RU2739242C1 - Method of producing high-density and high-energy rocket and aviation fuel component based on methyl-substituted 2,2'-bis (norbornanyl) (versions) - Google Patents

Abstract

FIELD: fuel industry.

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

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

4 cl, 2 tbl, 8 ex, 4 dwg

Description

The invention relates to a new method for the synthesis of methyl-substituted 2,2'-bis (norbornanyl) (hereinafter NBAMeNBA), 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 with a complex 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 is still 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 such fuels can be methyl-substituted 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 during the rupture of strained C-C bonds during combustion.

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

Only one example of obtaining NBAMeNBA is described in the literature. He, like the methods currently described in the literature for the preparation of 2,2'-bis (norbornanyl), uses metal complex catalysis reactions. The disadvantages of the approaches to the synthesis of these compounds 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, the synthesis in an inert atmosphere, and, in some cases, the use of organometallic reagents in stoichiometric amounts.

Methods for preparing methyl-substituted 2,2'-bis (norbornanyl)

In the work [S. Bianchini, G. Giambastini, A. Meli, A. Toti. Diastereoselective alkylation-vinylation of norbornene catalyzed by a tetrahedral cobalt (II) pyridinimine complex. // Organometallics. 2007. T. 26. C. 1303-1305] describes the synthesis of exo / exo-2-methyl-substituted bis (norbornanyl) by the interaction of 2-norbornene with 6 equivalents of methylaluminoxane in the presence of 3% cobalt catalyst (1).

Methods for producing 2,2'-bis (norbornanyl)

In [A. Tenaglia, E. Terranova, B. Waegell. Nickel-catalyzed dimerization of norbomene. // 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 by dimerization of 2-norbornene in the presence of Ni complexes.

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. T. 57. S. 1763-1768] describes the synthesis of a mixture of exo / endo isomers of 2,2'-bis (norbornanyl) by hydroaluminization of 2-norbornene in the presence of ZrCl ₄ , followed by oxidation of the resulting alane with oxygen.

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.

In [S. Derien, J.C. Clinet, E. Dunach, J. Perichon. Electrochemical incorporation of carbon dioxide into alkenes by nickel complexes V / 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.

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 exo / endo isomers of 2,2'-bis (norbornanyl) by UV photolysis of norbornene in hexane in the presence of triplet sensitizers, for example, benzophenone.

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.

In the work [DJ Huang, C.H. 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 .

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.

Obtaining NBAMeNBA by hydrogenation of a mixture of exo / endo isomers of methyl-substituted 5- (2'-norbornanyl) -norbornene

A common disadvantage of all the described technical solutions for obtaining NBAMeNBA and 2,2'-bis (norbornanyl) is the use of expensive ctatalysts, 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.

The products obtained are not used as fuel or its components.

The objective of the present invention is to develop an economical and convenient method for producing NBAMeNBA with a high yield and purity with the possibility of using it as a high-density and high-energy 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), including carrying out a thermal Diels-Alder reaction of a mixture of exo / endo isomers of 2-vinylnorbornane (hereinafter VNBa) with a mixture of isomers methyldicyclopentadiene upon heating and subsequent hydrogenation of the resulting mixture of isomers of methyl-substituted 5- (2'-norbornanyl) -norbornene in the presence of hydrogen and a hydrogenation catalyst taken in a ratio of 0.5-10 wt%. with respect to methyl-substituted 5- (2'-norbornanyl) -norbornene at room temperature and hydrogen pressure of 30-60 atm.

According to a second embodiment of the invention, a method for producing a component of 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 a mixture of methyldicyclopentadiene isomers upon heating and subsequent hydrogenation

the resulting mixture of isomers of methyl-substituted 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%. with respect to methyl-substituted 5- (2'-norbornanyl) -norbornene at room temperature and 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 NBMeNB was 45%. Analysis by gas chromatography-mass spectrometry made it possible to establish that the reaction product is 11 isomers of NBMeNBa. These compounds have close retention times and almost identical mass spectra. 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 7 isomers of NBAMeNB (GLC) (Fig. 4).

The technical result is the possibility of obtaining a high-density and high-energy component of rocket and aviation fuel - NBAMeNBA - with a high yield with a simple method.

It should be noted that our proposed method for producing 2,2'-NBAMeNBA does not require an inert atmosphere, the use of organometallic compounds, and 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.

Preparation of methyl-substituted 5- (2'-norbornanyl) -norbornene (NBMeNBa)

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 are recorded on Varian Inova 500, Bruker Avance DRX 400 NMR spectrometers and on Bruker MSL-300. 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 are assigned to the residual protons of CDCl ₃ (7.24 ppm).

Chromato-mass spectrometric analysis is carried out on a Finnigan MAT 95 XL gas chromatograph-mass spectrometer (ionization energy 70 eV, mass range 20-800 amu, resolution 1000, source temperature 200 ° C, scanning speed 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 is carried out 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 methyldicyclopentadiene (MDCPD) and a two-fold amount of VNBa and distilling off the unreacted VNBa and isolating the target NBMeNBA.

In a steel autoclave with a volume of 100 ml, equipped with a magnetic stirrer, a screw neck for injecting 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) 30 ml (25.2 g 0.20 mmol) VNBa, 7.97 g (0.10 mol) methyldicyclopentadiene in the form of a mixture of isomers and 0.1 g of hydroquinone. The reaction mass is stirred at a speed of 50 rpm and heated to 220 ° C. Heating is continued for 6 hours. After 6 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 "Khromatek-Kristall-5000" version 2 with a capillary column "SGE Analytical Science" and a flame ionization detector (FID) is 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 contained unreacted VNBa, ethylnorbornane, a mixture of 11 product isomers, and a small amount of impurities. The reaction mixture is transferred to a distillation apparatus - a 100 ml Claisen flask equipped with a reflux condenser, a descending condenser, a "spider" type allonge and 3 receivers, and unreacted VNBa and ethylnorbornane are distilled off at 50 mm, collecting the fraction boiling in the range of 60-80 ° C. Replace the receivers and distill the cube at 0.2 mm Hg, collecting the fraction boiling in the range of 80-100 ° C. Yield 9.05 g (45%).

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

In a steel autoclave with a volume of 100 ml, equipped with a magnetic stirrer), a screw neck for introducing reagents, a pressure gauge and a nozzle for introducing hydrogen with a reducer (it is assumed to use an autoclave in which the condensation stage was carried out, having previously washed it, while the heating jacket and thermocouple are not used) load a mixture of 9.00 g (44.5 mmol) of NBMeNBA isomers, 0.24 g (2% by weight) 10% Pd / C and 20 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 in step 4.1. The reaction product comes out in the form of 7 closely spaced peaks (Fig. 4). In the absence of NBMeNBA, 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 transferred from the autoclave with compressed air (nitrogen) to a 200 ml flat-bottomed flask. The autoclave is washed three times with hexane in 15 ml portions and the wash extracts are combined with the reaction mixture. Filter under vacuum of a water-jet pump into a 500 ml Bunsen flask through a Schott filter with a diameter of 5 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 3 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 150 ml of hexane. Approximately 220 ml of a solution of NBAMeNBA in hexane, filtered from the catalyst, are obtained. From the solution obtained at this stage, hexane is distilled off on a rotary evaporator. The residue was transferred into a 25 ml Claisen flask equipped with a reflux condenser, a descending condenser, a spider and receivers and distilled in a vacuum at a pressure of 0.1 mm Hg. A fraction with a boiling point of 82-84 ° C is collected. The product yield is 8.27 g (91%). According to GLC data, the resulting substance is a mixture of 7 isomers.

Example 2

Differs from example 1 in that at the stage of hydrogenation take 1% (by weight of NBMeNBA) 10% Pd / C. The hydrogenation is carried out for 10 days at room temperature and a hydrogen pressure of 30 atm. Output 90%.

Example 3

Differs from example 1 in that at the stage of hydrogenation take 2% (by weight of NBMeNBA) 5% Pd / C. The hydrogenation is carried out for 10 days at room temperature and a hydrogen pressure of 30 atm. Yield 88%.

Example 4

It 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. The yield is 91%.

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. Yield 91%.

Example 6

Differs from example 1 in that at the stage of hydrogenation take 2% (by weight of NBMeNBA) 5% Pt / C. The hydrogenation is carried out for 10 days at room temperature and a hydrogen pressure of 30 atm. Output 92%.

Example 7

Differs from example 1 in that at the stage of hydrogenation take 10% (by weight of NBMeNBA) Raney nickel. Hydrogenation is carried out for 10 days at room temperature and a hydrogen pressure of 60 atm. Output 92%.

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 NBMeNBA (15 g 0.07 mol) was added dropwise a solution of copper sulfate pentahydrate (0.21 g in 10 ml of methanol) or 2% of the mass for hydrazine hydrate. Then, with stirring, air is passed 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 of NBMeNBA - 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 in vacuo, as described in example 1.

85% yield.

¹ H NMR spectrum (Fig. 1). The ¹ H NMR spectrum of NBAMeNBA contains the signals of the protons of the norbornane fragment in the region of 0.98-2.23 ppm. The spectrum does not contain signals from protons of the norbornene double bond (region 6.0-6.2 ppm), which indicates the absence of the initial NBMeNBa.

¹³ C NMR spectrum (Fig. 2). The ¹³ C NMR spectrum of NBAMeNBA contains signals of aliphatic carbon atoms of the norbornane fragment in the range of 15.6-45.5 ppm. The spectrum does not contain signals of alkenyl carbon atoms, which indicates the absence of the starting NBAMeNBA.

Mass spectrum (Fig. 3). Molecular ion М ⁺ 204 (13), 175 (42), 109 (64), 95 (52), 81 (100), 67 (82), 41 (27), 28 (51).

Measurement of calorific value and density of methyl-substituted 2,2'-bis (norbornanyl)

The highest specific heat of combustion of methyl-substituted 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 methyl-substituted 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 methyl-substituted 2,2'-bis (norbornanyl) is measured using a Kristall-20E apparatus according to the standard procedure in accordance with GOST 18995.5-73.

Some basic properties of NBAMeNBA are presented in Table 1.

The properties of the obtained NBAMeNBA as a high-energy fuel are shown in Table 2. In a number of parameters, they are superior to the known JP-10 propellant, which is structurally related to the obtained hydrocarbon.

Claims (4)

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

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