CN115109101B - Diferrocenyl high-nitrogen energetic ionic compound and preparation method thereof - Google Patents

Diferrocenyl high-nitrogen energetic ionic compound and preparation method thereof Download PDF

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CN115109101B
CN115109101B CN202210832336.9A CN202210832336A CN115109101B CN 115109101 B CN115109101 B CN 115109101B CN 202210832336 A CN202210832336 A CN 202210832336A CN 115109101 B CN115109101 B CN 115109101B
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ionic compound
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ferrocene
nitrogen
bisferrocenyl
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CN115109101A (en
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张国防
何倩
李吉祯
许锐哲
方海超
王娇
鲁彩红
杨蕗菲
米之元
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Shaanxi Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B29/00—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate
    • C06B29/22—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate the salt being ammonium perchlorate
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/49—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
    • C07C205/57—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/06—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and unsaturated carbon skeleton
    • C07C255/09—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and unsaturated carbon skeleton containing at least two cyano groups bound to the carbon skeleton
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Abstract

The invention discloses a bisferrocenyl high-nitrogen energetic ionic compound and a preparation method thereof, wherein the compound contains high-nitrogen azole energetic groups, and has higher heat of generation and combustion, so that the compound has better combustion catalysis effect on ammonium perchlorate, and can contribute energy to a solid propellant to improve the energy level of the solid propellant; simultaneously contains two ferrocene groups, and has better thermal stability than a mononuclear ferrocene ionic compound; the anions and cations depend on coulomb electrostatic interaction, so that the ionic liquid has lower vapor pressure and lower volatility and mobility under natural conditions; the compound is synthesized based on click reaction and ion exchange reaction, has simple reaction condition, high synthesis yield, low cost and easy amplification, overcomes the problems of high mobility and volatility of ferrocene flame-retardant catalysts such as active carboxin and the like, and has the defects of complex synthesis process, high price, high cost and the like, and is expected to be put into solid propellant to replace commercial carboxin.

Description

Diferrocenyl high-nitrogen energetic ionic compound and preparation method thereof
Technical Field
The invention belongs to the technical field of solid propellants, and particularly relates to a bisferrocenyl high-nitrogen energetic ionic compound and a preparation method thereof.
Background
The solid propellant (solid gunpowder) is gradually developed as a composite energetic material for propulsion, mainly provides driving force for rockets, shells, firearms and missiles, plays a very important role in the development of missiles and aerospace industry, has decisive role in the fight capability of weapon missiles and occupies important positions in national defense science and technology industry. In order to ensure the ballistic performance of solid rocket engines and the stability of engine operation, most strategies and tactics desire a low fuel pressure index for solid propellants. The combustion speed catalyst can play a role in reducing the pressure index of the propellant, is an additive for regulating the combustion speed of the propellant through physical or chemical action, and can improve or reduce the combustion speed of the propellant by changing the structure of combustion waves, so that the influence of the pressure index on the combustion speed is greatly weakened, and the addition amount is generally between 1 and 5 percent by mass. As an indispensable component in the formulation of solid propellant, the research of the burning rate catalyst is an important content of the research of solid propellant, and has been greatly developed in China and abroad in recent decades.
Compared with other burning rate catalysts, the ferrocene compound has the advantages of better combustibility, dispersibility, uniformity, compatibility and the like, becomes the most used one of the current composite propellants, especially AP/Al/HTPB propellant, and is widely applied to strategic and tactical weapon systems as the most main burning rate catalyst of solid propellants (especially composite propellants), and plays a great role in weapons of various ballistic missiles (including war zones, short ranges, medium ranges, intercontinental ballistic missiles and the like), airborne tactical missiles, reverse-conduction high-speed kinetic energy missiles, sea water torpedoes, torpedoes and the like. However, the ferrocene fuel rate catalyst applied at present has the problems of easy migration, easy volatilization, easy crystallization at low temperature and the like, seriously influences the storage life, the use reliability and the environmental adaptability of various missile propellant charges in China, and also invisibly greatly increases the expenditure of basic reserve of national defense. Therefore, scientific researchers have made a great deal of research work to try to develop ferrocene combustion speed catalysts with better mechanical properties, simpler process properties and better combustion performance, and the problems of improving ferrocene and derivatives thereof are solved.
The American researchers firstly introduce alkyl into ferrocene molecules to obtain 2, 2-bis (ethyl ferrocene) -propane (Catocene ), and the Catocene is a ferrocene combustion regulator with excellent performance which is commercialized at present, is liquid at room temperature, has low vapor pressure and high iron content, and can greatly improve the comprehensive performance of the propellant. However, the problem of easy migration, easy oxidation and short service life of the propellant exists in the cartomide. At the beginning of the 70 s, huskin et al synthesized liquid ferrocene derivatives containing allyl alcohol building blocks, overcoming the problems of migration and low temperature crystallization. Subsequently, a combustion regulator containing butyl isocyanate units of the double ferrocene has been synthesized, which has high catalytic activity but reduced mechanical properties. One of the more common methods used today is to attach ferrocene groups to the side chains or backbone of macromolecules to form ferrocene-containing polymers. Butacene developed by French explosive society is a graft copolymer of ferrocene derivatives and low molecular weight hydroxyl-terminated polybutadiene, and when the propellant is prepared, the copolymer can partially replace a common adhesive (such as hydroxyl-terminated polybutadiene (HTPB)) in a composite propellant, and can enter a curing network in the process of curing the propellant, but the preparation process of the derivative is complex, is sensitive to an oxidant, has low iron content and low catalytic efficiency, and the existence of iron can cause degradation reaction of a butyl hydroxy adhesive in the process of storage, so that the performance of the butyl hydroxy adhesive is reduced. In 2008, li Fengsheng et al report on solid rocket technology that ferrocene is grafted to SBA-15 through condensation reaction, a catalyst with low mobility is prepared. However, the catalyst has low iron content, and the catalyst has not good catalytic effect due to the introduction of silicon oxide without energy. In addition, the ferrocene compound is introduced with active functional groups such as epoxy ethyl, mercapto, aza and the like which are easy to polymerize, and the test of the compound in a solid propellant finds that the compound can partially solve the migration problem, but no perfect combination of mechanical property, technological property and combustion property can be obtained. In 2012 Yuan Yaofeng et al, ferrocene is used as a raw material to obtain propyl bridged dicyclopentadienyl carbonitrile and propyl bridged dicyclopentadienyl tetrazole through formylation, condensation, dehydration and other processes, and the combustion catalytic performance of the compound when added into ammonium perchlorate is tested, and the decomposition peak temperature of the ammonium perchlorate after the addition is shown to be advanced by about 50 ℃, but the synthesis process is complex. In 2016, gao Xiaoni et al synthesized two types of compounds, namely, a high nitrogen content type compound and a high iron content type compound, by using ferrocene tetrazolium as an anion, a nitrogen-rich group and ferrocene quaternary ammonium salt as cations. Through tests, both compounds have good combustion catalysis effect on the main component ammonium perchlorate of the propellant, and have low migration and volatility. In 2019 Muhammad Usman, li Wang et al synthesize five ferrocenyl compounds by condensation reaction of ferrocenylcarbonyl chloride and corresponding hydroquinone derivatives, research the influence of polar element (oxygen) and electronegative halogen groups on migration resistance of small ferrocenyl hydroquinone compounds, and TG and DTG results show that the five small molecular compounds have good catalytic performance on thermal decomposition of AP. And is less mobile and volatile. 2021, dan Xiaoling et al designed 20 products with mono-and di-azidomethylferrocene and nitrogen-containing compounds such as imidazole, pyrazole and triazole using click reaction, and expected to increase the overall energy level of the molecule by increasing the nitrogen content of the compound; meanwhile, the migration resistance of the compounds is enhanced, and the products are subjected to combustion catalysis performance and migration resistance tests, so that the compounds are found to have certain catalysis effect and have lower migration and volatility.
Disclosure of Invention
The invention aims to overcome the defect of easy volatilization of the existing ferrocene derivative solid propellant, provides a biferrocenyl high-nitrogen energetic ionic compound which is not easy to volatilize under natural conditions and has good thermal stability, and provides a preparation method for the ionic compound.
In view of the above, the bisferrocenyl high nitrogen energetic ionic compound adopted by the invention is any one of the following compounds 1 to 3:
the preparation method of the bisferrocenyl high-nitrogen energetic ionic compound comprises the following steps:
1. at N 2 Under the atmosphere, dissolving the 1, 3-dipropynylimidazole bromide shown in the formula II and the azidomethylferrocene shown in the formula I in methanol, uniformly stirring, then adding copper sulfate pentahydrate and sodium ascorbate, stirring for 24-48 hours at room temperature, reacting to generate precipitate, and filtering to obtain an intermediate product A.
2. Dissolving the intermediate product A in N, N-dimethylformamide, then adding 2-sodium nitrobenzoate or 3, 5-dinitrobenzoate or aqueous solution of 1, 3-potassium tetracyanoacrylate under stirring, stirring at room temperature for reaction for 20-24 hours, evaporating and concentrating after the reaction is finished to remove the solvent, centrifuging and washing, and vacuum drying to obtain the bisferrocenyl high-nitrogen energetic ionic compound.
In the above step 1, the molar ratio of the 1, 3-dipropynylimidazole bromide to the azidomethylferrocene, the copper sulfate pentahydrate, and the sodium ascorbate is preferably 1:2 to 2.5:0.4 to 0.8:0.4 to 0.8.
In the above step 2, the molar ratio of the intermediate product A to sodium 2-nitrobenzoate or sodium 3, 5-dinitrobenzoate or potassium 1, 3-tetracyanoacrylate is preferably 1:1 to 1.5.
The beneficial effects of the invention are as follows:
1. the double ferrocenyl high nitrogen energetic ionic compound is a molecule composed of a ferrocenyl group, a 1,2, 3-triazole group, an alkyl imidazole group and a nitro group, and contains not only the ferrocenyl group required by a ferrocene type combustion speed catalyst, but also a nitrogen-rich heterocyclic group with positive formation enthalpy, such as 1,2, 3-triazole and imidazole. Because of the introduction of the high-nitrogen azole energetic group, the higher combustion heat and the generated heat can improve the energy level of the propellant during decomposition; because two ferrocene groups are introduced, the thermal stability is better than that of a mononuclear ferrocene ionic compound; the anions and cations depend on coulomb electrostatic interaction, so that the ionic liquid has lower vapor pressure and lower volatility and mobility under natural conditions.
2. The double ferrocenyl high-nitrogen energetic ionic compound is synthesized by adopting a click reaction and an ion exchange reaction, is easy to carry out molecular design and modification, regulates and controls the catalytic performance of a target product, meets the formula requirements of different types of solid propellants, and is therefore applied to the solid propellants. Based on the advantages of simple reaction condition, high synthesis yield, low cost and easy amplification of 'click reaction', 3 novel biferrocene high-nitrogen energetic ionic compounds are synthesized by adopting ion exchange reaction, and the defects of high mobility and volatility of ferrocenyl fuel rate catalysts such as active carboxin and the like, as well as complex synthesis process, high price, high cost and the like of the ferrocenyl fuel rate catalysts are overcome.
3. The bisferrocenyl high-nitrogen energetic ionic compound prepared by the invention has higher thermal stability and migration resistance and better combustion catalytic performance on ammonium perchlorate, so that the bisferrocenyl high-nitrogen energetic ionic compound is expected to be put into a solid propellant to replace commercial catoxin.
Drawings
FIG. 1 is a plot of differential scanning calorimetry analysis of compounds of examples 1-3 with 5% addition to ammonium perchlorate.
FIG. 2 is a thermogravimetric curve of the compounds of examples 1-3.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, but the scope of the present invention is not limited to these examples.
The 1, 3-dipropynylimidazole bromide used in the examples below was prepared according to the following procedure:
2.1142g (32.03 mmol) imidazole was added to a solution of 30mL acetonitrileInto the reaction flask, 7.6250g (64.08 mmol) of 3-bromopropyne, N at 50℃were then added dropwise 2 Stirring for 24 hours under the condition, evaporating and concentrating to remove the solvent after the reaction is finished, recrystallizing with acetonitrile and diethyl ether, and drying in vacuum at 40 ℃ for 4 hours to obtain white solid 1, 3-dipropynylimidazole bromide, wherein the yield is 96%, and the reaction equation is as follows:
the structural characterization data of the obtained 1, 3-dipropynylimidazole bromide are as follows: 1 H NMR(600MHz,DMSO):δ8.92(s,1H),7.92(s,1H),7.80(s,1H),5.57(s,2H),4.47(s,2H),3.14(s,2H)。
example 1
1. 2.1133g (8.768 mmol) of azidomethylferrocene and 0.9820g (4.384 mmol) of 1, 3-dipropynylimidazole bromide were dissolved completely in a 250mL round-bottom flask containing 50mL of methanol under N 2 Stirring uniformly under atmosphere, then dropwise adding 15mL of an aqueous solution containing 0.6568g (2.630 mmol) of copper sulfate pentahydrate and 15mL of an aqueous solution containing 0.5725g (2.890 mmol) of sodium ascorbate, stirring at room temperature for 24h, suction-filtering, washing a filter cake with methanol and water, and vacuum-drying at 40 ℃ for 24h to obtain an intermediate product A with a yield of 84%.
Maldi-TOF value for intermediate A: 627.5000g/mol (627.1365 g/mol); the structural characterization data are: 1 H NMR(600MHz,DMSO-d 6 ):δ9.28(s,1H),8.14(s,2H),7.70(s,2H),5.46(s,4H),5.29(s,4H),4.29(s,4H),4.15(s,14H)。
2. 0.1293g (0.1829 mmol) of intermediate A was dissolved in 3mL of DMF and placed in a 50mL round bottom flask, and then 20mL of an aqueous solution containing 0.0389g (0.206 mmol) of sodium 2-nitrobenzoate was added, the reaction was stirred at room temperature for 24 hours, after the reaction was completed, the solvent was removed by evaporation and concentration, and the mixture was centrifugally washed and dried at 40℃for 24 hours to give 0.1142g of a tan solid bisferrocenyl energetic ionic compound 1 with a yield of 78%.
T of Compound 1 dec =159.8 ℃, infrared spectrum data are: FT-IR (KBr, cm) -1 ) 3778w,3079w,2956vs,1628vs,1524s,1453s,1342m,1229s,1090s,812vs,740m, 470 vs; elemental analysis (theoretical calculation in brackets): c%57.15 (57.52), H%4.60 (4.45), N%15.98 (15.89).
Example 2
1. Intermediate a was prepared according to step 1 of example 1.
2. 0.1638g (0.2317 mmol) of intermediate A is dissolved in 3mL of DMF and placed in a 50mL round bottom flask, 20mL of an aqueous solution containing 0.0611g (0.2610 mmol) of 3, 5-dinitro-sodium benzoate is added, the reaction is stirred at room temperature for 24h, after the reaction is completed, the solvent is removed by evaporation and concentration, centrifugal washing is carried out, drying is carried out at 40 ℃ for 24h, and 0.1655g of a tan solid bisferrocenyl high nitrogen energetic ionic compound 2 is obtained, and the yield is 85%.
T of Compound 2 dec =165.6 ℃, infrared spectrum data are: FT-IR (KBr, cm) -1 ) 3754w,3060w,2948vs,1661vs,1533s,1450s,1342m,1229s,1090s,805vs, holding distance, 470 vs; elemental analysis (theoretical calculation in brackets): c%54.58 (54.44), H%4.25 (4.09), N%16.52 (16.71).
Example 3
1. Intermediate a was prepared according to step 1 of example 1.
2. 0.2065g (0.2922 mmol) of intermediate A was dissolved with 3mL of MF and placed in a 50mL round bottom flask, and then 20mL of an aqueous solution containing 0.0594g (0.330 mmol) of potassium 1, 3-tetracyanoacrylate was added thereto, the reaction was stirred at room temperature for 24 hours, the solvent was removed by evaporation and concentration after the reaction was completed, and the mixture was washed by centrifugation and dried at 40℃for 24 hours to give 0.2018g of a tan solid bisferrocenyl energetic ionic compound 3 in 89% yield.
T of Compound 3 dec =176.3 ℃, infrared spectrum data are: FT-IR (KBr, cm) -1 ) 3698w,3095w,2951vs,1653vs,1546s,1442s,1316m,1254s,1078s,805vs,730m,472vs; elemental analysis (theoretical calculation in brackets): c%59.68 (59.39), H%4.25 (4.20), N%21.54 (21.87).
5mg of each of the bisferrocenyl high-nitrogen energetic ionic compounds prepared in examples 1-3 was ground and mixed uniformly with 95mg of powdery Ammonium Perchlorate (AP), 3mg of the mixture was taken and the catalytic performance was tested by a differential scanning calorimeter, and the results are shown in FIG. 1. As can be seen from fig. 1, the thermal decomposition of the AP can be divided into three phases: the first process is a phase change endothermic process of the AP, the peak temperature is 243.7 ℃, the peak temperature of the second stage is 292.5 ℃, the low-temperature decomposition process of the AP is carried out, the peak temperature of the third stage is 406.6 ℃, the high-temperature decomposition stage is called, after 5% of the compounds of examples 1-3 are respectively added into the AP, the crystal form transition temperature of the AP is basically unchanged and slightly moved backwards; the pyrolysis stage of the AP is moved backward from the original 292.5 ℃ to about 13-18 ℃. The maximum change is the exothermic peak of the original AP in the high-temperature decomposition stage, the peak temperature is 406.6 ℃, and after 5 percent of the compounds of examples 1 to 3 are added, the decomposition peak temperature is respectively advanced to 319.2 ℃, 330.8 ℃ and 331.9 ℃, and the maximum advance is 87.4 ℃; the heat release amounts are up to 2027.58J/g, 2060.01J/g and 2466.28J/g respectively, and the heat release amount of example 3 is up to 2466.28J/g, which is increased by 1719.75J/g compared with 746.53J/g of pure AP, indicating that the compounds of examples 1-3 have remarkable catalytic effect on the thermal decomposition of AP as a combustion rate catalyst. Compared with pure AP, the compound of the invention is added as a burning rate catalyst to form a concentrated exothermic phenomenon in the high-temperature decomposition stage of the system, the exothermic peak temperature is advanced, and the exothermic heat is obviously increased, which proves that the compound of the invention has good combustion catalysis effect on the thermal decomposition of the AP when being used as the burning rate catalyst.
The thermal stability of each of the bisferrocenyl high-nitrogen energetic ionic compounds prepared in examples 1 to 3 was measured by a thermogravimetric analyzer, and the results are shown in FIG. 2. As can be seen from FIG. 2, the compounds of the present invention have good thermal stability at weight loss temperatures above 160 ℃.

Claims (4)

1. The double ferrocenyl high-nitrogen energetic ionic compound is characterized in that the ionic compound is any one of the following compounds 1 to 3:
2. a method of preparing a bisferrocenyl energetic ionic compound of claim 1, comprising the steps of:
(1) At N 2 Under the atmosphere, dissolving 1, 3-dipropynyl imidazole bromide shown in a formula II and azidomethylferrocene shown in a formula I in methanol, uniformly stirring, then adding copper sulfate pentahydrate and sodium ascorbate, stirring for 24-48 hours at room temperature, reacting to generate precipitate, and filtering to obtain an intermediate product A;
(2) Dissolving the intermediate product A in N, N-dimethylformamide, then adding 2-sodium nitrobenzoate or 3, 5-dinitrobenzoate or aqueous solution of 1, 3-potassium tetracyanoacrylate under stirring, stirring at room temperature for reaction for 20-24 hours, evaporating and concentrating after the reaction is finished to remove the solvent, centrifuging and washing, and vacuum drying to obtain the bisferrocenyl high-nitrogen energetic ionic compound.
3. The method for preparing the bisferrocenyl high-nitrogen energetic ionic compound according to claim 2, wherein in the step (1), the molar ratio of the 1, 3-dipropynyl imidazole bromide to the azidomethylferrocene, the copper sulfate pentahydrate and the sodium ascorbate is 1:2-2.5:0.4-0.8:0.4-0.8.
4. The method for preparing a bisferrocenyl high nitrogen energetic ionic compound according to claim 2, wherein in the step (2), the molar ratio of the intermediate product A to sodium 2-nitrobenzoate or sodium 3, 5-dinitrobenzoate or potassium 1, 3-tetracyanoacrylate is 1:1-1.5.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106831889A (en) * 2017-03-28 2017-06-13 陕西师范大学 Biferrocene Triazole ligand and its ionic type metal complex and preparation method
CN108558958A (en) * 2018-04-12 2018-09-21 陕西师范大学 High nitrogen biferrocene triazole ionic type metal complex and preparation method thereof
CN110294780A (en) * 2019-07-09 2019-10-01 陕西师范大学 The aromatic amine burningrate catalyst and preparation method thereof of the triazole group of -1,2,3- containing ferrocenylmethyl
CN110385144A (en) * 2019-07-09 2019-10-29 陕西师范大学 The fatty ethers burningrate catalyst and preparation method thereof of the triazole group of -1,2,3- containing ferrocenylmethyl

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106831889A (en) * 2017-03-28 2017-06-13 陕西师范大学 Biferrocene Triazole ligand and its ionic type metal complex and preparation method
CN108558958A (en) * 2018-04-12 2018-09-21 陕西师范大学 High nitrogen biferrocene triazole ionic type metal complex and preparation method thereof
CN110294780A (en) * 2019-07-09 2019-10-01 陕西师范大学 The aromatic amine burningrate catalyst and preparation method thereof of the triazole group of -1,2,3- containing ferrocenylmethyl
CN110385144A (en) * 2019-07-09 2019-10-29 陕西师范大学 The fatty ethers burningrate catalyst and preparation method thereof of the triazole group of -1,2,3- containing ferrocenylmethyl

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