane.
(2) Adding 12.4ml of 2.5mol/L n-butyllithium solution into a 100ml reaction eggplant bottle filled with nitrogen, adding 0.98ml of trichloroethylene and 20ml of tetrahydrofuran into a 50ml constant pressure funnel filled with nitrogen, placing the reaction bottle in a low-temperature reactor at the temperature of-80 ℃, dropwise adding the tetrahydrofuran solution of trichloroethylene into the n-butyllithium within one second, raising the temperature to 30 ℃ after the dropwise adding is finished, and reacting for 16 hours.
(3) Adding 2g of tetramethyl dichlorosilazane and 20ml of tetrahydrofuran into a 50ml constant pressure funnel filled with nitrogen, dripping into the system (2) at room temperature, heating to 80 ℃, refluxing, reacting for 16h, draining, extracting, concentrating, recrystallizing, filtering, draining to obtain the alkynyl-containing polysilazane.
(4) 0.65g of decaborane dodecahydrodiacetonitrile complex, 0.50g of polysilazane and 20ml of xylene are added into a reaction flask with 100ml of nitrogen inert atmosphere, heated to 120 ℃ and reacted for 8 hours, and then the decaborane dodecahydrodiacetonitrile complex is removed by pumping and sublimation to obtain a reaction product SiBCN (1: 1).
The reaction product obtained in example 1 was characterized, as shown in FIGS. 1 to 4, from the FT-IR chart, the N-H peak of 3344, the saturated C-H peak of 2962, and the Si-H peak of 1257 were observed, indicating that the polysilazane structure synthesized in the third step still exists, and the B-H peak of 2526 preliminarily indicated that decaborane was grafted to the polysilazane structure. From the nuclear magnetic hydrogen spectrum figure 2, B-H of the boron cage at 1.3-3 and N-H at 5 can be seen, further, the boron cage is not disintegrated and completely grafted on the structure of polysilazane, and the target compound is successfully synthesized. B of the boron cage at-2- < 4 >, -8- < 12 > can be seen from the nuclear magnetic boron spectrogram 3, and the boron cage is determined not to be disintegrated. From graph 4 of argon TG it can be seen that the polymer loses less weight after volatilization of small molecules at 400 ℃.
Example 2
This example prepares a high boron content carborane polymer by:
(1) adding 21ml hexamethyldisilazane, 0.15g aluminum trichloride and 25ml dimethyldichlorosilane into a 100ml reaction eggplant bottle filled with nitrogen, raising the temperature to 50 ℃, reacting for 75 hours, vacuumizing, and distilling under reduced pressure at 40 ℃ to obtain the product, namely the tetramethyldichlorosilazane.
(2) Adding 12.4ml of 2.5mol/L n-butyllithium solution into a 100ml reaction eggplant bottle filled with nitrogen, adding 0.98ml of trichloroethylene and 25ml of tetrahydrofuran into a 50ml constant pressure funnel filled with nitrogen, placing the reaction bottle in a low-temperature reactor at the temperature of-75 ℃, dropwise adding the tetrahydrofuran solution of trichloroethylene into the n-butyllithium within one second, raising the temperature to 30 ℃ after the dropwise adding is finished, and reacting for 18 hours.
(3) Adding 2g of tetramethyl dichlorosilazane and 25ml of tetrahydrofuran into a 50ml constant pressure funnel filled with nitrogen, dripping into the system (2) at room temperature, heating to 75 ℃, refluxing, reacting for 17 hours, draining, extracting, concentrating, recrystallizing, filtering, and draining to obtain the alkynyl-containing polysilazane.
(4) 0.60g of decaboron dodecahydrodiacetonitrile complex, 0.62g of polysilazane and 30ml of xylene are added into a reaction flask with 100ml of nitrogen inert atmosphere, heated to 100 ℃ and reacted for 10 hours, and then the decaboron dodecahydrodiacetonitrile complex is removed by pumping and sublimation to obtain a reaction product SiBCN (1: 0.75).
The reaction products obtained in example 2 were characterized as shown in FIGS. 5-8, FIG. 5 is a FT-IR plot of the carborane-containing polymer with high boron content in SiBCN (1:0.75), FIG. 6 is a nuclear magnetic hydrogen spectrum in a deuterated DMSO solvent of the carborane-containing polymer with high boron content in SiBCN (1:0.75) in example 2, FIG. 7 is a nuclear magnetic boron spectrum in a deuterated DMSO solvent of the carborane-containing polymer with high boron content in SiBCN (1:0.75) in example 2, and FIG. 8 is an argon TG plot of the carborane-containing polymer with high boron content in SiBCN (1:0.75) in example 2.
Example 3
This example prepares a high boron content carborane polymer by:
(1) adding 21ml hexamethyldisilazane, 0.18g aluminum trichloride and 25ml dimethyldichlorosilane into a 100ml reaction eggplant bottle filled with nitrogen, raising the temperature to 55 ℃, reacting for 70 hours, vacuumizing, and distilling under reduced pressure at 40 ℃ to obtain the product, namely the tetramethyldichlorosilazane.
(2) Adding 12.4ml of 2.5mol/L n-butyllithium solution into a 100ml reaction eggplant bottle filled with nitrogen, adding 0.98ml of trichloroethylene and 30ml of xylene into a 50ml constant pressure funnel filled with nitrogen, placing the reaction bottle in a low-temperature reactor at the temperature of-70 ℃, dropwise adding a tetrahydrofuran solution of trichloroethylene into the n-butyllithium within one second, raising the temperature to 30 ℃ after the dropwise adding is finished, and reacting for 15 hours.
(3) Adding 2g of tetramethyl dichlorosilazane and 30ml of tetrahydrofuran into a 50ml constant-pressure funnel filled with inert gas, dripping into the system (2) at room temperature, heating to 85 ℃, refluxing, repeatedly using for 15 hours, draining, extracting, concentrating, recrystallizing, filtering, and draining to obtain the alkynyl-containing polysilazane.
(4) 0.71g of decaborane dodecahydrodiacetonitrile complex, 1.09g of polysilazane and 20ml of toluene are added into a reaction flask with 100ml of nitrogen inert atmosphere, heated to 80 ℃ and reacted for 12 hours, and then the decaborane dodecahydrodiacetonitrile complex is removed by pumping and sublimation, thus obtaining the reaction product SiBCN (1: 0.5).
The reaction products obtained in example 3 were characterized as shown in FIGS. 9-12, FIG. 9 is a FT-IR plot of the carborane-containing polymer with high boron content in SiBCN (1:0.5), FIG. 10 is a nuclear magnetic hydrogen spectrum in a deuterated DMSO solvent of the carborane-containing polymer with high boron content in SiBCN (1:0.5) in example 3, FIG. 11 is a nuclear magnetic boron spectrum in a deuterated DMSO solvent of the carborane-containing polymer with high boron content in SiBCN (1:0.5) in example 2, and FIG. 12 is an argon TG plot of the carborane-containing polymer with high boron content in SiBCN (1:0.5) in example 3.
Example 4
This example prepares a high boron content carborane polymer by:
(1) adding 21ml hexamethyldisilazane, 0.20g aluminum trichloride and 25ml dimethyldichlorosilane into a 100ml reaction eggplant bottle filled with nitrogen, raising the temperature to 50 ℃, reacting for 80 hours, vacuumizing, and distilling under reduced pressure at 40 ℃ to obtain the product, namely the tetramethyldichlorosilazane.
(2) Adding 12.4ml of 2.5mol/L n-butyllithium solution into a 100ml reaction eggplant bottle filled with nitrogen, adding 0.98ml of trichloroethylene and 35ml of tetrahydrofuran into a 50ml constant pressure funnel filled with nitrogen, placing the reaction bottle in a low-temperature reactor at the temperature of-80 ℃, dropwise adding the tetrahydrofuran solution of trichloroethylene into the n-butyllithium within one second, raising the temperature to 30 ℃ after the dropwise adding is finished, and reacting for 14 hours.
(3) Adding 2g of tetramethyl dichlorosilazane and 35ml of xylene into a 50ml constant-pressure funnel filled with inert gas, dripping into the system (2) at room temperature, heating to 90 ℃, refluxing, reversely using for 14 hours, draining, extracting, concentrating, recrystallizing, filtering, draining to obtain the alkynyl-containing polysilazane.
(4) 0.32g of decaborane dodecahydrodiacetonitrile complex, 1.00g of polysilazane and 35ml of toluene are added into a reaction flask with 100ml of nitrogen inert atmosphere, heated to 60 ℃ and reacted for 14h, and then the decaborane dodecahydrodiacetonitrile complex is removed by pumping and sublimation to obtain a reaction product SiBCN (1: 0.25).
The reaction products obtained in example 4 were characterized as shown in FIGS. 13-16, FIG. 13 is a FT-IR plot of the carborane-containing polymer with high boron content in SiBCN (1:0.25), FIG. 14 is a nuclear magnetic hydrogen spectrum in a deuterated DMSO solvent of the carborane-containing polymer with high boron content in SiBCN (1:0.25) in example 4, FIG. 15 is a nuclear magnetic boron spectrum in a deuterated DMSO solvent of the carborane-containing polymer with high boron content in SiBCN (1:0.25) in example 4, and FIG. 16 is an argon TG plot of the carborane-containing polymer with high boron content in SiBCN (1:0.25) in example 4.
Finally, it should be noted that the specific examples described herein are merely illustrative of the spirit of the invention and do not limit the embodiments of the invention. Various modifications, additions and substitutions for the embodiments described herein will occur to those skilled in the art, and all such embodiments are neither required nor possible. While the invention has been described with respect to specific embodiments, it will be appreciated that various changes and modifications may be made without departing from the spirit and scope of the invention, as defined by the appended claims.
Claims (10)
1. A high boron carborane polymer having the formula:
wherein x is any integer of 1-10000, and y is any integer of 0-10000; r1、R3、R4、R6Is independently selected from-CzH2z+1、-COOCzH2z+1、-COCzH2z+1、-Ph、-NHCzH2z+1、-OCzH2z+1、-OH-NH2Wherein z is more than or equal to 0.
2. A method of synthesizing a carborane polymer of claim 1, comprising the steps of:
and reacting the alkynyl-containing polysilazane, decaborane complex and reaction solvent in an inert atmosphere at 60-120 ℃ for 7-15 h, and carrying out suction drying and sublimation to obtain the carborane polymer with high boron content.
3. The method of claim 2, wherein the decaborane complex is (CH)3CN)2B10H12And/or ((CH)3CH2)2S)2B10H12。
4. The method of claim 2, wherein said alkynyl-containing polysilazane has the formula:
wherein n is any integer of 1-10000; r1、R3、R4、R6Is independently selected from-CzH2z+1、-COOCzH2z+1、-COCzH2z+1、-Ph、-NHCzH2z+1、-OCzH2z+1、-OH-NH2Wherein z is more than or equal to 0.
5. The method of claim 4, wherein the alkynyl group-containing polysilazane is prepared by a process comprising the steps of:
(1) reacting silazane, dichlorosilane and aluminum trichloride at 40-60 ℃ for 60-80 h in an inert atmosphere, drying, and carrying out reduced pressure distillation to obtain dichlorosilazane;
(2) under the inert atmosphere, dissolving trichloroethylene in a reaction solvent, slowly dropping the trichloroethylene into a reaction bottle containing n-butyl lithium, placing the reaction bottle in a low-temperature reactor at the temperature of-60 to-80 ℃, heating to 15 to 37 ℃ after dropping, and reacting for 10 to 18 hours;
(3) and dissolving dichlorosilazane in a reaction solvent under an inert atmosphere, dripping the dichlorosilazane into the reaction system (2) at 15-37 ℃, heating to 70-90 ℃ after dripping, reacting for 10-18 h, draining, extracting, concentrating, recrystallizing, filtering, and draining to obtain the alkynyl-containing polysilazane.
6. The method of claim 5, wherein the silazane has the following formula:
wherein R is1、R2、R3、R4、R5、R6Is independently selected from-CzH2z+1、-COOCzH2z+1、-COCzH2z+1、-Ph、-NHCzH2z+1、-OCzH2z+1、-OH-NH2Wherein z is more than or equal to 0.
7. The method of claim 5, wherein the dichlorosilane has the formula:
wherein R is7、R8Is independently selected from-CzH2z+1、-COOCzH2z+1、-COCzH2z+1、-Ph、-NHCzH2z+1、-OCzH2z+1、-OH-NH2Wherein z is more than or equal to 0.
8. The synthesis process according to claim 5, characterized in that the molar ratio of silazane to dichlorosilane is 1: (2-3).
9. The synthesis method according to claim 5, wherein the molar ratio of n-butyllithium to trichloroethylene is (2.5-3.5): 1.
10. the synthesis method according to claim 2 or 5, wherein the reaction solvent is one or more of xylene, benzene, dimethylether, tetrahydrofuran, toluene, and dimethylformamide.
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| CN115784157A (en) * | 2022-11-28 | 2023-03-14 | 郑州原理生物科技有限公司 | Preparation method of decahydrodecaboron diammonium salt |
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