CN108329360B - Ferrocene picrate ionic compound and preparation method thereof - Google Patents
Ferrocene picrate ionic compound and preparation method thereof Download PDFInfo
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- -1 Ferrocene picrate ionic compound Chemical class 0.000 title claims abstract description 34
- 229940075930 picrate Drugs 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OXNIZHLAWKMVMX-UHFFFAOYSA-N Picric acid Chemical group OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 claims abstract description 8
- IXHMHWIBCIYOAZ-UHFFFAOYSA-N Styphnic acid Chemical group OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C(O)=C1[N+]([O-])=O IXHMHWIBCIYOAZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229940114148 picric acid Drugs 0.000 claims abstract description 8
- 229950002929 trinitrophenol Drugs 0.000 claims abstract description 8
- 150000008040 ionic compounds Chemical class 0.000 claims abstract description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 16
- OXNIZHLAWKMVMX-UHFFFAOYSA-M picrate anion Chemical compound [O-]C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-M 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000005457 ice water Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000001184 potassium carbonate Substances 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229940093956 potassium carbonate Drugs 0.000 claims description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N Ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 abstract description 19
- 239000003054 catalyst Substances 0.000 abstract description 14
- 238000002485 combustion reaction Methods 0.000 abstract description 10
- 239000004449 solid propellant Substances 0.000 abstract description 8
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- HHEFNVCDPLQQTP-UHFFFAOYSA-N Ammonium perchlorate Chemical compound [NH4+].[O-]Cl(=O)(=O)=O HHEFNVCDPLQQTP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000000460 chlorine Substances 0.000 abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 abstract description 3
- 125000001309 chloro group Chemical group Cl* 0.000 abstract description 3
- 150000001768 cations Chemical class 0.000 abstract description 2
- WTZXGPNJQZACFU-UHFFFAOYSA-M cyclopenta-1,3-diene;iron;2,4,6-trinitrophenolate Chemical compound [Fe].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1.[O-]C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O WTZXGPNJQZACFU-UHFFFAOYSA-M 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 description 26
- 230000003197 catalytic Effects 0.000 description 14
- 239000003380 propellant Substances 0.000 description 12
- 238000005979 thermal decomposition reaction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 8
- 239000000028 HMX Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K Aluminium chloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 230000027455 binding Effects 0.000 description 3
- 238000010192 crystallographic characterization Methods 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- ZVUUCUFDAHKLKT-UHFFFAOYSA-M sodium;2,4,6-trinitrophenolate Chemical compound [Na+].[O-]C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O ZVUUCUFDAHKLKT-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000002194 synthesizing Effects 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- JFQLVOODHKKQLO-UHFFFAOYSA-N 1-ethyl-2-[2-(2-ethylcyclopentyl)propan-2-yl]cyclopentane;iron Chemical compound [Fe].CC[C]1[CH][CH][CH][C]1C(C)(C)[C]1[C](CC)[CH][CH][CH]1 JFQLVOODHKKQLO-UHFFFAOYSA-N 0.000 description 2
- 238000006418 Brown reaction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- VUJLGCHOGQEAED-UHFFFAOYSA-N ferrocenecarboxylic acid Chemical compound C12C3C4C5C1[Fe]16782345C2C1(C(=O)O)C8C7C62 VUJLGCHOGQEAED-UHFFFAOYSA-N 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- WFUDBPZFGCNRDM-UHFFFAOYSA-N 1-butylcyclopenta-1,3-diene;cyclopenta-1,3-diene;iron(2+) Chemical compound [Fe+2].C=1C=C[CH-]C=1.CCCCC1=CC=C[CH-]1 WFUDBPZFGCNRDM-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N 2,2'-bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N 420-05-3 Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- XXROGKLTLUQVRX-UHFFFAOYSA-N Allyl alcohol Chemical group OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 1
- 241001120493 Arene Species 0.000 description 1
- 229940095259 Butylated Hydroxytoluene Drugs 0.000 description 1
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N Cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000024881 catalytic activity Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000000536 complexating Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000005712 crystallization Effects 0.000 description 1
- BOXSCYUXSBYGRD-UHFFFAOYSA-N cyclopenta-1,3-diene;iron(3+) Chemical compound [Fe+3].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 BOXSCYUXSBYGRD-UHFFFAOYSA-N 0.000 description 1
- DRTCLTAOSAKXCN-UHFFFAOYSA-N cyclopentane;iron;octylcyclopentane Chemical compound [Fe].[CH]1[CH][CH][CH][CH]1.CCCCCCCC[C]1[CH][CH][CH][CH]1 DRTCLTAOSAKXCN-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229940093909 gynecological antiinfectives and antiseptics Triazole derivatives Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- UZGLIIJVICEWHF-UHFFFAOYSA-N octogen Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UZGLIIJVICEWHF-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229940042055 systemic antimycotics Triazole derivatives Drugs 0.000 description 1
- BXILREUWHCQFES-UHFFFAOYSA-J tetrachloroaluminate(1-) Chemical class Cl[Al-](Cl)(Cl)Cl BXILREUWHCQFES-UHFFFAOYSA-J 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/10—Treating solid fuels to improve their combustion by using additives
Abstract
The invention discloses a kind of ferrocenyl picrate ionic compound and a preparation method thereof, wherein the structural formula of the ionic compound is as follows:wherein R represents chlorine, 2,4, 6-trinitrophenol group or 2,4, 6-trinitroresorcinol group. The complex of the invention has simple preparation method, low cost and high yield, the ferrocenium picrate reduces the mobility and volatility of the ferrocene burning rate catalyst by introducing ferrocenium cations and picric acid radical anions and ionizing, and the picric acid radical anions and the cations also contain energetic groups, so the complex has higher generated heat and combustion heat, can improve the energy level of the solid propellant in the combustion process, and has better combustion catalysis effect on the main components of the composite solid propellant, such as ammonium perchlorate, hexogen and the like.
Description
Technical Field
The invention belongs to the technical field of solid propellants, and particularly relates to an iron arylcene picrate ionic compound and a preparation method thereof.
Background
The hydroxyl-terminated polybutadiene (HTPB) composite solid propellant (a hydroxyl-terminated propellant for short) in the solid propellant is popular in the aerospace field at home and abroad due to excellent process performance, mechanical property and aging property, low price and low viscosity of a prepolymer body HTPB, and the composite solid propellant is suitable for high-solid-content formula charging and large-scale pouring process charging and becomes a propellant widely used in military strategy and tactical missile systems at home and abroad at present. Compared with other burning rate catalysts, the ferrocene compound has the advantages of better flammability, dispersibility, uniformity, compatibility and the like, becomes the most used burning rate catalyst of the existing composite propellant, particularly the AP/Al/HTPB hydroxyl butyl propellant, and is widely applied to various military medium and remote missile propulsion systems.
The ferrocene burning rate catalysts applied in the solid propellant so far mainly include n-butyl ferrocene, tert-butyl ferrocene, 2-bis (ethyl ferrocenyl) propane (Catocene), octyl ferrocene and bis-ethyl ferrocenyl methane (Hycat 6D). Although the commercial ferrocene burning rate catalysts can greatly improve the burning rate of propellants such as butylated hydroxytoluene and the like, the commercial ferrocene burning rate catalysts have the serious defects of easy migration, easy volatilization, low-temperature crystallization, no energy and the like in application, and researchers put forward a series of improvement schemes aiming at the problems.
A U.S. patent published in Huskins in 1972 proposed the introduction of allyl alcohol structure into ferrocene to produce mononuclear ferrocene containing bisallyl alcohol, the introduction of hydroxyl groups significantly reducing migration and volatility. In 1974, Huskens subsequently tried to introduce an isopropylcyano group into ferrocenylbutadiene, reduce the mobility and volatility by increasing the carbon chain and introducing an active group, cyanic acid, and obtain better catalytic activity. Bis- (methylferrocenyl) -methane, 2-bis- (methylferrocenyl) -propane and 2, 2-bis (methylferrocenyl) -butane were also synthesized by wu shong et al in 1989. Two high-efficiency burning rate catalysts, BBFPr (2, 2-bis- (butylferrocene) propane) and BBFPe (1, 1-bis- (butylferrocene) pentane), were synthesized by modifying Catocene in Brutode oil Co., Ltd., Germany in 1995. In 2001, 1, 4-bisferrocenyl imidazole is synthesized by Klimova and the like for the reference of the Yuanfeng and the like, so that three bisferrocene high-nitrogen derivatives are designed and prepared, and the stability and the burning rate catalysis effect of the synthesized compound are tested. Two series of compounds, 2-bis- (monoalkylferrocenyl) -propane and 2, 2-bis (alkylferrocenyl) -propane, were successfully synthesized by people on the verge of happiness in 2004. A novel ethylidene ferrocene derivative is prepared in a patent published in 2009 by Lizang and Tangxiaoming, and the product has the advantages of low synthesis cost, relatively simple preparation process and good catalytic action. In 2010, ferrocene alkynone compounds are modified and improved while occupying a topic group, ferrocene triazole derivatives are synthesized, and are combined with transition metals Cu and Zn in a coordination mode to prepare a series of ferrocene complexes, and the electrochemical performance and the combustion catalytic performance of the ferrocene complexes are researched. Then the subject group synthesizes a novel ferrocene burning-rate catalyst biferrocene unsaturated beta-diketone transition metal complex and a ferrocene aryl beta-diketone metal complex by introducing active groups with large polarity (ferrocene beta-diketone) and metal (Cu and Ni) in a coordination mode. In 2011, Zhang rock et al prepared an epoxidized hydroxyl-terminated polybutadiene ferrocenecarboxylic acid (EHTPB) burning rate catalyst by in-situ grafting ferrocenecarboxylic acid and high-performance adhesive epoxidized hydroxyl-terminated polybutadiene EHTPB. In 2014, Wangchun swallow takes ferrocene tetrazole as a main ligand, 2, 2-bipyridine and 1, 10-phenanthroline as auxiliary ligands, and forms a series of ferrocene tetrazole metal complexes with transition metals.
Disclosure of Invention
The invention aims to overcome the defects of easy migration, easy volatilization and no energy per se of the existing ferrocene catalyst, provide the ferrocenium picrate ionic compound which has good thermal stability under natural conditions, higher heat of formation and combustion and adjustable catalytic performance, and provide a preparation method which is simple to operate and has lower cost for the ionic compound.
The structural formula of the aromatic ferrocene picrate ionic compound adopted for solving the technical problems is as follows:
wherein R represents chlorine, 2,4, 6-trinitrophenol group or 2,4, 6-trinitroresorcinol group.
When R represents chlorine, the preparation method of the ferrocenyl picrate ionic compound comprises the following steps: uniformly mixing ferrocene, aluminum powder, anhydrous aluminum trichloride and chlorobenzene, refluxing for 3-4 hours at 120-140 ℃, adding methanol and ice water, filtering, separating filtrate to obtain a water phase, extracting the water phase with cyclohexane, adding a sodium picrate water solution into the extracted water phase under a dark condition, stirring at normal temperature for reacting for 20-30 minutes, filtering, and drying in vacuum to obtain a cyclopentadienyl iron picrate ionic compound, namely [ cyclopentadiene-iron-chlorobenzene ] picrate; wherein the molar ratio of the ferrocene, the aluminum powder, the anhydrous aluminum trichloride, the chlorobenzene and the sodium picrate is 1: 2.5-3.5: 1-1.5: 1.
When R represents 2,4, 6-trinitrophenol, the preparation method of the ferrocenium picrate ionic compound comprises the following steps: under the condition of keeping out of the sun, dissolving [ cyclopentadiene-iron-chlorobenzene ] picrate, picric acid and potassium carbonate in N, N-dimethylformamide according to the molar ratio of 1: 1-1.5: 2.5-3.5, reacting for 2-3 hours, adding ice water, filtering, washing with absolute ethyl alcohol, and drying in vacuum to obtain the aromatic cyclopentadienyl iron picrate ionic compound.
When R represents 2,4, 6-trinitroresorcinol group, the preparation method of the ferrocenium picrate ionic compound comprises the following steps: under the condition of keeping out of the sun, dissolving [ cyclopentadiene-iron-chlorobenzene ] picrate, trinitroresorcinol and potassium carbonate in N, N-dimethylformamide according to the molar ratio of 1: 1-1.5: 2.5-3.5, reacting for 2-3 hours, adding ice water, filtering, washing with absolute ethyl alcohol, and drying in vacuum to obtain the aromatic cyclopentadienyl iron picrate ionic compound.
The invention has the following advantages:
1. the ferrocenium in the ferrocenium picrate has a sandwich structure similar to ferrocene, and is mainly formed by complexing negatively charged cyclopentadiene negative ions and electrically neutral arene ligands with metallic iron to form stable cations with a positive charge, and then combining with anionic picric acid radicals. The ionic compound takes picric acid radicals as anions, has high nitrogen content, also takes the picric acid radicals and trinitroresorcinol ions of a cation aromatic ring part as nitrogen-rich energetic groups, has extremely low vapor pressure and volatility, has higher generated heat and combustion heat, and is beneficial to solving the problems of easy migration and easy volatilization of ferrocene combustion regulators in propellants.
2. The ionic compound can regulate and control the catalytic performance of ammonium perchlorate, hexogen and otto gold which are main components of the composite solid propellant, change the chemical reaction speed of the propellant during low-pressure combustion, reduce the sensitivity of the burning rate of the propellant influenced by temperature and pressure, improve the ignition performance of the propellant, improve the combustion stability of the propellant and regulate the burning rate of the propellant, thereby realizing different thrust schemes required by the design of the propellant.
3. The ionic compound of the invention has simple preparation method, lower cost and higher yield, and overcomes the defects of complicated synthesis process, high cost, long synthesis period and the like of the existing ferrocene burning-rate catalyst.
Drawings
FIG. 1 is a differential scanning calorimetry analysis of ammonium perchlorate with 5% of the compounds of examples 1 to 3 added thereto.
FIG. 2 is a differential scanning calorimetry analysis of hexogen with 5% of the compound of examples 1-3 added.
FIG. 3 is a differential scanning calorimetry analysis of Auktogin with 5% of the compound of examples 1-3 added.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
Adding 0.93g (5.0mmol) of ferrocene, 0.405g (15.0mmol) of aluminum powder, 2g (15.0mmol) of anhydrous aluminum trichloride and 5mL of chlorobenzene into a 50mL round-bottom flask, magnetically stirring uniformly, heating the flask in an oil bath to 130 ℃, refluxing for 4 hours, transferring the flask into an ice water bath for full cooling, slowly injecting 2mL of methanol into the flask in batches through a condensation tube under the condition of continuous stirring, then pouring 20mL of ice water into the flask, removing the aluminum powder by reduced pressure filtration after the reaction liquid does not release heat any more and is fully cooled, separating the filtrate, extracting the separated water phase for 3 times (10 mL each time) by cyclohexane to obtain [ cyclopentadiene-iron-chlorobenzene ] aluminum tetrachloride salt, wherein the reaction equation is as follows:
dissolving 1.255g (5.0mmol) of sodium picrate in 2.5mL of distilled water, adding the extracted water phase in a dark place, wherein a large amount of light yellow solid can be separated out, continuously stirring in the dark place for 30 minutes, filtering under reduced pressure, and drying in a vacuum drying oven at 40 ℃ to obtain a light yellow powdery solid product [ cyclopentadiene-ferrum-chlorobenzene ] picrate, wherein the yield is 49.5%, and the reaction equation is as follows:
the above-mentioned [ cyclopentadiene-iron-chlorobenzene ]]The solubility of the picrate in water is very small, the picrate can be dissolved in acetonitrile, acetone and DMSO, and the structural characterization data is as follows:1H NMR(400MHz,CDCl3-d6):8.55(s,2H),6.78(s,2H),6.42(s,2H),66.28(m,1H),5.19(s,5H)。
example 2
0.461g (1.0mmol) of [ cyclopentadiene-iron-chlorobenzene ] picrate, 0.287g (1.25mmol) of picric acid, 0.382g (2.77mmol) of potassium carbonate and 5mLN, N-dimethylformamide are added into a 10mL brown reaction flask, stirred at room temperature in a dark place for 2 hours, then 5mL of ice water is added into the reaction flask, at which time a large amount of dark yellow solid is separated out, and then the mixture is filtered under reduced pressure, and after being washed with absolute ethyl alcohol, the filter cake is dried in a vacuum drying oven at 40 ℃ to obtain a yellow flocculent solid product [ cyclopentadiene-iron-2, 4, 6-trinitrodiphenyl ether ] picrate, the yield of which is 82.4%, and the reaction equation is as follows:
the above-mentioned [ cyclopentadiene-Fe-2, 4, 6-trinitrodiphenyl ether ]]The solubility of the picrate in water is very small, the picrate can be dissolved in acetonitrile, acetone and DMSO, and the structural characterization data is as follows:1H NMR(400MHz,CDCl3-d6):8.59(s,4H),6.83(s,2H),6.48(s,2H),6.35(s,1H),5.23(s,5H)。
example 3
Adding 0.461g (1.0mmol) of [ cyclopentadiene-iron-chlorobenzene ] picrate, 0.306g (1.25mmol) of trinitroresorcinol, 0.382g (2.77mmol) of potassium carbonate and 5mLN, N-dimethylformamide into a 10mL brown reaction flask, stirring at room temperature in the dark for 2 hours to ensure that a large amount of dark yellow solid is separated out, then adding 5mL of ice water into the reaction flask, standing, filtering under reduced pressure, washing a filter cake with a small amount of absolute ethyl alcohol, and drying in a vacuum drying oven at 40 ℃ to obtain a yellow solid product [ cyclopentadiene-iron-2, 4, 6-trinitro-3-hydroxydiphenyl ether ] picrate, wherein the yield is 62.6%, and the reaction equation is as follows:
the above-mentioned [ cyclopentadiene-Fe-2, 4, 6-trinitro-3-hydroxydiphenyl ether ]]The solubility of the picrate in water is very small, the picrate can be dissolved in ethanol, acetonitrile, acetone and DMSO, and the structural characterization data is as follows:1H NMR(400MHz,CDCl3-d6):8.59(s,1H),8.55(s,2H),6.74(s,2H),6.40(s,2H),6.29(s,1H),5.17(s,5H)。
in order to prove the beneficial effects of the invention, the inventors tested the catalytic performance of the ferrocenium picrate ionic compound prepared in examples 1-3, and the specific test is as follows:
(1) respectively taking 5mg of each compound prepared in the examples 1-3 and 95mg of powdery AP, and uniformly grinding and mixing;the catalytic performance of the catalyst was measured by a differential scanning calorimeter, and the results are shown in FIG. 1. As can be seen from fig. 1, the thermal decomposition of AP can be divided into three stages: the first process is the phase transition endothermic process of AP, the peak temperature is 237.9 ℃, the peak temperature of the second stage is 286.0 ℃, the process is the low-temperature decomposition process of AP, the peak temperature of the third stage is 404.6 ℃, the process is called the pyrolysis stage, the downward endothermic peak is shown from the low-temperature pyrolysis stage to the pyrolysis stage, and the gas (HCl, NH) formed by the thermal decomposition of AP at the stage is the endothermic peak3) The absorbed heat is larger than the released heat by the decomposition of the AP, so the heat release of the AP by the thermal decomposition process is not obvious. After 5% of the compound of example 1-3 was added to AP, the crystal transition temperature of AP shifted backwards from 237.9 ℃ to about 10 ℃. Meanwhile, the pyrolysis stage of AP is shifted backwards from the original 286.0 ℃ by about 5 ℃. The most varied is that the original heat absorption peak of AP at the high-temperature decomposition stage disappears, namely the peak at 404.6 ℃ in the figure shows new heat release peaks at 358.4 ℃, 374.5 ℃ and 366.1 ℃, and the heat release peaks are advanced to a greater extent than the heat absorption peak at 404.6 ℃ of AP, and the heat release amount is up to 990.3-1092.2J/g, so that the compounds 1-3 can be analyzed to have obvious catalytic action on the thermal decomposition of AP. Therefore, compared with pure AP, the compound of the invention has the advantages that the high-temperature decomposition stage of the system shows a concentrated heat release phenomenon after the compound is added, the heat release peak temperature is advanced, and the released heat is obviously increased, which shows that the compound of the invention has good combustion catalysis effect on the thermal decomposition of AP.
(2) Respectively taking 5mg of each compound prepared in the examples 1-3 and 95mg of powdered hexogen (RDX), grinding and uniformly mixing; the catalytic performance of the catalyst was measured by a differential scanning calorimeter, and the results are shown in FIG. 2. As can be seen from figure 2, RDX has a remarkable exothermic decomposition peak at 229.2 ℃, and the heat released is 803.6J/g; when 5% of the compound of examples 1 to 3 was added to RDX, the heat release of RDX was increased, and the compound of example 1 maximized the heat release of RDX to 1278.3J/g. After the compounds of examples 1-3 were added, the peak temperature values of pure RDX at 230.0 ℃ were increased by 1.9 ℃, 2.8 ℃ and 2.3 ℃ respectively, but the heat release was changed from 803.6J/g to 1278.3J/g, 925.2J/g and 893.3J/g, respectively, which were all improved to some extent, and particularly, the increase was very significant after the compound of example 1 was added. It can be seen that the compounds of examples 1-3 play a certain catalytic role in RDX thermal decomposition in the aspect of heat release.
(3) Respectively taking 1mg of each compound prepared in the embodiments 1-3 and 99mg of powdered octogen (HMX), grinding and uniformly mixing; the catalytic performance of the catalyst was measured by a differential scanning calorimeter, and the results are shown in FIG. 3. It can be seen from the figure that, when 1% of the compounds of examples 1 to 3 was added to HMX under the same external conditions, the decomposition temperature of HMX was lowered although the amount of heat release did not change much before and after the addition. The addition of the compounds of examples 1 and 2 reduced the decomposition temperature by 0.2 ℃ and 2 ℃ respectively, while the addition of the compound of example 3 resulted in a partial decomposition of HMX at 241.8 ℃ and a reduction of the peak temperature by 5.1 ℃ when it was completely decomposed. The compounds of examples 1-3 are shown to have a certain catalytic effect on HMX at the thermal decomposition temperature.
From the above series of catalytic performance test experiments, it can be concluded that: the catalytic action of the compounds of the embodiments 1 to 3 on AP is most obvious, so that the peak temperature of thermal decomposition is more concentrated, and the heat release is also obviously increased; the compounds of examples 1 to 3 did not lower the peak temperature of RDX, but increased the amount of heat release of RDX to some extent; the compounds of examples 1-3 lead to a thermal decomposition temperature of HMX.
Claims (3)
1. An iron arylcyclopentadienyl picrate ionic compound, which is characterized in that the structure of the ionic compound is as follows:
wherein R represents 2,4, 6-trinitrophenol group or 2,4, 6-trinitroresorcinol group.
2. A process for the preparation of an iron arylmetallocene picrate ionic compound of claim 1, wherein R represents a 2,4, 6-trinitrophenol group, characterized in that: under the condition of keeping out of the sun, dissolving [ cyclopentadiene-iron-chlorobenzene ] picrate, picric acid and potassium carbonate in N, N-dimethylformamide according to the molar ratio of 1: 1-1.5: 2.5-3.5, reacting for 2-3 hours, adding ice water, filtering, washing with absolute ethyl alcohol, and drying in vacuum to obtain the aromatic cyclopentadienyl iron picrate ionic compound.
3. A process for the preparation of an iron arylmetallocene picrate ionic compound of claim 1, wherein R represents 2,4, 6-trinitroresorcinol group, characterized in that: under the condition of keeping out of the sun, dissolving [ cyclopentadiene-iron-chlorobenzene ] picrate, trinitroresorcinol and potassium carbonate in N, N-dimethylformamide according to the molar ratio of 1: 1-1.5: 2.5-3.5, reacting for 2-3 hours, adding ice water, filtering, washing with absolute ethyl alcohol, and drying in vacuum to obtain the aromatic cyclopentadienyl iron picrate ionic compound.
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Non-Patent Citations (4)
| Title |
|---|
| 二茂铁唑类富氮含能离子化合物的合成、结构表征、迁移性及其燃烧催化性能;刘学林;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20170331(第03期);第17页1.5.3节，第24页2.3.4节第1段，第71页图4-4，第95页化合物3 * |
| 刘学林.二茂铁唑类富氮含能离子化合物的合成、结构表征、迁移性及其燃烧催化性能.《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2017,(第03期),第1-115页. * |
| 含芳醚配体的芳茂铁盐的合成研究;徐金雷 等;《化学试剂》;20070131;第29卷(第1期);第1-3；6页 * |
| 新型稠环芳茂铁阳离子光引发剂的合成及其光学性能研究;李治全;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20111231(第S1期);第B014-158-28页第2.2.2.1节，第B014-158-35页第3.1.2节 * |
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