CN-115595609-B - Method for synthesizing caged tetraacetyl hexaazaisowurtzitane TAIW based on electrochemical path

CN115595609BCN 115595609 BCN115595609 BCN 115595609BCN-115595609-B

Abstract

A process for synthesizing cage-shaped tetraacetyl hexaazaisowurtzitane TAIW based on electrochemical route includes such steps as in-situ growth of Pd catalyst on carbon felt by electrodeposition method, preparing PdCl 2 solution, adding Na 2 SO 4 to form electroplating liquid, cyclic voltammetry scanning for 50 circles to obtain Pd catalyst-loaded working electrode, adding acetonitrile and water as solvent and supporting electrolyte to cathode and anode chambers of H-electrolyzer, adding benzylamine and acetic anhydride to cathode chamber, magnetically stirring at ordinary temp for 10min, dropping 40% glyoxal water solution, introducing argon gas to cathode chamber to remove dissolved oxygen, applying negative current to prepared working electrode, filtering, washing filter cake twice with cold acetonitrile, and air drying at room temp.

Inventors

JIN ZHONG
WANG MIAO
LI JIARUI
TIE ZUOXIU

Assignees

南京铁鸣能源科技有限公司
苏州铁睿新能源科技有限公司
镇江索锂德新能源科技有限公司
滁州极鑫新能源科技有限公司
南京大學天长新材料与能源技术研发中心

Dates

Publication Date: 20260508
Application Date: 20220909

Claims (5)

1. A method for synthesizing caged tetraacetyl hexaazaisowurtzitane TAIW by an electrochemical route, comprising the steps of: s1, preparing an electrode, namely, in-situ growing a Pd catalyst on a carbon felt by an electrodeposition method to serve as a working electrode, and using a graphite rod and a saturated silver chloride solution electrode as a counter electrode and a reference electrode; S2, preparing an electroplating solution, namely adding a PdCl 2 solution with the concentration of 20mmol/L into a glass bottle, then adding Na 2 SO 4 as a supporting electrolyte, and keeping Na 2 SO 4 at the concentration of 0.5mol/L in the solution without stirring; S3, preparing a working electrode, namely carrying out 50-circle cyclic voltammetry scanning on the electroplating solution prepared in the step S1 within a potential range of-0.5 to 1.7V at a scanning rate of 0.1V.S -1 so as to obtain a Pd catalyst-loaded working electrode; S4, preparing an H-type electrolytic tank, namely firstly adding acetonitrile and water mixed solution serving as a solvent into a cathode chamber and an anode chamber of the H-type electrolytic tank respectively, and adding two parts of supporting electrolyte with the same amount into the cathode chamber respectively, then adding 5g of benzylamine and 2.2g of acetic anhydride into the cathode chamber, magnetically stirring the mixture at normal temperature for 10min, then dropwise adding 3.05g of glyoxal aqueous solution with the concentration of 40% by using an atmospheric dropping funnel, dropwise adding the glyoxal aqueous solution for about five minutes, and reacting the reaction solution at the room temperature of not more than 25 ℃ in the feeding process; After the dripping is finished, argon is introduced into the electrolytic solution in the cathode chamber for 30min to remove dissolved oxygen in the solution; And S5, performing electrocatalytic reaction, namely applying a certain negative current to the working electrode prepared in the step S1, after reacting for 1h, collecting a product solution, filtering, washing a filter cake twice by using 50mL of cold acetonitrile, and air-drying the product at room temperature to obtain the product caged tetraacetyl hexaazaisowurtzitane TAIW.
2. The method for synthesizing caged tetraacetyl hexaazaisowurtzitane TAIW according to claim 1, wherein the working electrode and the reference electrode in step S1 are placed in a cathode reaction tank, the counter electrode is placed in an anode reaction tank, and the two electrodes are separated by a Nafion-117 membrane, and the graphite rod has a length of 10cm and a diameter of 1cm.
3. The method for synthesizing a caged tetraacetyl hexaazaisowurtzitane TAIW according to claim 1, wherein the filtration in step S3 is carried out by a sand-core funnel pressure-reducing filtration method.
4. The method for synthesizing a caged tetraacetyl hexaazaisowurtzitane TAIW according to claim 1, wherein the supporting electrolyte in step S4 is sodium chloride particles in an amount of 1.6g per serving.
5. The method for synthesizing caged tetraacetyl hexaazaisowurtzitane TAIW according to claim 1, wherein the volume ratio of acetonitrile to water is 10:1 in step S4, the stirring speed is 1000r/min, and the constant negative current density is maintained at-50 mA/cm 2 in step S5.

Description

Method for synthesizing caged tetraacetyl hexaazaisowurtzitane TAIW based on electrochemical path Technical Field The application belongs to the field of electrochemical synthesis, and particularly relates to a method for synthesizing caged tetraacetyl hexaazaisowurtzitane TAIW based on an electrochemical path. Background The cage-shaped compound structure tightly has a three-dimensional cage-shaped carbon skeleton, and each molecule is composed of a plurality of carbocycles, so that great attention is paid to the characteristics of high energy and high tension. The hexanitrohexaazaisowurtzitane (HNIW or CL-20) has better heat stability and lower detonation sensitivity because the output energy is much larger than that of the traditional energetic compounds such as oxtropine (HMX) and Hemsleyamine (RDX), and the like, and the improved optimization research on the synthesis method and the synthesis process of Nielsen mainly comprises the improvements of synthesis routes, nitrosating agents, nitrifying agents, nitrosating processes and the like and the changes of solvents and catalysts. After the synthetic route of CL-20 is improved, four-step synthesis method is adopted, namely, firstly, benzyl amine and glyoxal are condensed in acetonitrile/water azeotropic liquid by taking formic acid as a catalyst to synthesize hexabenzyl hexaaza-isowurtzitane (HBIW), b, under the coexistence of hydrogen atmosphere and acetic anhydride, six benzyl groups on HBIW are partially or completely converted into acetyl groups or other substituents (such as TAIW) through palladium/carbon catalyst, c, TAIW is subjected to nitrolysis of Cheng-CL-20 or gamma-CL-20 crude products in nitrosulfuric mixed acid or fuming nitric acid, d, finally, alpha-CL-20 or gamma-CL-20 is subjected to recrystallization under the condition of specific solution to convert into epsilon-CL-20 with the best performance. By summarizing the current processes, we can see that the step of CL-20 synthesis is relatively complex and that explosion-risky hydrogen is required as a hydrogen source to participate in the dissociation of the benzyl group on the caged compound. The high production process cost and safety risk are also a major factor restricting CL-20 to large-scale practical application. Therefore, the improvement of the reaction path is very economic and has great national defense and economic values. In the electrocatalytic process, protons (H +) are generated continuously in situ on the surface of a catalyst in the electrolyte under the condition of applying a certain negative voltage to a working electrode, so as to trigger further hydrogenation reaction. The avoidance of hydrogen use also allows the safety problem to be greatly solved under electrocatalytic pathway conditions. On the other hand, the selectivity or the yield of the hydrogenation intermediate product can be effectively regulated and controlled by adjusting different voltages. More importantly, the unique advantage of the electrocatalytic system is utilized to avoid the necessity of feeding a large amount of catalyst in the traditional catalytic system, thereby greatly reducing the use cost of the catalyst in the CL-20 production process. Disclosure of Invention The application provides a method for synthesizing caged tetraacetyl hexaazaisowurtzitane TAIW based on an electrochemical path, which solves the technical problems of high production cost and high safety risk in the prior art. The technical scheme is as follows: The method for synthesizing caged tetraacetyl hexaazaisowurtzitane TAIW based on electrochemical path comprises S1 preparing electrode by in situ growing Pd catalyst on carbon felt by electrodeposition method as working electrode, and graphite rod and saturated silver chloride solution electrode as counter electrode and reference electrode; S2, preparing an electroplating solution, namely adding a PdCl 2 solution with the concentration of 20mmol/L into a glass bottle, then adding Na 2SO4 as a supporting electrolyte, and keeping Na 2SO4 at the concentration of 0.5mol/L in the solution without stirring; S3, preparing a working electrode, namely carrying out 50-circle cyclic voltammetry scanning on the electroplating solution prepared in the step S1 within a potential range of-0.5 to 1.7V at a scanning rate of 0.1V.S -1 so as to obtain a Pd catalyst-loaded working electrode; S4, preparing an H-type electrolytic tank, namely firstly adding acetonitrile and water mixed solution serving as a solvent into a cathode chamber and an anode chamber of the H-type electrolytic tank respectively, and adding two parts of supporting electrolyte with the same amount into the cathode chamber respectively, then adding 5g of benzylamine and 2.2g of acetic anhydride into the cathode chamber, magnetically stirring the mixture at normal temperature for 10min, then dropwise adding 3.05g of glyoxal aqueous solution with the concentration of 40% by using an atmospheric dropping funnel, dropwise