Cage alkane structure fuel, preparation method thereof and aerospace fuel

Abstract

The invention provides a caged alkane structure fuel, a preparation method thereof and an aerospace fuel, and belongs to the technical field of liquid fuels. The cage-shaped alkane structure fuel provided by the invention is 3, 8-dimethyl pentacyclic [5.3. 0.02, 5.03, 9.04.8] decane, and has two four-membered rings and four five-membered rings, and molecules have higher tension energy; the polyhedral oligomeric alkane structure fuel provided by the invention has a branched chain, the introduction of the branched chain can reduce the intermolecular acting force, increase the flexibility of molecules and improve the low-temperature performance of polyhedral oligomeric alkane, so that the polyhedral oligomeric alkane structure fuel has high specific impulse and better low-temperature performance while the density is not lower than 0.960 g / cm < 3 > and the net mass calorific value is not lower than 42.63 MJ / kg. Results of the embodiment show that the polyhedral oligomeric alkane structure fuel provided by the invention has high density and high calorific value, and the problem that liquid fuel is difficult to have high density and high calorific value at the same time is solved.

Description

Technical Field

[0001] The present invention relates to the technical field of liquid fuels, and in particular to a caged alkane structure fuel, a preparation method thereof, and an aerospace fuel. Background Art

[0002] Liquid fuel is a crucial component of liquid propellants, and its fuel density and volumetric calorific value directly impact aerospace vehicle performance (such as range, speed, and payload). For aerospace vehicles with a given fuel tank capacity, a higher volumetric calorific value of liquid fuel is more beneficial for improving the range, speed, and payload of high-density fuels. While maintaining all aspects of vehicle performance, using liquid fuel with a higher volumetric calorific value can reduce the fuel tank capacity, miniaturizing the vehicle and improving its penetration capability and maneuverability.

[0003] Currently, traditional liquid fuels are primarily based on five- and six-membered ring structures. While these fuels have relatively high density, the increased number of rings reduces the hydrogen content within the hydrocarbon molecules, leading to a decrease in the calorific value of the liquid fuel. Therefore, it is difficult for current liquid fuels to achieve both high density and high calorific value. Summary of the Invention

[0004] The purpose of the present invention is to provide a caged alkane structure fuel, a preparation method thereof, and an aerospace fuel. The caged alkane structure fuel provided by the present invention has both high density and high calorific value and can be used as an aerospace fuel.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2,5 .0 3,9 .0 4.8 ] decane, having a chemical structure as shown in Formula I:

[0007]

[0008] The density of the caged alkane structure fuel is not less than 0.960 g / cm 3 , the mass net calorific value is not less than 42.63MJ / kg, and the specific impulse is not less than 328s.

[0009] The present invention provides a method for preparing the caged alkane structure fuel described in the above technical solution, comprising the following steps:

[0010] (1) mixing methylcyclopentadiene dimer, a catalyst and a solvent to obtain a mixed solution; wherein the catalyst is a photosensitizer or a photocatalyst;

[0011] (2) irradiating the mixed solution obtained in step (1) with ultraviolet light to carry out an addition reaction to obtain a caged alkane structure fuel.

[0012] Preferably, the photosensitizer in step (1) comprises at least one of acetophenone, xanthanone, benzophenone, 2-isopropylthioxanthone and 2-acetonapthone.

[0013] Preferably, the photocatalyst in step (1) comprises at least one of cysteine-induced chiral TiO2, tartaric acid-induced chiral TiO2, methionine-induced chiral TiO2 and glycerol / cysteine-induced metal-deficient chiral TiO2.

[0014] Preferably, the molar ratio of the photosensitizer to the methylcyclopentadiene dimer in step (1) is 0.6 to 1:1.

[0015] Preferably, the mass ratio of the photocatalyst to the methylcyclopentadiene dimer in step (1) is 0.005-0.025:1.

[0016] Preferably, the concentration of methylcyclopentadiene dimer in the mixed solution of step (1) is 0.05 to 0.9 mol / L.

[0017] Preferably, the incident intensity of the ultraviolet light in step (2) is 70 to 170 mW / cm 2 .

[0018] Preferably, the temperature of the addition reaction in step (2) is 10 to 30° C., and the time of the addition reaction is 1 to 12 hours.

[0019] The present invention also provides an aerospace fuel, which includes the caged alkane structure fuel described in the above technical solution or the caged alkane structure fuel prepared by the preparation method described in the above technical solution.

[0020] The present invention provides a caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2,5 .0 3,9 .0 4.8 Decane has a chemical structure as shown in Formula I. The caged alkane structure fuel having the structure shown in Formula I has two four-membered rings and four five-membered rings, and the molecule has higher tension energy; the caged alkane structure fuel provided by the present invention has a branched chain, and the introduction of the branched chain can reduce the intermolecular force, while increasing the flexibility of the molecule, improving the low-temperature performance of the caged alkane, so that the caged alkane structure fuel has a density of not less than 0.960g / cm 3, with a net calorific value of no less than 42.63 MJ / kg, high specific impulse (no less than 328 seconds) and good low-temperature performance. The results of the examples show that the caged alkane structured fuel provided by the present invention has both high density and high calorific value, resolving the problem of liquid fuels being unable to achieve both high density and high calorific value. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is a chromatogram of the caged alkane structure fuel prepared in Example 1 of the present invention;

[0022] Figure 2 This is the mass spectrum of the caged alkane structure fuel prepared in Example 1 of the present invention;

[0023] Figure 3 The caged alkane structure fuel prepared in Example 1 of the present invention 1 H NMR spectrum;

[0024] Figure 4 The caged alkane structure fuel prepared in Example 1 of the present invention 13 C NMR spectrum. DETAILED DESCRIPTION

[0025] The present invention provides a caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2,5 .0 3,9 .0 4.8 ] decane, having a chemical structure as shown in Formula I:

[0026]

[0027] The density of the caged alkane structure fuel is not less than 0.960 g / cm 3 , the mass net calorific value is not less than 42.63MJ / kg, and the specific impulse is not less than 328s.

[0028] In the present invention, the density of the caged alkane structure fuel is not less than 0.960 g / cm 3 , preferably 0.960~1g / cm 3 .

[0029] In the present invention, the net calorific value of the caged alkane structure fuel is not less than 42.63 MJ / kg, preferably 42.63 to 43 MJ / kg.

[0030] In the present invention, the specific impulse of the caged alkane structure fuel is not less than 328s, preferably 328-335s.

[0031] The caged alkane structure fuel provided by the present invention has two four-membered rings and four five-membered rings. The molecules of this structure have higher tension energy. At the same time, the two methyl groups in the structure can improve the low-temperature performance of the caged alkane, making the caged alkane structure fuel have a density of not less than 0.960g / cm 3 The net calorific value of the caged alkane structure fuel is not less than 42.63 MJ / kg, and the caged alkane structure fuel has a high specific impulse (specific impulse not less than 328s) and good low-temperature performance. In the present invention, the freezing point of the caged alkane structure fuel is preferably not higher than -30°C.

[0032] The present invention also provides a method for preparing the caged alkane structure fuel described in the above technical solution, comprising the following steps:

[0033] (1) mixing methylcyclopentadiene dimer, a catalyst and a solvent to obtain a mixed solution; wherein the catalyst is a photosensitizer or a photocatalyst;

[0034] (2) irradiating the mixed solution obtained in step (1) with ultraviolet light to carry out an addition reaction to obtain a caged alkane structure fuel.

[0035] The invention mixes methylcyclopentadiene dimer, a photosensitizer catalyst and a solvent to obtain a mixed solution; the catalyst is a photosensitizer or a photocatalyst.

[0036] In the present invention, the structural formula of the methylcyclopentadiene dimer is preferably as shown in Formula II:

[0037]

[0038] In the present invention, the photosensitizer preferably includes at least one of acetophenone, xanthone, benzophenone, 2-isopropylthioxanthone, and 2-acetonapthone, and more preferably at least one of acetophenone, xanthone, and benzophenone. In the present invention, the photocatalyst preferably includes at least one of cysteine-induced chiral TiO2, tartaric acid-induced chiral TiO2, methionine-induced chiral TiO2, and glycerol / cysteine-induced metal-deficient chiral TiO2.

[0039] The present invention has no particular limitation on the source of the photocatalyst, and any conventional source or synthesis method may be used. In an embodiment of the present invention, the preparation method of the photocatalyst preferably comprises: mixing an inducer, tetrabutyl titanate, and ethanol, and sequentially performing a solvent thermal reaction, washing, and calcining to obtain the photocatalyst.

[0040] In an embodiment of the present invention, the inducer is preferably one of cysteine, tartaric acid, methionine and glycerol / cysteine.

[0041] In an embodiment of the present invention, the temperature of the solvothermal reaction may be 180° C.; and the time of the solvothermal reaction may be 24 hours.

[0042] In an embodiment of the present invention, the washing reagent may be ethanol.

[0043] In an embodiment of the present invention, the calcination temperature may be 470° C., and the calcination time may be 1 hour.

[0044] The present invention adds a photosensitizer or photocatalyst. After ultraviolet light excitation in a mixed solution, the singlet state is excited to a triplet state through an intersystem crossing process. Subsequently, energy transfer occurs with the ground-state methylcyclopentadiene dimer, exciting the triplet state to a triplet state, leading to an intramolecular [2+2] cycloaddition reaction. The present invention utilizes the above-mentioned photosensitizer, which has good sensitization effect, strong photosensitizer stability, and fewer side reactions, thereby facilitating the production of a higher yield of caged alkane structure fuel.

[0045] In the present invention, the molar ratio of the photosensitizer to the methylcyclopentadiene dimer is preferably 0.6 to 1:1. As one embodiment of the present invention, the molar ratio of the photosensitizer to the methylcyclopentadiene dimer can be 0.6:1, 0.7:1, 0.8:1, 0.9:1, or 1:1. Controlling the molar ratio of the photosensitizer to the methylcyclopentadiene dimer within the above range is beneficial for increasing the yield of the target product, the caged alkane structure fuel, and can prevent waste caused by excessive use of the photosensitizer.

[0046] In the present invention, the mass ratio of the photocatalyst to the methylcyclopentadiene dimer is preferably 0.005 to 0.025:1. As one embodiment of the present invention, the mass ratio of the photocatalyst to the methylcyclopentadiene dimer can be 0.005:1, 0.01:1, 0.015:1, 0.02:1, or 0.025:1. Controlling the mass ratio of the photocatalyst to the methylcyclopentadiene dimer within the above range is beneficial for increasing the yield of the target product, the caged alkane structure fuel, and can prevent waste caused by excessive photocatalyst usage.

[0047] In the present invention, the solvent preferably includes at least one of methanol, acetonitrile, ethanol, acetone, isopropanol, dichloromethane, cyclohexane, n-hexane, and isooctane, and more preferably at least one of acetonitrile, acetone, isopropanol, dichloromethane, and isooctane. The above solvents can dissolve the methylcyclopentadiene dimer and the photosensitizer and provide a suitable reaction environment for the addition reaction.

[0048] The present invention has no particular limitation on the method for mixing the methylcyclopentadiene dimer, photosensitizer and solvent, as long as the methylcyclopentadiene dimer and photosensitizer are completely dissolved in the solvent to form a mixed solution.

[0049] In the present invention, the concentration of methylcyclopentadiene dimer in the mixed solution is preferably 0.05 to 0.9 mol / L. As one embodiment of the present invention, the concentration of methylcyclopentadiene dimer in the mixed solution can be 0.05 mol / L, 0.1 mol / L, 0.3 mol / L, 0.5 mol / L, 0.7 mol / L, or 0.9 mol / L. The present invention controls the concentration of methylcyclopentadiene dimer in the mixed solution within the above range, thereby improving the conversion rate and yield of the target product, the caged alkane structure fuel, and preventing waste caused by excessive use of methylcyclopentadiene dimer.

[0050] After obtaining the mixed solution, the present invention irradiates the mixed solution with ultraviolet light to carry out an addition reaction to obtain a caged alkane structure fuel.

[0051] The present invention preferably first introduces nitrogen into the mixed solution and then performs ultraviolet irradiation. By introducing nitrogen into the mixed solution, the present invention can discharge the residual oxygen in the mixed solution and reduce the adverse effect of oxygen on the addition reaction. The present invention does not particularly limit the time for introducing the nitrogen, as long as the gas in the mixed solution can be fully discharged. In an embodiment of the present invention, the time for introducing nitrogen can be 30 minutes.

[0052] The present invention uses ultraviolet light to irradiate the mixed solution, causing the methylcyclopentadiene dimer in the mixed solution and the catalyst to undergo an addition reaction to obtain a caged alkane structure fuel. In the present invention, the reaction formula of the addition reaction is preferably as shown in Formula III:

[0053]

[0054] In the present invention, the incident intensity of the ultraviolet light is preferably 70 to 170 mW / cm 2 As an embodiment of the present invention, the incident intensity of the ultraviolet light can be 70mW / cm 2 , 75mW / cm 2 , 80mW / cm 2 、85mW / cm 2 , 90mW / cm 2 , 95mW / cm 2 , 100mW / cm 2 、105mW / cm 2 、110mW / cm 2 、115mW / cm 2 , 120mW / cm 2 、125mW / cm 2 、130mW / cm 2 、135mW / cm2 、140mW / cm 2 、145mW / cm 2 、150mW / cm 2 、155mW / cm 2 、160mW / cm 2 、165mW / cm 2 or 170mW / cm 2 The present invention controls the incident intensity of ultraviolet light within the above range, which can improve the efficiency of the addition reaction.

[0055] In the present invention, the ultraviolet light is preferably provided by a single-wavelength LED light source. In the present invention, the wavelength of the single-wavelength LED light source can be 365nm. The present invention uses a single-wavelength LED light source to provide ultraviolet light, which has the characteristics of low heat generation and high energy efficiency.

[0056] In the present invention, the temperature of the addition reaction is preferably 10 to 30°C. As an embodiment of the present invention, the temperature of the addition reaction can be 10°C, 15°C, 20°C, 25°C or 30°C. In the present invention, the time of the addition reaction is preferably 1 to 12 hours. As an embodiment of the present invention, the time of the addition reaction can be 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours. The present invention can make the addition reaction more sufficient at the above temperature and time.

[0057] The present invention preferably carries out rotary evaporation and vacuum distillation in sequence to the product obtained by the addition reaction to obtain a caged alkane structure fuel. The present invention removes the solvent in the product obtained by the reaction by rotary evaporation, and removes volatile impurities and residual solvent by vacuum distillation. The present invention has no particular restrictions on the specific operating methods of the rotary evaporation and vacuum distillation, and the operating methods of conventional rotary evaporation and vacuum distillation can be adopted. Since the methylcyclopentadiene dimer and the photosensitizer react more fully under ultraviolet light irradiation, impurities are less, the caged alkane structure fuel of high purity can be obtained by the rotary evaporation and vacuum distillation.

[0058] The method provided by the present invention is simple to operate. It uses ultraviolet light irradiation to cause an addition reaction between methylcyclopentadiene dimer and a photosensitizer. This addition reaction is an intramolecular [2+2] cycloaddition reaction with high reaction efficiency, thereby obtaining a caged alkane structure fuel, namely 3,8-dimethylpentacyclo[5.3.0.0 2,5 .0 3,9 .0 4.8 ]Decane.

[0059] The present invention also provides an aerospace fuel, which includes the caged alkane structure fuel described in the above technical solution or the caged alkane structure fuel prepared by the preparation method described in the above technical solution.

[0060] In the present invention, the aerospace fuel is preferably a caged alkane structure fuel or a mixture of a caged alkane structure fuel and a high-density aerospace fuel.

[0061] The caged alkane structure fuel provided by the present invention has two four-membered rings and four five-membered rings, and the molecule has higher tension energy; the caged alkane structure fuel provided by the present invention has high density and high mass net calorific value, so it can be directly used as aerospace fuel, or it can be a mixture of caged alkane structure fuel and high-density aerospace fuel.

[0062] In the present invention, the high-density aerospace fuel is preferably one or more of HD-01, HD-03 and RP-3.

[0063] In the present invention, the weight ratio of the caged alkane fuel to the high-density aerospace fuel in the mixture is preferably 0-0.4:0.6-1, and more preferably 0.2-0.4:0.6-0.8. The present invention utilizes a mixture of the caged alkane fuel and the high-density aerospace fuel to enhance the combustion performance of the aerospace fuel through compounding.

[0064] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions of the present invention. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0065] In an embodiment of the present invention, the preparation method of cysteine-induced chiral TiO2 is as follows: 0.00586 mol of cysteine and 2 mL of tetrabutyl titanate are dissolved in 55 mL of ethanol and reacted at 180°C for 24 hours. After the reaction is completed, the mixture is washed with ethanol and then calcined at 470°C for 1 hour to obtain cysteine-induced chiral TiO2.

[0066] The preparation method of glycerol / cysteine induced chiral TiO2 is as follows: 10g glycerol, 0.00586mol cysteine and 2mL tetrabutyl titanate are dissolved in 55mL ethanol and reacted at 180℃ for 24h. After the reaction is completed, it is washed with ethanol and then calcined at 470℃ for 1h to obtain glycerol / cysteine induced chiral TiO2.

[0067] Example 1

[0068] A caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2, 5 .0 3,9 .0 4.8 ] decane, having a chemical structure as shown in Formula I:

[0069]

[0070] The preparation method of the caged alkane structure fuel comprises the following steps:

[0071] (1) Add 0.5 mol / L methylcyclopentadiene dimer and 0.4 mol / L acetophenone to a 25 mL volumetric flask, and dilute to 25 mL with isooctane to obtain a mixed solution;

[0072] (2) The mixed solution obtained in step (1) was transferred to a 50 mL single-mouth quartz glass reactor, and nitrogen was continuously bubbled for 30 min under stirring. Then, a condenser was connected and sealed. The condenser was opened so that the reaction temperature was 20 ° C. The incident light intensity of the 365 nm LED lamp was 170 mW / cm 2 After irradiation for 12 hours, the caged alkane fuel was obtained by rotary evaporation and vacuum distillation with a yield of 60.06%; it was named 3,8-dimethylpentacyclo[5.3.0.0 2,5 .0 3,9 .0 4.8 ] decane, the chromatographic results are as follows Figure 1 The mass spectrometry results are shown in Figure 2 As shown; 1 H NMR spectrum Figure 3 As shown; 13 C NMR spectrum Figure 4 shown.

[0073] The density of the caged alkane fuel prepared in this example is 0.964 g / cm 3 The mass calorific value is higher than 42.63MJ / kg, the freezing point is lower than -30℃, and the theoretical specific impulse is 328.19s (engine pressure: 7MPa; excess oxygen coefficient is 0.7; engine outlet expansion pressure ratio is 0.7).

[0074] Example 2

[0075] A caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2, 5 .0 3,9 .0 4.8 ] decane, having a chemical structure as shown in Formula I:

[0076]

[0077] The preparation method of the caged alkane structure fuel comprises the following steps:

[0078] (1) Add 0.3 mol / L methylcyclopentadiene dimer and 0.24 mol / L acetophenone to a 25 mL volumetric flask, and dilute to 25 mL with isooctane to obtain a mixed solution;

[0079] (2) The mixed solution obtained in step (1) was transferred to a 50 mL single-mouth quartz glass reactor, and nitrogen was continuously bubbled for 30 min under stirring. Then, a condenser was connected and sealed. The condenser was opened so that the reaction temperature was 20 ° C. The incident light intensity of the 365 nm LED lamp was 170 mW / cm 2 , irradiated for 12 hours, and after the reaction was completed, the caged alkane structure fuel was obtained by rotary evaporation and reduced pressure distillation with a yield of 69.66%.

[0080] Example 3

[0081] A caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2, 5 .0 3,9 .0 4.8 ] decane, having a chemical structure as shown in Formula I:

[0082]

[0083] The preparation method of the caged alkane structure fuel comprises the following steps:

[0084] (1) Add 0.7 mol / L methylcyclopentadiene dimer and 0.56 mol / L acetophenone to a 25 mL volumetric flask, and dilute to 25 mL with isooctane to obtain a mixed solution;

[0085] (2) The mixed solution obtained in step (1) was transferred to a 50 mL single-mouth quartz glass reactor, and nitrogen was continuously bubbled for 30 min under stirring. Then, a condenser was connected and sealed. The condenser was opened so that the reaction temperature was 20 ° C. The incident light intensity of the 365 nm LED lamp was 170 mW / cm 2 , irradiated for 12 hours, and after the reaction was completed, the caged alkane structure fuel was obtained by rotary evaporation and vacuum distillation with a yield of 52.59%.

[0086] Example 4

[0087] A caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2, 5 .03,9 .0 4.8 ] decane, having a chemical structure as shown in Formula I:

[0088]

[0089] The preparation method of the caged alkane structure fuel comprises the following steps:

[0090] (1) Add 0.5 mol / L methylcyclopentadiene dimer and 0.3 mol / L acetophenone to a 25 mL volumetric flask, and dilute to 25 mL with isooctane to obtain a mixed solution;

[0091] (2) The mixed solution obtained in step (1) was transferred to a 50 mL single-mouth quartz glass reactor, and nitrogen was continuously bubbled for 30 min under stirring. Then, a condenser was connected and sealed. The condenser was opened so that the reaction temperature was 20 ° C. The incident light intensity of the 365 nm LED lamp was 170 mW / cm 2 , irradiated for 12 hours, and after the reaction was completed, the caged alkane structure fuel was obtained by rotary evaporation and vacuum distillation with a yield of 55.57%.

[0092] Example 5

[0093] A caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2, 5 .0 3,9 .0 4.8 ] decane, having a chemical structure as shown in Formula I:

[0094]

[0095] The preparation method of the caged alkane structure fuel comprises the following steps:

[0096] (1) Add 0.5 mol / L methylcyclopentadiene dimer and 0.5 mol / L acetophenone to a 25 mL volumetric flask, and dilute to 25 mL with isooctane to obtain a mixed solution;

[0097] (2) The mixed solution obtained in step (1) was transferred to a 50 mL single-mouth quartz glass reactor, and nitrogen was continuously bubbled for 30 min under stirring. Then, a condenser was connected and sealed. The condenser was opened so that the reaction temperature was 20 ° C. The incident light intensity of the 365 nm LED lamp was 170 mW / cm 2 , irradiated for 12 hours, and after the reaction was completed, the caged alkane structure fuel was obtained by rotary evaporation and reduced pressure distillation with a yield of 60.50%.

[0098] Example 6

[0099] A caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2, 5 .0 3,9 .0 4.8 ] decane, having a chemical structure as shown in Formula I:

[0100]

[0101] The preparation method of the caged alkane structure fuel comprises the following steps:

[0102] (1) Same as Example 1;

[0103] (2) The mixed solution obtained in step (1) was transferred to a 50 mL single-mouth quartz glass reactor, and nitrogen was continuously bubbled for 30 min under stirring. Then, a condenser was connected and sealed. The condenser was opened so that the reaction temperature was 20 ° C. The incident light intensity of the 365 nm LED lamp was 170 mW / cm 2 , irradiated for 6 hours, and after the reaction was completed, the caged alkane structure fuel was obtained by rotary evaporation and reduced pressure distillation with a yield of 41.55%.

[0104] Example 7

[0105] A caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2, 5 .0 3,9 .0 4.8 ] decane, having a chemical structure as shown in Formula I:

[0106]

[0107] The preparation method of the caged alkane structure fuel comprises the following steps:

[0108] (1) Same as Example 1;

[0109] (2) The mixed solution obtained in step (1) was transferred to a 50 mL single-mouth quartz glass reactor, and nitrogen was continuously bubbled for 30 min under stirring. Then, a condenser was connected and sealed. The condenser was opened so that the reaction temperature was 20 ° C. The incident light intensity of the 365 nm LED lamp was 170 mW / cm 2 , irradiated for 10 hours, and after the reaction was completed, the caged alkane structure fuel was obtained by rotary evaporation and reduced pressure distillation with a yield of 56.37%.

[0110] Example 8

[0111] A caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2,5 .0 3,9 .0 4.8 ] decane, having a chemical structure as shown in Formula I:

[0112]

[0113] The preparation method of the caged alkane structure fuel comprises the following steps:

[0114] (1) Same as Example 1;

[0115] (2) The mixed solution obtained in step (1) was transferred to a 50 mL single-mouth quartz glass reactor, and nitrogen was continuously bubbled for 30 min under stirring. Then, a condenser was connected and sealed. The condenser was opened so that the reaction temperature was 10 ° C. and the incident light intensity of the 365 nm LED lamp was 170 mW / cm 2 , irradiated for 12 hours, and after the reaction was completed, the caged alkane structure fuel was obtained by rotary evaporation and reduced pressure distillation with a yield of 58.50%.

[0116] Example 9

[0117] A caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2, 5 .0 3,9 .0 4.8 ] decane, having a chemical structure as shown in Formula I:

[0118]

[0119] The preparation method of the caged alkane structure fuel comprises the following steps:

[0120] (1) Same as Example 1;

[0121] (2) The mixed solution obtained in step (1) was transferred to a 50 mL single-mouth quartz glass reactor, and nitrogen was continuously bubbled for 30 min under stirring. Then, a condenser was connected and sealed. The condenser was opened so that the reaction temperature was 30 ° C and the incident light intensity of the 365 nm LED lamp was 170 mW / cm 2 , irradiated for 12 hours, and after the reaction was completed, the caged alkane structure fuel was obtained by rotary evaporation and reduced pressure distillation with a yield of 58.73%.

[0122] Example 10

[0123] A caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2, 5 .0 3,9 .0 4.8] decane, having a chemical structure as shown in Formula I:

[0124]

[0125] The preparation method of the caged alkane structure fuel comprises the following steps:

[0126] (1) Same as Example 1;

[0127] (2) The mixed solution obtained in step (1) was transferred to a 50 mL single-mouth quartz glass reactor, and nitrogen was continuously bubbled for 30 min under stirring. Then, a condenser was connected and sealed. The condenser was opened so that the reaction temperature was 20 ° C. The incident light intensity of the 365 nm LED lamp was 130 mW / cm 2 , irradiated for 12 hours, and after the reaction was completed, the caged alkane structure fuel was obtained by rotary evaporation and reduced pressure distillation with a yield of 47.61%.

[0128] Example 11

[0129] A caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2, 5 .0 3,9 .0 4.8 ] decane, having a chemical structure as shown in Formula I:

[0130]

[0131] The preparation method of the caged alkane structure fuel comprises the following steps:

[0132] (1) Add 0.05 mol / L methylcyclopentadiene dimer and 0.04 mol / L acetophenone to a 25 mL volumetric flask, and dilute to 25 mL with isooctane to obtain a mixed solution;

[0133] (2) The mixed solution obtained in step (1) was transferred to a 50 mL single-mouth quartz glass reactor, and nitrogen was continuously bubbled for 30 min under stirring. Then, a condenser was connected and sealed. The condenser was opened so that the reaction temperature was 20 ° C. The incident light intensity of the 365 nm LED lamp was 170 mW / cm 2 , irradiated for 12 hours, and after the reaction was completed, the caged alkane structure fuel was obtained by rotary evaporation and reduced pressure distillation with a yield of 49.90%.

[0134] Example 12

[0135] A caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2, 5 .0 3,9 .0 4.8]Decane;

[0136] The preparation method of the caged alkane structure fuel comprises the following steps:

[0137] (1) Add 0.5 mol / L methylcyclopentadiene dimer and 0.1 mol / L acetophenone to a 25 mL volumetric flask, and dilute to 25 mL with dichloromethane to obtain a mixed solution;

[0138] (2) As in Example 1, a caged alkane structure fuel was obtained with a yield of 21.19%.

[0139] Example 13

[0140] A caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2, 5 .0 3,9 .0 4.8 ]Decane;

[0141] The preparation method of the caged alkane structure fuel comprises the following steps:

[0142] (1) Add 0.5 mol / L methylcyclopentadiene dimer and 0.1 mol / L xanthanone to a 25 mL volumetric flask, and dilute to 25 mL with dichloromethane to obtain a mixed solution;

[0143] (2) The same method as in Example 1 was used to obtain a caged alkane structure fuel with a yield of 6.10%.

[0144] Example 14

[0145] A caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2, 5 .0 3,9 .0 4.8 ]Decane;

[0146] The preparation method of the caged alkane structure fuel comprises the following steps:

[0147] (1) Add 0.5 mol / L methylcyclopentadiene dimer and 0.1 mol / L benzophenone to a 25 mL volumetric flask, and dilute to 25 mL with dichloromethane to obtain a mixed solution;

[0148] (2) The same method as in Example 1 was used to obtain a caged alkane structure fuel with a yield of 0.14%.

[0149] Example 15

[0150] A caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.02, 5 .0 3,9 .0 4.8 ]Decane;

[0151] The preparation method of the caged alkane structure fuel comprises the following steps:

[0152] (1) Add 0.5 mol / L methylcyclopentadiene dimer and 0.1 mol / L acetophenone to a 25 mL volumetric flask, and dilute to 25 mL with acetonitrile to obtain a mixed solution;

[0153] (2) The same method as in Example 1 was used to obtain a caged alkane structure fuel with a yield of 18.74%.

[0154] Example 16

[0155] A caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2, 5 .0 3,9 .0 4.8 ]Decane;

[0156] The preparation method of the caged alkane structure fuel comprises the following steps:

[0157] (1) Add 0.5 mol / L methylcyclopentadiene dimer and 0.1 mol / L xanthanone to a 25 mL volumetric flask, and dilute the volume to 25 mL with acetone to obtain a mixed solution;

[0158] (2) As in Example 1, a caged alkane structure fuel was obtained with a yield of 21.83%.

[0159] Example 17

[0160] A caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2, 5 .0 3,9 .0 4.8 ]Decane;

[0161] The preparation method of the caged alkane structure fuel comprises the following steps:

[0162] (1) Add 0.5 mol / L methylcyclopentadiene dimer and 0.1 mol / L xanthanone to a 25 mL volumetric flask, and dilute to 25 mL with isopropyl alcohol to obtain a mixed solution;

[0163] (2) As in Example 1, a caged alkane structure fuel was obtained with a yield of 15.29%.

[0164] Example 18

[0165] A caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2, 5 .0 3,9 .0 4.8 ]Decane;

[0166] The preparation method of the caged alkane structure fuel comprises the following steps:

[0167] (1) Add 0.5 mol / L methylcyclopentadiene dimer and 0.1 mol / L acetophenone to a 25 mL volumetric flask, and dilute to 25 mL with cyclohexane to obtain a mixed solution;

[0168] (2) As in Example 1, a caged alkane structure fuel was obtained with a yield of 24.87%.

[0169] Example 19

[0170] A caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2, 5 .0 3,9 .0 4.8 ]Decane;

[0171] The preparation method of the caged alkane structure fuel comprises the following steps:

[0172] (1) Add 0.5 mol / L methylcyclopentadiene dimer and 0.1 mol / L acetophenone to a 25 mL volumetric flask, and dilute to 25 mL with isooctane to obtain a mixed solution;

[0173] (2) The mixed solution obtained in step (1) was transferred to a 50 mL single-mouth quartz glass reactor, and nitrogen was continuously bubbled for 30 min under stirring. Then, a condenser was connected and sealed. The condenser was opened so that the reaction temperature was 20 ° C. The incident light intensity of the 365 nm LED lamp was 170 mW / cm 2 , irradiated for 12 hours, and after the reaction was completed, the caged alkane structure fuel was obtained by rotary evaporation and reduced pressure distillation with a yield of 35.12%.

[0174] Example 20

[0175] A caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2, 5 .0 3,9 .0 4.8 ]Decane;

[0176] The preparation method of the caged alkane structure fuel comprises the following steps:

[0177] (1) Add 1 mol / L methylcyclopentadiene dimer and 0.8 mol / L acetophenone to a 25 mL volumetric flask, and dilute to 25 mL with isooctane to obtain a mixed solution;

[0178] (2) The mixed solution obtained in step (1) was transferred to a 50 mL single-mouth quartz glass reactor, and nitrogen was continuously bubbled for 30 min under stirring. Then, a condenser was connected and sealed. The condenser was opened so that the reaction temperature was 20 ° C. The incident light intensity of the 365 nm LED lamp was 170 mW / cm 2 , irradiated for 12 hours, and after the reaction was completed, the caged alkane structure fuel was obtained by rotary evaporation and reduced pressure distillation with a yield of 21.04%.

[0179] Example 21

[0180] A caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2, 5 .0 3,9 .0 4.8 ]Decane;

[0181] The preparation method of the caged alkane structure fuel comprises the following steps:

[0182] (1) Add 0.3 mol / L methylcyclopentadiene dimer and 0.03 mol / L acetophenone to a 25 mL volumetric flask, and dilute to 25 mL with isooctane to obtain a mixed solution;

[0183] (2) The mixed solution obtained in step (1) was transferred to a 50 mL single-mouth quartz glass reactor, and nitrogen was continuously bubbled for 30 min under stirring. Then, a condenser was connected and sealed. The condenser was opened so that the reaction temperature was 20 ° C. The incident light intensity of the 365 nm LED lamp was 170 mW / cm 2 , irradiated for 12 hours, and after the reaction was completed, the caged alkane structure fuel was obtained by rotary evaporation and vacuum distillation with a yield of 15.54%.

[0184] Example 22

[0185] A caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2, 5 .0 3,9 .0 4.8 ]Decane;

[0186] The preparation method of the caged alkane structure fuel comprises the following steps:

[0187] (1) Add 0.3 mol / L methylcyclopentadiene dimer and 0.45 mol / L acetophenone to a 25 mL volumetric flask, and dilute to 25 mL with isooctane to obtain a mixed solution;

[0188] (2) The mixed solution obtained in step (1) was transferred to a 50 mL single-mouth quartz glass reactor, and nitrogen was continuously bubbled for 30 min under stirring. Then, a condenser was connected and sealed. The condenser was opened so that the reaction temperature was 20 ° C. The incident light intensity of the 365 nm LED lamp was 170 mW / cm 2 , irradiated for 12 hours, and after the reaction was completed, the caged alkane structure fuel was obtained by rotary evaporation and reduced pressure distillation with a yield of 31.57%.

[0189] Example 23

[0190] A caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2, 5 .0 3,9 .0 4.8 ]Decane;

[0191] The preparation method of the caged alkane structure fuel comprises the following steps:

[0192] (1) Add 0.3 mol / L methylcyclopentadiene dimer and 0.24 mol / L acetophenone to a 25 mL volumetric flask, and dilute to 25 mL with isooctane to obtain a mixed solution;

[0193] (2) The mixed solution obtained in step (1) was transferred to a 50 mL single-mouth quartz glass reactor, and nitrogen was continuously bubbled for 30 min under stirring. Then, a condenser was connected and sealed. The condenser was opened so that the reaction temperature was 5 ° C. The incident light intensity of the 365 nm LED lamp was 170 mW / cm 2 , irradiated for 12 hours, and after the reaction was completed, the caged alkane structure fuel was obtained by rotary evaporation and reduced pressure distillation with a yield of 40.90%.

[0194] Example 24

[0195] A caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2, 5 .0 3,9 .0 4.8 ]Decane;

[0196] The preparation method of the caged alkane structure fuel comprises the following steps:

[0197] (1) Add 0.3 mol / L methylcyclopentadiene dimer and 0.24 mol / L acetophenone to a 25 mL volumetric flask, and dilute to 25 mL with isooctane to obtain a mixed solution;

[0198] (2) The mixed solution obtained in step (1) was transferred to a 50 mL single-mouth quartz glass reactor, and nitrogen was continuously bubbled for 30 min under stirring. Then, a condenser was connected and sealed. The condenser was opened so that the reaction temperature was 40 ° C and the incident light intensity of the 365 nm LED lamp was 170 mW / cm 2 , irradiated for 12 hours, and after the reaction was completed, the caged alkane structure fuel was obtained by rotary evaporation and reduced pressure distillation with a yield of 41.64%.

[0199] Example 25

[0200] A caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2, 5 .0 3,9 .0 4.8 ]Decane;

[0201] The preparation method of the caged alkane structure fuel comprises the following steps:

[0202] (1) Add 0.5 mol / L methylcyclopentadiene dimer and 40 mg of cysteine-induced chiral TiO2 to a 25 mL volumetric flask, and dilute to 25 mL with isooctane to obtain a mixed solution;

[0203] (2) The mixed solution obtained in step (1) was transferred to a 50 mL single-mouth quartz glass reactor, and nitrogen was continuously bubbled for 30 min under stirring. Then, a condenser was connected and sealed. The condenser was opened so that the reaction temperature was 20 ° C. The incident light intensity of the 365 nm LED lamp was 170 mW / cm 2 , irradiated for 12 hours, and after the reaction was completed, the caged alkane structure fuel was obtained by rotary evaporation and vacuum distillation with a yield of 25.17%.

[0204] Example 26

[0205] A caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2, 5 .0 3,9 .0 4.8 ]Decane;

[0206] The preparation method of the caged alkane structure fuel comprises the following steps:

[0207] (1) Add 0.5 mol / L methylcyclopentadiene dimer and 40 mg of glycerol / cysteine-induced metal-deficient chiral TiO2 to a 25 mL volumetric flask, and dilute to 25 mL with isooctane to obtain a mixed solution;

[0208] (2) The mixed solution obtained in step (1) was transferred to a 50 mL single-mouth quartz glass reactor, and nitrogen was continuously bubbled for 30 min under stirring. Then, a condenser was connected and sealed. The condenser was opened so that the reaction temperature was 20 ° C. The incident light intensity of the 365 nm LED lamp was 170 mW / cm 2 , irradiated for 12 hours, and after the reaction was completed, the caged alkane structure fuel was obtained by rotary evaporation and reduced pressure distillation with a yield of 39.58%.

[0209] Example 27

[0210] A caged alkane structure fuel, wherein the caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2, 5 .0 3,9 .0 4.8 ]Decane;

[0211] The method for preparing the caged alkane structure fuel is different from that of Example 2 in that 9-fluorenone is used instead of acetophenone in step (1). The remaining steps and parameters are the same as those of Example 2, and the caged alkane structure fuel is obtained with a yield of 0.02%.

[0212] From the above results, it can be seen that the caged alkane structure fuel obtained by the preparation method provided by the present invention has a high yield and the density of the caged alkane structure fuel is not less than 0.960 g / cm 3 The net calorific value of the mass is not less than 42.63MJ / kg, and it also has a high specific impulse (specific impulse is not less than 328s) and good low-temperature performance. It has high density and high calorific value, which solves the problem that liquid fuel is difficult to have both high density and high calorific value.

[0213] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A caged alkane structure fuel, characterized in that: The caged alkane structure fuel is 3,8-dimethylpentacyclic [5.3.0.0 2,5 .0 3,9 .0 4.8 ] decane, having a chemical structure as shown in Formula I: The density of the caged alkane structure fuel is not less than 0.960 g / cm 3 , the mass net calorific value is not less than 42.63MJ / kg, and the specific impulse is not less than 328s.

2. The method for preparing the caged alkane structure fuel according to claim 1, comprising the following steps: (1) mixing methylcyclopentadiene dimer, a catalyst and a solvent to obtain a mixed solution; wherein the catalyst is a photosensitizer or a photocatalyst; (2) irradiating the mixed solution obtained in step (1) with ultraviolet light to carry out an addition reaction to obtain a caged alkane structure fuel.

3. The preparation method according to claim 2, characterized in that The photosensitizer in step (1) includes at least one of acetophenone, xanthanone, benzophenone, 2-isopropylthioxanthone and 2-acetonapthone.

4. The preparation method according to claim 2, characterized in that The photocatalyst in step (1) includes at least one of cysteine-induced chiral TiO2, tartaric acid-induced chiral TiO2, methionine-induced chiral TiO2 and glycerol / cysteine-induced metal-deficient chiral TiO2.

5. The preparation method according to claim 2, characterized in that The molar ratio of the photosensitizer to the methylcyclopentadiene dimer in the step (1) is 0.6 to 1:

1.

6. The preparation method according to claim 2, characterized in that The mass ratio of the photocatalyst to the methylcyclopentadiene dimer in the step (1) is 0.005-0.025:

1.

7. The preparation method according to claim 2, characterized in that The concentration of methylcyclopentadiene dimer in the mixed solution of step (1) is 0.05 to 0.9 mol / L.

8. The preparation method according to claim 2, characterized in that The incident intensity of the ultraviolet light in step (2) is 70 to 170 mW / cm 2 .

9. The preparation method according to claim 2, characterized in that The temperature of the addition reaction in step (2) is 10 to 30° C.; the time of the addition reaction is 1 to 12 hours.

10. An aerospace fuel, comprising the caged alkane structure fuel according to claim 1 or the caged alkane structure fuel prepared by the preparation method according to any one of claims 2 to 9.

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