CN113716581B - High-ceramic-yield carbon-free boron nitride precursor and synthesis method thereof - Google Patents
High-ceramic-yield carbon-free boron nitride precursor and synthesis method thereof Download PDFInfo
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- CN113716581B CN113716581B CN202111065991.8A CN202111065991A CN113716581B CN 113716581 B CN113716581 B CN 113716581B CN 202111065991 A CN202111065991 A CN 202111065991A CN 113716581 B CN113716581 B CN 113716581B
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Abstract
The invention discloses a high-ceramic-yield carbon-free boron nitride precursor and a synthesis method thereof, and the method comprises the following steps: 1. carrying out anionic polymerization on ammonia borane under the excitation of strong alkali; 2. ammonium chloride replaces sodium ions to prepare oligomeric ammonia borane; 3. the oligomeric ammonia borane and trichloroborazine are copolymerized to prepare the non-carbon boron nitride precursor. The invention can realize high ceramic yield of the boron nitride precursor, simplify the preparation process of the BN ceramic, save the non-melting process and the decarburization process in the traditional process of the precursor conversion method and lay a foundation for preparing the high-performance BN ceramic.
Description
Technical Field
The invention belongs to the field of high molecular polymers, and particularly relates to a high-ceramic-yield boron nitride-free precursor and a synthesis method thereof.
Background
Precursor conversion Processes (PDCs) are a very attractive method for preparing ceramics, particularly in non-oxide systems, and are commonly used to design advanced ceramics, such as SiC, si, with compositional and structural uniformity 3 N 4 BN, etc. The precursor conversion method can prepare a complex BN ceramic shape which cannot be obtained by the traditional process by designing the molecular structure and the chemical property of the precursor.
BN ceramic precursors include borazine and trichloroborazine and their polymeric derivatives, namely polyborazine and poly [ tri (alkylamino) borazine ], which vary widely in chemical properties. And the specific functional groups and structural motifs in the polymer molecule determine the shaping potential of conventional shaping methods (liquid phase processes and plastic shaping techniques). To date, nanotubes, nanofibers, coatings, monoliths and fiber reinforced ceramic matrix composites have been prepared from different precursors. Therefore, the synthesis of the precursor has great engineering significance. However, it is generally not possible to integrate all the characteristics (i.e. solubility, meltability, high ceramic yield, stability) required to produce BN ceramics of various shapes into only one polymer precursor.
Miele et al firstly adopt boron trichloride and ammonium chloride to prepare trichloroborazine, then react with methylamine to prepare methylamino borazine monomer, finally heat and polymerize the monomer under the protection of inert gas to obtain poly [ tri (methylamino) borazine]. The precursor has meltability and is easy to process and form by a plastic forming process. However, since the precursor contains more carbon, the ceramic yield is relatively low (54%), and the precursor contains more active groups, is not resistant to water and oxygen, and is easily oxidized and hydrolyzed. Therefore, after the processing and forming, the BN ceramic needs to be prepared by respectively performing non-melting treatment, decarburization treatment and high-temperature heat treatment. The process flow is relatively complicated. Sneddon et al isolated solid polyboroazenes by borazine self-condensation at 70 ℃ under vacuum for about 48H, which have very high ceramic yields (84% -93%) due to their perhydro structure, but due to the B-H and N-H bonds both sp 2 Hybridization and strong activity, so the stability of the precursor is poor. In addition, due to the rigid molecular chain structure of perhydro-poly-borazine, the processing and forming process is difficult to control. The formed ceramic precursor can be subjected to pyrolysis to obtain BN ceramic, the whole preparation process needs to be carried out in an inert atmosphere, and the water oxygen content is strictly controlled.
Therefore, how to prepare the carbon-free boron nitride precursor with high ceramic yield, higher stability and certain water and oxygen resistance has significant meaning for the preparation process and the development application of the boron nitride ceramic.
Disclosure of Invention
The invention aims to solve the problems that the precursor of the BN ceramic prepared by the current precursor conversion method is sensitive to water and oxygen and has poor stability, and researches show that: the ammonia borane commonly used for the hydrogen storage material has excellent stability and does not contain carbon element, and the carbon-free boron nitride precursor with high ceramic yield is obtained through anion polymerization initiated by strong alkali and copolymerization with trichloroborazine. Therefore, the synthesis method of the non-carbon boron nitride precursor with high ceramic yield is provided, so that the prepared BN precursor has the characteristics of high ceramic yield and water and oxygen resistance, the preparation process of the BN ceramic is simplified, and non-melting and decarburization treatment is not needed.
The invention adopts the technical scheme that a carbon-free boron nitride precursor with high ceramic yield is provided, and the structural component unit of the precursor is represented by the following general formula:
compared with the prior art that the precursor of the bridged six-membered ring structure contains more carbon elements, the structure of the invention does not contain carbon elements. The molecular formula of the precursor does not contain carbon element, and the precursor can be kept stable in air and not decomposed. Most of boron nitride precursors in the prior art contain more carbon elements, and a small part of the precursors which do not contain the carbon elements are abnormally active in the air and can release heat and decompose unstably.
The invention also provides a synthesis method of the carbon-free boron nitride precursor with high ceramic yield, which comprises the following specific steps:
s1, carrying out anionic polymerization on ammonia borane under strong alkali excitation:
firstly, sodium bis (trimethylsilyl) amide (NaHMDS) and Ammonia Borane (AB) are added into a first solvent according to a certain molar ratio, the concentration of a suspension formed by the AB in the solvent is 0.05-0.5mol/L, and the mixture is stirred for 12-48h at the temperature of 30-90 ℃. The solution was then diluted with toluene and filtered, and the remaining solid was washed with toluene and ether respectively and dried under vacuum to give a white solid 1.
The reaction process is as follows:
preferably, the molar ratio of sodium bis (trimethylsilyl) amide (NaHMDS) to Ammonia Borane (AB) is 1.
S2, preparing oligomeric ammonia borane by replacing sodium ions with ammonium chloride:
reacting NH 4 Adding Cl and a white solid 1 into a solvent dimethoxyethane according to a certain molar ratio,the suspension of white solid 1 in dimethoxyethane has a concentration of 0.05 to 0.5mol/L and the mixture is stirred at 30 to 90 ℃ for 12 to 48h. The solution was then filtered and the remaining white solid was washed with dimethoxyethane and diethyl ether, respectively. Vacuum drying to remove all traces of solvent gave the oligomeric ammonia borane as a white color.
The reaction process is as follows:
preferably NH 4 The molar ratio of Cl to white solid 1 was 1.5.
S3, copolymerizing and polymerizing oligomeric ammonia borane and trichloroborazine:
adding oligomeric ammonia borane and Trichloroborazine (TCB) into a second solvent according to a certain molar ratio, wherein the concentration of the trichloroborazine in the solvent is 0.05-0.5mol/L, stirring the mixture at 30-90 ℃ for 12-48h, and evaporating the solution in vacuum to obtain the carbonless boron nitride precursor with high ceramic yield.
The reaction process is as follows:
the molar ratio of the oligomeric ammonia borane to the trichloroborazine is preferably 3.
Preferably, the solvent in step S3 includes one or a mixture of toluene, xylene, fluorobenzene and chlorobenzene.
The invention has the following advantages:
1. the precursor provided by the invention is a carbon-free precursor with a six-membered ring structure connected by a multi-element boron-nitrogen bridge, has high ceramic yield (> 70%), and is beneficial to increasing the density and improving the mechanical property of ceramics;
2. the prepared novel carbon-free precursor has excellent water and oxygen resistance, and the storage, forming and processing processes of the precursor do not require inert atmosphere protection, thereby being beneficial to simplifying the ceramic forming and processing process and reducing the production cost;
3. the prepared novel carbon-free precursor does not contain carbon, oxygen and other miscellaneous elements, does not need melting and decarburization treatment, and obviously simplifies the heat treatment ceramic process flow of preparing BN ceramic by the precursor conversion method.
Description of the drawings:
FIG. 1 is a graph showing the thermogravimetric curves of the precursor obtained in the example of the present invention;
FIG. 2 is a FT-IR spectrum of a precursor obtained in an example of the present invention;
FIG. 3 is a FT-IR spectrum of a precursor placed in an external environment for different times;
fig. 4 is an XRD spectrum of the precursor after heat treatment.
Detailed Description
The invention is further illustrated by the following examples and figures.
The following examples and comparative examples were conducted in accordance with the above-described one of the non-carbon boron nitride precursors with high ceramic yield and the synthesis method thereof, except that the reagents and conditions used were different; in the experiment, the operations of sample adding, transferring and the like are all carried out in an argon glove box, and the used argon is high-purity argon with the purity of more than or equal to 99.99 percent; the protective atmosphere in each example and each comparative example is nitrogen, and the purity of the used nitrogen is more than or equal to 99.9 percent; other chemicals used, unless otherwise specified, were obtained from conventional commercial sources.
The ammonia borane and ammonium chloride used in the examples were prepared according to the methods provided in the following reference examples.
Reference example 1
(a) Placing 10g of ammonia borane in a ball mill at the rotation speed of 500rpm for ball milling for 30min at normal temperature;
(b) And (3) drying the ball-milled ammonia borane powder for 24 hours in vacuum at normal temperature.
Reference example 2
(a) Placing 20g of ammonium chloride in a ball mill at the rotating speed of 500rpm, and carrying out ball milling at normal temperature for 30min;
(b) The ball-milled ammonium chloride powder was dried under vacuum at 110 ℃ for 24h.
Example 1
The embodiment comprises the following steps:
1. anionic polymerization of ammonia borane under strong base excitation:
sodium bis (trimethylsilyl) amide (NaHMDS) and Ammonia Borane (AB) were first added to the solvent fluorobenzene in a molar ratio of 1. The solution was then diluted with toluene and filtered, and the remaining solid was washed with toluene and diethyl ether, respectively, and dried under vacuum to give 1 as a white solid.
2. Ammonium chloride was used to replace sodium ion to prepare oligomeric ammonia borane:
reacting NH 4 Cl and white solid 1 were added to the solvent dimethoxyethane in a molar ratio of 1.5. The solution was then filtered and the remaining white solid was washed with dimethoxyethane and diethyl ether, respectively. Vacuum drying to remove all traces of solvent gave white oligomeric ammonia borane, the majority of which was dimer.
3. Copolymerization of oligomeric ammonia borane and trichloroborazine:
adding oligomeric ammonia borane and Trichloroborazine (TCB) into dimethylbenzene according to the molar ratio of 3.
Example 2
The embodiment comprises the following steps:
1. anionic polymerization of ammonia borane under strong base excitation:
sodium bis (trimethylsilyl) amide (NaHMDS) and Ammonia Borane (AB) were first added to the solvent fluorobenzene in a molar ratio of 1. The solution was then diluted with toluene and filtered, and the remaining solid was washed with toluene and ether respectively and dried under vacuum to give a white solid 1.
2. Ammonium chloride was substituted for sodium ion to prepare oligomeric ammonia borane:
reacting NH 4 Cl and whiteThe coloured solid 1 was added to the solvent dimethoxyethane in a molar ratio of 1.5, the suspension of white solid 1 in dimethoxyethane had a concentration of 0.05mol/L and the mixture was stirred at 90 ℃ for 12h. The solution was then filtered and the remaining white solid was washed with dimethoxyethane and diethyl ether, respectively. Vacuum drying to remove all traces of solvent gave white oligomeric aminoborane in 20% conversion yield.
3. Copolymerization of oligomeric ammonia borane and trichloroborazine:
adding oligomeric ammonia borane and Trichloroborazine (TCB) into toluene according to the molar ratio of 1.
Example 3
The embodiment comprises the following steps:
1. anionic polymerization of ammonia borane under strong base excitation:
sodium bis (trimethylsilyl) amide (NaHMDS) and Ammonia Borane (AB) were first added to the solvent fluorobenzene in a molar ratio of 1. The solution was then diluted with toluene and filtered, and the remaining solid was washed with toluene and diethyl ether, respectively, and dried under vacuum to give 1 as a white solid.
2. Ammonium chloride was substituted for sodium ion to prepare oligomeric ammonia borane:
reacting NH 4 Cl and white solid 1 were added to the solvent dimethoxyethane in a molar ratio of 1. The solution was then filtered and the remaining white solid was washed with dimethoxyethane and diethyl ether, respectively. Vacuum drying to remove all traces of solvent and obtain white oligomeric ammonia borane, wherein partial cyclization of oligomeric ammonia borane (trimer and tetramer) exists.
3. Copolymerization of oligomeric ammonia borane and trichloroborazine:
adding oligomeric ammonia borane and Trichloroborazine (TCB) into fluorobenzene according to the molar ratio of 1.
Example 4
The embodiment comprises the following steps:
1. anionic polymerization of ammonia borane under strong base excitation:
sodium bis (trimethylsilyl) amide (NaHMDS) and Ammonia Borane (AB) were first added to the solvent fluorobenzene at a molar ratio of 1. The solution was then diluted with toluene and filtered, and the remaining solid was washed with toluene and ether respectively and dried under vacuum to give a white solid 1.
2. Ammonium chloride was substituted for sodium ion to prepare oligomeric ammonia borane:
reacting NH 4 Cl and white solid 1 were added to the solvent dimethoxyethane at a molar ratio of 1. The solution was then filtered and the remaining white solid was washed with dimethoxyethane and diethyl ether, respectively. Vacuum drying to remove all traces of solvent gave white oligomeric ammonia borane in a conversion yield of 64%.
3. Copolymerization of oligomeric ammonia borane and trichloroborazine:
adding oligomeric ammonia borane and Trichloroborazine (TCB) into toluene according to the molar ratio of 1.
Example 5
The embodiment comprises the following steps:
1. anionic polymerization of ammonia borane under strong base excitation:
sodium bis (trimethylsilyl) amide (NaHMDS) and Ammonia Borane (AB) were first added to the solvent fluorobenzene in a molar ratio of 1. The solution was then diluted with toluene and filtered, and the remaining solid was washed with toluene and diethyl ether, respectively, and dried under vacuum to give 1 as a white solid.
2. Ammonium chloride was used to replace sodium ion to prepare oligomeric ammonia borane:
reacting NH 4 Cl and white solid 1 were added to the solvent dimethoxyethane in a molar ratio of 1. The solution was then filtered and the remaining white solid was washed with dimethoxyethane and diethyl ether, respectively. Vacuum drying to remove all traces of solvent gave white oligomeric ammonia borane in 82% conversion yield.
3. Copolymerization and polymerization of oligomeric ammonia borane and trichloroborazine:
adding oligomeric ammonia borane and Trichloroborazine (TCB) into toluene according to the molar ratio of 2.
Example 6
The embodiment comprises the following steps:
1. anionic polymerization of ammonia borane under strong base excitation:
sodium bis (trimethylsilyl) amide (NaHMDS) and Ammonia Borane (AB) were first added to the solvent fluorobenzene in a molar ratio of 1. The solution was then diluted with toluene and filtered, and the remaining solid was washed with toluene and ether respectively and dried under vacuum to give a white solid 1.
2. Ammonium chloride was substituted for sodium ion to prepare oligomeric ammonia borane:
reacting NH 4 Cl and white solid 1 were added to the solvent dimethoxyethane in a molar ratio of 1. Then the solution is filtered and separatedThe remaining white solid was washed with dimethoxyethane and diethyl ether. Vacuum drying to remove all traces of solvent and obtain white oligomeric ammonia borane, wherein the oligomeric ammonia borane is mostly tripolymer and is partially cyclized.
3. Copolymerization and polymerization of oligomeric ammonia borane and trichloroborazine:
adding oligomeric ammonia borane and Trichloroborazine (TCB) into toluene according to the molar ratio of 2.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (8)
1. A method for synthesizing a carbon-free boron nitride precursor with high ceramic yield is characterized in that,
the method comprises the following steps:
s1, carrying out anionic polymerization on ammonia borane under strong alkali excitation:
adding sodium bis (trimethylsilyl) amide and ammonia borane into a first solvent, stirring the mixture, diluting the solution with toluene, filtering, washing the separated solid with toluene and diethyl ether respectively, and drying in vacuum to obtain a white solid 1;
s2, substituting sodium ions in the white solid 1 with ammonium chloride to prepare oligomeric ammonia borane:
reacting NH 4 Adding Cl and the white solid 1 in the step S1 into a solvent dimethoxyethane, stirring the mixture, filtering the solution, washing the remained white solid with dimethoxyethane and diethyl ether respectively, and finally performing vacuum drying to remove all trace solvents to obtain white oligomeric ammonia borane;
s3, copolymerizing and polymerizing oligomeric ammonia borane and trichloroborazine:
and (4) adding the oligomeric ammonia borane obtained in the step (S3) and trichloroborazine into a second solvent, stirring the mixture, and then evaporating the solution to dryness in vacuum to obtain the carbonless boron nitride precursor with high ceramic yield.
2. The method for synthesizing a high ceramic yield boron nitride precursor according to claim 1, wherein in step S1, the molar ratio of sodium bis (trimethylsilyl) amide to ammonia borane is (1.
3. The method for synthesizing a high ceramic yield boron nitride precursor as claimed in claim 1, wherein in step S1, ammonia borane is suspended in the first solvent at a concentration of 0.05-0.5 mol/L; the stirring temperature is 30-90 ℃ and the stirring time is 12-48h.
4. The method for synthesizing a high ceramic yield boron nitride precursor as claimed in claim 1, wherein in step S2, the NH is introduced into the reaction chamber 4 The molar ratio of Cl to white solid 1 was (1.5.
5. The method for synthesizing a high ceramic yield boron nitride precursor as claimed in claim 1, wherein in step S2, white solid 1 is suspended in dimethoxyethane at a concentration of 0.05-0.5 mol/L; stirring the mixture at 30-90 deg.C for 12-48h.
6. The method for synthesizing a high ceramic yield boron nitride-free precursor according to claim 1, wherein in step S3, the molar ratio of the oligomeric aminoborane to the trichloroborazine is (3.
7. The method for synthesizing a high ceramic yield carbon-free boron nitride precursor according to claim 1, wherein in step S3, the concentration of trichloroborazine in the second solvent is 0.05-0.5 mol/L; stirring the mixture at 30-90 deg.C for 12-48h.
8. The method for synthesizing a high ceramic yield boron nitride-free precursor according to claim 1, wherein in the steps S1 and S3, the first solvent and the second solvent are selected from one or more of toluene, xylene, fluorobenzene and chlorobenzene.
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