RU2739190C1 - Method of producing high-density and high-energy rocket and aviation fuel based on 2-vinyl norbornane (versions) - Google Patents

Abstract

FIELD: fuel industry.

SUBSTANCE: invention relates to a novel two-step method of synthesis of components of high-density and high-energy rocket and aviation fuel based on 2,2'-bis(norbornanyl), which can be used as high-energy fuel, particularly rocket fuel and for long-range aviation. Described is a method of producing a high-density and high-energy rocket and aviation fuel component based on 2- vinyl norbornane, involving a Diels—Alder thermal reaction of a mixture of exo-/endo-isomers of 2-vinyl norbornane with dicyclopentadiene while heating and subsequent hydrogenation of the obtained mixture of 5-(2'-norbornanyl)norbornene isomers in the presence of hydrogen and a hydrogenation catalyst taken in ratio of 0.5–10 wt %. in relation to 5-(2'-norbornanyl)-norbornene, at room temperature and hydrogen pressure of 30–60 atm (versions).

EFFECT: technical result is high output of obtained high-density and high-energy component of rocket and aviation fuel—2,2'-bis(norbornanyl)—up to 92 % with simplicity of method, which does not require large amounts of catalyst, inert atmosphere or anhydrous reagents.

4 cl, 3 dwg, 1 tbl, 8 ex

Description

The invention relates to a new method for the synthesis of 2,2'-bis (norbornanyl), which can be used in various sectors of the national economy and, in particular, as a component of high-energy rocket or aviation fuel, including for long-range aviation, which has a set of useful properties ( high volumetric heat of combustion, density and boiling point, low toxicity).

At present, the active development of aviation and cosmonautics continues. First of all, this is due to the need to develop the far corners of the Earth, create advanced types of weapons, as well as modern space information systems - communication systems, meteorology, navigation, systems for monitoring the use of natural resources and environmental protection and much more. It should be noted that the development of aviation and astronautics is impossible without the creation of energy-intensive fuel with a high level of performance.

Liquid fuels are widely used in various aerospace vehicles, and engine power is highly dependent on the properties of the fuel used, for which the most important characteristics are high density, energy characteristics, low freezing points and viscosity. Air and aerospace vehicles are highly limited in volume, so their fuel tanks should be as small as possible to leave enough room for electronics, weaponry, and other critical components.

One of the most widely used aviation fuels, especially in developed countries, is exo-tetrahydrodicyclopentadiene (JP-10) [T.J. Bruno, M.L. Huber, A. Laesecke, E. W. Lemmon, RA Perkins. Thermochemical and thermophysical properties of JP-10. National Institute of Standards and Technology Internal Report. June 2006.]. Low freezing point (-79 ° C), high flash point (54 ° C) and density (0.92-0.93 g / cm ³ ) satisfy the requirements for its use at both low and high altitudes.

Despite a significant number of works devoted to methods for the synthesis of exo-tetrahydrodicyclopentadiene, the search for more efficient and safer synthetic approaches remains an urgent task.

The development of new high-energy-consuming fuels that exceed JP-10 in density, heat of combustion, efficiency and safety of production and storage also remains an urgent task.

One of these fuels can be 2,2'-bisnorbornanyl, containing two strained bicyclic fragments with high energy content (19-20 kcal / mol), only slightly inferior to highly stressed small cycles - cyclopropane and cyclobutane (26-28 kcal / mol), and due to the release of additional thermal energy upon rupture of strained C-C bonds during combustion.

In addition, 2,2'-bisnorbornanyl can exist in the form of 3 structural isomers, and if a mixture of isomers is obtained, the latter will have a lower melting point, which is an important criterion for a high-energy fuel.

Methods for producing 2,2'-bis (norbornanyl) currently described in the literature use metal complex catalysis reactions. The disadvantages of the approaches to the synthesis of 2,2'-bis (norbornanyl) presented in the literature are the insufficient yield of the target product, the need to use expensive catalysts containing complex ligands, high catalyst concentrations in the mixture, synthesis in an inert atmosphere, and in some cases the use of organometallic reagents in stoichiometric amounts.

Methods for preparing 2,2'-bis (norbornanyl).

In [A. Tenaglia, E. Terranova, B. Waegell. Nickel-catalyzed dimerization of norbornene. // Journal of Molecular Catalysis. 1987. T. 40. P. 281-287] describes the synthesis (exo / endo-2,2'-bis (norbornanyl) by hydrogenation of 2- (exo-2'-norbornanyl) norbornene. The latter was obtained according to a two-step scheme with a total 38% yield by dimerization of 2-norbornene in the presence of Ni complexes followed by hydrogenation with hydrogen on a platinum catalyst The proposed method uses large loads of nickel catalyst, which limits the possibilities of this approach.

In the work [A.V. Kuchin, R.A. Nurushev, L.M. Khalilov, G.A. Tolstikov. Comparative study of the stereo- and regioselectivity of hydroalumination with various reagents of olefins of norbornane structure. // Journal of General Chemistry. 1987. V. 57. S. 1763-1768] describes the synthesis of a mixture of exo / endo isomers of 2,2'-bis (norbornanyl) by hydroalumination of 2-norbornene in the presence of ZrCl ₄ , followed by oxidation of the resulting alane with oxygen and hydrolysis. The proposed approach does not allow to obtain 2,2'-bis (norbornanyl) in acceptable yields.

In [J.E. Corey, H.H. Zhu. Reaction of hydrosilanes and olefins in the presence of Cp ₂ MCl ₂ / n-BuLi. // Organometallics. 1992. T. 11. C. 672-683] describes the synthesis of a mixture of exo / endo isomers of 2,2'-bis (norbornanyl) by dimerization of 2-norbornene in the presence of a system of di-n-propylsilane / titanocene dichloride / n-butyllithium. Although this method is a one-step method, the target product is obtained in very low yields and at the same time, large loads of catalyst and n-butyllithium are used.

In [S. Derien, J.C. Clinet, E. Dunach, J. Perichon. Electrochemical incorporation of carbon dioxide into alkenes by nickel complexes. // Tetrahedron. 1992. T. 48. C. 5235-5248] describes the preparation of a mixture of exo / endo isomers of 2,2'-bis (norbornanyl) by electrolysis of norbornene in the presence of CO ₂ and nickel complexes, probably by a radical mechanism. The approach proposed by the authors made it possible to obtain the target 2,2'-bis (norbornanyl) in one stage with an average yield; however, to achieve this result, it is necessary to use the catalyst practically as a reagent (20 mol%), which is not of interest for further use.

In [Y.L. Chow, X.E. Cheng. The reaction pattern of norbornene with excited states carbonyl compounds: photochemical preparations of norbornene derivatives. // Research on chemical intermediates. 1993. T. 19. C. 211-234] describes the preparation of a mixture of lzo- / endo-isomers of 2,2'-bis (norbornanyl) by UV photolysis of norbornene in hexane in the presence of triplet sensitizers, for example, benzophenone. The disadvantages of this method are both low product yields and the need to use ultraviolet radiation and a special quartz reactor.

In the work [U.М. Dzhemilev, R. M. Sultanov, RG Gaimaldinov. Catalytic synthesis and transformations of magnesacycloalkanes. 3. Cyclomagnesation of norbornenes catalyzed by Cp ₂ ZrCl ₂ . // Russian Chemical Bulletin. 1993. T. 42. C. 149-153] describes the preparation of a mixture of exo / endo-isomers of 2,2'-bis (norbornanyl) by the reaction of 2-norbornene with dipropyl magnesium, in the presence of Cp ₂ ZrCl ₂ , followed by acid hydrolysis. This method allows to obtain 2,2'-bis (norbornanyl) in good yield in two stages, but the reaction requires large loads of catalyst and Grignard reagent, and the reaction must also be carried out in an inert atmosphere and in dry solvents. This significantly limits the potential of this transformation scheme.

In the work [DJ Huang, S.N. Cheng. [2 + 2] Dimerization of norbornadiene and its derivatives in the presence of nickel complexes and zinc metal. // Journal of organometallic chemistry. 1995. T. 490. C. C1-C7] describes the preparation of a mixture of exo / endo isomers of 2,2'-bis (norbornanyl) by reductive dimerization of 2-norbornene with zinc, in the presence of NiCl ₂ (PPh ₃ ) ₂ . Low yields and high catalyst loadings markedly reduce the possibilities of this approach.

In [A. Malinowska, I. Czelusniak, M. Gorski, T. Szymanska-Buzar. W (II) -Catalyzed hydroarylation of bicycle [2.2.1] -hept-2-ene by simple arenes. // Tetrahedron Letters. 2005. T. 46. C. 1427-1431] describes the preparation of a mixture of exo / endo isomers of 2,2'-bis (norbornanyl) by the reaction of 2-norbornene with a heterobimetallic complex (CO) ₄ W (Cl) ₃ W (SnCl ₃ ) (CO) ₃ in chlorobenzene. The target compound was obtained in good yield. However, to achieve such yields, it is necessary to use large loads of tungsten catalyst and tin-containing cocatalyst.

Preparation of 2,2'-bis (norbornanyl) by hydrogenation of a mixture of exo / endo isomers of 5- (2'-norbornanyl) -norbornene

A common disadvantage of all the described technical solutions for obtaining 2,2'-bis (norbornanyl) is the use of expensive catalysts, magnesium or organolithium compounds, and in some cases low product yields. (3-5%).

In addition, the synthesis is carried out in an inert atmosphere using absolute (not containing water and dissolved oxygen) solvents.

From the presented analysis of scientific and patent literature, it can be seen that the highest yield of 2,2'-bis (norbornanyl) is achieved in a two-stage synthesis starting from norbornene using a zirconocene catalyst and an organomagnesium compound.

In [A. Bell, L. Langsdorf, O. Burtovyy. Cycloalkylnorbornene monomers, polymers derived therefrom and their use in pervaporation. // Patent. WO 2014/025735 A1] describes the preparation of a mixture of isomers of 5- (2'-norbornanyl) -norbornene by the thermal Diels-Alder reaction from a mixture of exo / endotomers of 2-vinylnorbornane (hereinafter VNBa) with dicyclopentadiene with a product yield of 55%.

However, the resulting product cannot be used as a fuel or its component.

The objective of the present invention is to develop an economical and convenient method for producing 2,2'-bis (norbornanyl) with high yield and purity, with the possibility of using it as a high-density and high-energy component and a component of aviation and jet fuel.

The problem is solved by the fact that a method is proposed for producing a component of high-density and high-energy rocket and aviation fuel based on 2-vinylnorbornane (BNBA), which includes carrying out the thermal Diels-Alder reaction of a mixture of exo / endotomers of 2-vinylnorbornane (hereinafter VNBa) with dicyclopentadiene at heating and subsequent hydrogenation of the resulting mixture of isomers of 5- (2`-norbornanyl) -norbornene (hereinafter VNB-VNBa) in the presence of hydrogen and a hydrogenation catalyst, taken in a ratio of 0.5-10 wt%. in relation to 5- (2'-norbornanyl) -norbornene at room temperature and a hydrogen pressure of 30-60 atm.

According to a second embodiment of the invention, a method for producing a component of a high-density and high-energy rocket and aviation fuel based on 2-vinylnorbornane is proposed, including carrying out a thermal Diels-Alder reaction of a mixture of exo / endo isomers of 2-vinylnorbornane with dicyclopentadiene upon heating and subsequent hydrogenation of the resulting mixture of isomers 5 - (2`-norbornanyl) -norbornene in the presence of hydrazine hydrate, air, hydrazine decomposition catalyst and hydrogenation catalyst, taken in a ratio of 0.5-10 wt%. in relation to 5- (2'-norbornanyl) -norbornene at room temperature and a hydrogen pressure of 30-60 atm.

In both embodiments, a heterogeneous catalyst based on a transition metal supported on a support, including palladium on a carbon support, platinum on a carbon support, and Raney nickel, is used as a hydrogenation catalyst.

The reaction proceeds as follows. During the first stage, the yield of VNB-VNB was 55%. Analysis by gas chromatography-mass spectrometry made it possible to establish that the reaction product is three isomers of 5- (2`-norbornanyl) -norbornene, formed in the ratio

spectrometry made it possible to establish that the reaction product is three isomers of 5- (2'-norbornanyl) -norbornene, formed in a ratio of 33/47/20. These compounds have close retention times and almost identical mass spectra. We assume that the obtained isomers are a mixture of exo / endo, endo / exo, and endo / endo isomers, while the exo / exo isomer, as the most stressed, is not formed during the reaction.

Hydrogenation of the resulting mixture of 5- (2'-norbornyl)-norbornene isomers with hydrogen in the presence of Pd on activated carbon at room temperature, in hexane, with a yield of 91%, gives a mixture of two 2,2'-bisnorbornane isomers in the ratio 69/31 ( GLC).

The technical result is the possibility of obtaining a high-density and high-energy component of rocket and aviation fuel - 2,2'-bis (norbornanyl) with a high yield - up to 92% with the simplicity of the method.

It should be noted that our proposed method for producing 2,2'-bis (norbornanyl) does not require an inert atmosphere, the use of organometallic compounds, or expensive catalysts. The synthesis is carried out in two stages. The original 2-vinylnorbornane (VNBa) was obtained by the previously developed method [S.V. Shorunov, E.S. Piskunova, V.A. Petrov, V.I. Bykov, M.V. Bermeshev. Selective hydrogenation of 5-vinyl-2-norbornene to 2-vinylnorbomane. // Petroleum Chemistry. 2018. T. 58. C. 1056-1063]. VNBA consists of a mixture of exo / endo isomers with a ratio of 30/70. Selective hydrogenation of the endocyclic double bond results in a mixture of exo / endo-2-vinylnorbornane with the same isomer ratio. When a mixture of exo / endo-2-vinylnorbornane is introduced into the Diels-Alder reaction with dicyclopentadiene, a mixture of three isomers of 2- (2-norbornyl) -5-norbornene is obtained, the hydrogenation of which gives a mixture of 2 isomers of 2,2'-bis (norbornanyl) having a lower melting point than the individual isomers. This mixture can be used as a high-energy component of rocket and aviation fuels.

The following examples illustrate the invention.

Getting 2,2'-bis (norbornanyl)

Materials, preparation of reagents and solvents

All solvents used in the work, as well as copper (II) sulfate, were purchased from Komponent-Reaktiv and were used without preliminary purification.

Research methods

NMR spectra were recorded on Varian Inova 500, Bruker Avance DRX 400 and BrukerMSL-300 NMR spectrometers. For ¹ H-NMR spectra, the recording frequencies are 499.8 MHz, 400.1 MHz and 300 MHz, respectively. The signals in the ¹ H spectra were assigned to the residual protons of CDCl ₃ (7.24 ppm).

Chromato-mass spectrometric analysis was carried out on a Finnigan MAT 95 XL gas chromatography-mass spectrometer (ionization energy 70 eV, mass range 20-800 amu, resolution 1000, source temperature 200 ° C, scan rate 1 s / ten masses) and an HP 6890+ chromatograph with a 30 m × 0.25 mm capillary column with a DB-5 phase (polydimethylsiloxane containing 5% phenyl groups), carrier gas helium (flow division 1:30).

Gas chromatographic analysis was performed on a Kristall 5000 gas chromatograph with an SGE Analytical Science capillary column and a flame ionization detector (FID). Column length 25 m × 0.32 mm, phase HTE8 (polysiloxanecarborane containing 8% phenyl groups), carrier gas nitrogen. PID parameters: temperature at the detector - 200 ° С, hydrogen flow rate - 25 ml / min, air flow rate - 250 ml / min, nitrogen flow rate - 25 ml / min. Column parameters: column temperature control - 40 ° С, carrier gas pressure - 71.519 kPa, carrier gas flow - 2.5 ml / min, carrier gas velocity - 39.7 cm / s, discharge flow - 30 ml / min. Evaporator temperature - 250 ° С.

Example 1.

The stage of measuring and mixing the reagents, carrying out the Diels-Alder reaction between dicyclopentadiene (DCPD) and a 4-fold amount of VNBa and distillation of unreacted VNBa.

The Diels-Alder reaction between DCPD and VNBa is carried out similarly to the previously published procedure [A. Bell, L. Langsdorf, O. Burtovyy. Cycloalkylnorbornene monomers, polymers derived therefrom and their use in pervaporation. // Patent. WO 2014/025735 A1]. In a steel autoclave with a volume of 2000 ml, equipped with a magnetic stirrer, a screw neck for introducing reagents, a heating jacket, a thermocouple, a pressure gauge and a pipe for connecting a hydrogen cylinder with a reducer (a pipe for hydrogen is used in the next stage of hydrogenation, at this stage it is closed) 600 ml (504 g, 4.1 mol) VNBa, 140 ml (137.2 g, 1.03 mol) DCPD and 10 g hydroquinone. The reaction mass is stirred at a speed of 50 rpm and heated to 220 ° C. Heating is continued for 4 hours. After 4 hours, the heating is stopped, the reaction mixture is allowed to cool, and an aliquot (~ 0.05 ml) is taken through the throat with a syringe equipped with a long needle, the aliquot is poured into a clean vial with a capacity of 4-8 ml, with a screw cap, containing 3 ml of hexane, close the vial with a lid , shake, and inject 1 μl of the resulting solution of the reaction mixture in hexane into the gas chromatograph. Gas chromatograph "Chromatek-Kristall-5000" version 2 with a capillary column "SGE Analytical Science") and a flame ionization detector (FID) are used for gas chromatographic analysis. Column length 25 m × 0.32 mm, phase HTE8 (polysiloxanecarborane containing 8% phenyl groups), carrier gas nitrogen. PID parameters: temperature at the detector - 200 ° С, hydrogen flow rate - 25 ml / min, air flow rate - 250 ml / min, nitrogen flow rate - 25 ml / min. Column parameters: column temperature control - 40 ° С, carrier gas pressure - 71.519 kPa, carrier gas flow - 2.5 ml / min, carrier gas velocity - 39.7 cm / s, discharge flow - 30 ml / min. Evaporator temperature - 250 ° С. The reaction mixture should contain unreacted VNBa, ethylnorbornane, the product and a small amount of impurities. The reaction mixture is squeezed with compressed air from the throat for introducing the reagents into the distillation apparatus - a 1000 ml Claisen flask equipped with a reflux condenser, a descending condenser, an allonge and a receiver and the unreacted VNBa and ethylnorbornane are distilled off at 50 mm, collecting the fraction boiling in the range 60-80 ° FROM. The yield is usually 270-300 g. Bottom residue (340-370 g) is kept together with the flask.

The stage of re-introduction of the distilled VNBa into the reaction with the calculated amount of DCPD and distillation of the unreacted VNBa.

The distilled mixture of VNBa and ethylnorbornane is placed back into the autoclave, a new portion of DCPD is added, the volume of which is calculated by the formula M _VNBa × 0.27, where M _{VNB is the} mass of _VNBa distilled from the reaction and 5 g of hydroquinone. The reaction mass is stirred at a speed of 50 rpm and heated to 220 ° C. Heating is continued for 4 hours. After 4 hours, the heating is stopped, the reaction mixture is allowed to cool, an aliquot is taken, analyzed as described in step 4.1, and the reaction mixture is squeezed with compressed air from the throat for introducing the reagents into the distillation apparatus used previously, equipped with a 500 ml Claisen flask, a reflux condenser, a descending condenser, an allonge and a receiver and unreacted VNBa and ethylnorbornane are distilled off at 50 mm, collecting a fraction boiling in the range of 60-80 ° C. The yield is usually about 150-160 g. The bottoms (220-230 g) are combined with the bottoms obtained after the first condensation reaction in a 1500 ml Claisen flask. To transfer bottoms with high viscosity, you can dilute them with a small amount of hexane to an acceptable consistency.

The stage of the final introduction of the distilled VNB into the reaction with the calculated amount of DCPD.

The distilled mixture of VNBa and ethylnorbornane is placed back into the autoclave, a new portion of DCPD is added, the volume of which is calculated by the formula M _VNBa × 0.27, where M _{VNB is the} mass of _VNBa distilled from the reaction and 5 g of hydroquinone. The reaction mass is stirred at a speed of 50 rpm and heated to 220 ° C. Heating is continued for 4 hours. After 4 hours, the heating was stopped, the reaction mixture was allowed to cool, an aliquot was taken, analyzed as described, and proceeded to the next stage.

The stage of distillation of the reaction mixture of the final condensation and combined bottoms and the isolation of VNB-VNBa.

The reaction mixture obtained after the third condensation (180-200 g) is squeezed with compressed air or nitrogen from the throat for introducing reagents into a Claisen flask with a capacity of 1500 ml, containing the combined bottoms from the first and second charges, equipped with a reflux condenser, a descending condenser, a spider and receivers and dispersed under vacuum at a pressure of 1 mm. First, hexane is distilled off (if it was used to transfer bottoms), VNBa residues, ethylnorbornane and trace amounts of DCPD. Collect the fraction boiling in the range of 100-110 ° C. Receive 380-420 g (50-54%) VNB-VNBa in the form of a colorless liquid, with a purity of at least 90%. According to GLC and GC-MS data, the product is a mixture of three isomers in a 33/47/20 ratio.

The stage of hydrogenation of the obtained VNB-VNBa with hydrogen in the presence of 2% by weight (10% palladium on activated carbon) in hexane.

A mixture of 400 g (2.12 mol) of VNB-VNBa isomers, 8.0 g (2% by weight) 10% Pd / is loaded into a steel autoclave with a volume of 2000 ml, equipped with a magnetic stirrer), a screw neck for introducing reagents, a pressure gauge and a nozzle for introducing hydrogen with a reducer. C and 500 ml of hexane. Connect a balloon with hydrogen and stir the reaction mixture for 5 days at room temperature and a hydrogen pressure of 30 atm. At the end of 5 days, the pressure is released, an aliquot is taken, and analyzed as described above. The presence of VNB-VNBA is determined using gas-liquid chromatography. In the absence of VNB-VNB, proceed to the next stage.

Stage of filtration of the reaction mixture from the hydrogenation catalyst.

Upon completion of the hydrogenation process, the reaction mixture is pushed from the autoclave with compressed air (nitrogen) into a flat-bottomed flask with a capacity of 2000 ml. The autoclave is washed three times with 200 ml portions of hexane and the wash extracts are combined with the reaction mixture. Filter under vacuum of a water-jet pump into a 5000 ml Bunsen flask through a Schott filter with a diameter of 10 cm and a height of 6 cm, filled 3 cm in height with silica gel 40-63 μm. A paper filter with a diameter of 5 cm is placed on the top of the silica gel pillow, in the center, and during filtration, try to pour the reaction mixture onto the paper filter to avoid deformation of the silica gel pillow. It is important to turn on the vacuum before starting filtration. After filtration of the reaction mixture, the silica gel is washed with 1500 ml of hexane. Approximately 3000 ml of a solution of BNBA in hexane, filtered from the catalyst, is obtained.

The step of distilling off hexane and distilling the reaction mixture and isolating BNBA.

From the resulting solution, hexane is distilled off on a rotary evaporator in a flask with a capacity of 5000 ml to a residual volume of about 600 ml. The residue is transferred into a 1000 ml Claisen flask equipped with a reflux condenser, a descending condenser, a spider and receivers and dispersed in a vacuum at a pressure of 1 mm Hg. A fraction with a boiling point of 82-84 ° C is collected. The product yield is 360-370.0 g (89-92%). According to GLC data, the resulting substance is a mixture of two BNBA isomers in a 69/31 ratio.

¹ H NMR spectrum (Fig. ¹ : ¹ H NMR spectrum of 2,2'-bis (norbornanyl) in CDCl ₃ ). The ¹ H NMR spectrum of 2,2'-bis (norbornanyl) contains the signals of the protons of the norbornane fragment in the region of 0.64-2.18 ppm. The spectrum contains no signals from the protons of the norbornene double bond (region 6.0-6.2 ppm), which indicates the absence of the initial 5- (2'-norbornanyl) -norbornene.

¹³ C NMR spectrum (Fig. 2: ¹³ C NMR spectrum of 2,2'-bis (norbornanyl) in CDCl ₃ ). The ¹³ C NMR spectrum of 2,2'-bis (norbornanyl) contains signals of aliphatic carbon atoms of the norbornane fragment in the range of 22.8-46.0 ppm. The spectrum lacks signals of alkenyl carbon atoms, which indicates the absence of the starting 5- (2'-norbornanyl) -norbornene.

Mass Spectrum (Figure 3: Mass Spectrum of 2,2'-bis (norbornanyl).). Molecular ion М ⁺ 190 (22), 161 (22), 121 (38), 108 (23), 95 (60), 80 (53), 67 (100), 41 (25).

Calorific value and density measurement of 2,2'-bis (norbornanyl)

The highest specific heat of combustion of 2,2'-bis (norbornanyl) is measured using an IKA C200 calorimeter according to the standard procedure in accordance with GOST 21261-91. The lowest heat of combustion is calculated based on the mass fraction of hydrogen in the pure substance in accordance with GOST 21261-91.

The density of 2,2'-bis (norbornanyl) is measured on a VIP-2MR vibration density meter according to the standard method in accordance with GOST R 57037-2016.

The crystallization temperature of 2,2'-bis (norbornanyl) is measured using a Kristall-20E apparatus according to the standard procedure in accordance with GOST 18995.5-73.

The characteristics of the resulting component of high-energy rocket or aviation fuel are given in table. one.

Example 2

Differs from example 1 in that at the stage of hydrogenation take 0.5% (by weight of VNB-VNBa) 10% Pd / C.

The hydrogenation is carried out for 10 days at room temperature and a hydrogen pressure of 30 atm.

A component of high-energy rocket or aviation fuel is obtained with a yield of 90%.

The characteristics of the resulting component of high-energy rocket or aviation fuel are given in table. one.

Example 3

Differs from example 1 in that at the stage of hydrogenation take 2% (by weight of VNB-VNBa) 5% Pd / C.

The hydrogenation is carried out for 10 days at room temperature and a hydrogen pressure of 30 atm.

A high-energy rocket or aviation fuel component is obtained with a yield of 88%.

The characteristics of the resulting component of high-energy rocket or aviation fuel are given in table. one.

Example 4

Differs from example 1 in that pentane is used instead of hexane in the hydrogenation step.

The hydrogenation is carried out for 5 days at room temperature and a hydrogen pressure of 30 atm.

A high-energy rocket or aviation fuel component is obtained with a yield of 91%.

The characteristics of the resulting component of high-energy rocket or aviation fuel are given in table. one.

Example 5

Differs from example 1 in that no solvent is used in the hydrogenation step.

The hydrogenation is carried out for 5 days at room temperature and a hydrogen pressure of 30 atm.

Next, the reaction mixture is diluted twice with hexane and then filtered and distilled as described in example 1.

A high-energy rocket or aviation fuel component is obtained with a yield of 91%.

The characteristics of the resulting component of high-energy rocket or aviation fuel are given in table. one.

Example 6.

Differs from example 1 in that at the stage of hydrogenation take 2% (by weight of VNB-VNBa) 5% Pt / C.

The hydrogenation is carried out for 10 days at room temperature and a hydrogen pressure of 30 atm.

A high-energy rocket or aviation fuel component is obtained with a yield of 92%.

The characteristics of the resulting component of high-energy rocket or aviation fuel are given in table. one.

Example 7.

Differs from example 1 in that at the stage of hydrogenation take 10% (by weight of VNB-VNBa) Raney nickel.

Hydrogenation is carried out for 10 days at room temperature and a hydrogen pressure of 60 atm.

A high-energy rocket or aviation fuel component is obtained with a yield of 92%.

The characteristics of the resulting component of high-energy rocket or aviation fuel are given in table. one.

Example 8.

The reaction is carried out in a thermostated, three-necked glass reactor with a magnetic stirrer, reflux condenser and air bubbler. Into a mixture of methanol (60 ml), hydrazine hydrate 12 ml (12.0 g, 0.24 mol, 3 equivalents) and VNB-VNBA (15 g 0.08 mol) is added dropwise a solution of the catalyst for the decomposition of hydrazine - copper sulfate pentahydrate (0.21 g in 10 ml of methanol) or 2% of the mass for hydrazine hydrate. Then, with stirring, pass the oxidizing agent - air at a rate of 3.5 l / h. It should be noted that the reaction does not proceed in the absence of air. Samples are taken at regular intervals and analyzed by GLC.

Conversion VNB-VNBa 100% after 6 hours of reaction. To isolate the target product, the aqueous-alcoholic phase is separated from the organic phase, which is then neutralized with Dowex 50 polyacid and distilled under vacuum, as described in example 1. Catalyst — copper salt (copper sulfate).

A high-energy rocket or aviation fuel component is obtained with a yield of 85%.

The characteristics of the resulting 2,2'-bis (norbornanyl) - a component of high-energy rocket or aviation fuel are given in table. one.

From the results obtained on the study of the properties of BNBA, it can be seen that in a number of parameters this hydrocarbon is superior to the known JP-10 rocket fuel, which is similar in structure to the hydrocarbon obtained by us.

Thus, an effective approach to the synthesis of 2,2'-bis (norbornanyl) without expensive compounds and without the use of special equipment with high yields of a commercial product has been proposed.

- a high-density and high-energy component of aviation or jet fuel.

It is shown for the first time that this hydrocarbon is a promising component for the creation of liquid rocket and aviation fuels with a high density and energy intensity. 2,2'-Bis (norbornanyl) has a higher density and specific heats of combustion than a related hydrocarbon - tetrahydro-exo-dicyclopentadiene, which is currently actively used as the basis of JP-10 fuel. Higher values of density and calorific value found for 2,2'-bis (norbornanyl) will significantly increase the range and speed of flight of aerospace objects when 2,2'-bis (norbornanyl) is used as one of the propellants.

Claims (4)

1. A method of obtaining a component of high-density and high-energy rocket and aviation fuel based on 2-vinyl norbornane, including carrying out the thermal Diels-Alder reaction of a mixture of exo / endo isomers of 2-vinyl norbornane with dicyclopentadiene upon heating and subsequent hydrogenation of the resulting mixture of isomers 5- (2` -norbornanyl) -norbornene in the presence of hydrogen and a hydrogenation catalyst taken in a ratio of 0.5-10% of the mass. in relation to 5- (2`-norbornanyl) -norbornene, at room temperature and hydrogen pressure of 30-60 atm. 2. The method according to claim 1, characterized in that a heterogeneous catalyst based on a transition metal supported on a carrier, including palladium on a carbon carrier, platinum on a carbon carrier, Raney nickel, is used as the hydrogenation catalyst. 3. A method for producing a component of high-density and high-energy rocket and aviation fuel based on 2-vinyl norbornane, including carrying out the thermal Diels-Alder reaction of a mixture of exo / endo isomers of 2-vinyl norbornane with dicyclopentadiene upon heating and subsequent hydrogenation of the resulting mixture of isomers 5- (2` -norbornanyl) -norbornene in the presence of hydrazine hydrate, air, a catalyst for the decomposition of hydrazine and a hydrogenation catalyst taken in a ratio of 0.5-10 wt%. in relation to 5- (2`-norbornanyl) -norbornene, at room temperature and hydrogen pressure of 30-60 atm. 4. A method according to claim 3, characterized in that a heterogeneous catalyst based on a transition metal supported on a carrier, including palladium on a carbon carrier, platinum on a carbon carrier, Raney nickel, is used as the hydrogenation catalyst.

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