A gelator and its preparation method and application, a hydrocarbon fuel gel and its preparation method

Abstract

The present invention belongs to the technical field of hydrocarbon fuels, and particularly relates to a gelator, a preparation method and application thereof, and a hydrocarbon fuel gel and a preparation method thereof. The present invention provides a gelator; the gelator has the structure shown in Formula I. When the gelator provided by the present invention is added to a hydrocarbon fuel, if there are metal ions in the hydrocarbon fuel, there will be a fluorescence response, which is convenient for detecting whether there are metal ions in the hydrocarbon fuel gel.

Description

Technical Field

[0001] The present invention belongs to the technical field of hydrocarbon fuels, and particularly relates to a gelator, a preparation method and application thereof, and a hydrocarbon fuel gel and a preparation method thereof. Background Art

[0002] Propellants are one of the important research contents in the aerospace field, providing an important power source guarantee for the development of national defense forces. The development direction of propellants requires combustion performance as the main requirement, such as high energy density, high specific impulse, etc., and at the same time, safety and other special requirements need to be considered, such as low signature.

[0003] Conventional propellants are often divided into solid propellants and liquid propellants. The advantage of solid propellants is high safety factor, but their energy content is low and it is difficult to fill the fuel. In contrast, liquid propellants have excellent overall specific impulse and are easy to fill, but liquid propellants are extremely likely to leak during storage and filling, causing major safety accidents such as corrosion, poisoning, and explosion. Researchers have tried many methods to improve the use safety of propellants while maintaining good combustion performance, and among them, gelation treatment of liquid propellants is one of the important development directions at present.

[0004] During the storage and use of hydrocarbon fuels, they will come into direct contact with metal containers or metal pipes, resulting in the dissolution of metal elements in the fuel. In the storage of hydrocarbon fuels, metal elements will, on the one hand, play a catalytic effect on the oxidation process of fuel molecules, and on the other hand, participate in the oxidation process themselves to form deposits, seriously affecting the use safety of the fuel. Therefore, it is of great significance to quickly and conveniently detect whether metal ions exist in hydrocarbon fuels. Summary of the Invention

[0005] In view of this, the purpose of the present invention is to provide a gelator, a preparation method and application thereof, and a hydrocarbon fuel gel and a preparation method thereof. When the gelator provided by the present invention is added to a hydrocarbon fuel, if there are metal ions in the hydrocarbon fuel, there will be a fluorescence response, which is convenient for detecting whether metal ions exist in the hydrocarbon fuel gel.

[0006] To achieve the above purpose, the present invention provides a gelator having the structure shown in Formula I:

[0007]

[0008] In Formula I, R is an alkyl group with 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, or 14 carbon atoms.

[0009] The present invention also provides a preparation method of the above-mentioned gelator, including the following steps:

[0010] Under the condition of an alkaline catalyst, 1,3,5-benzenetricarbonyl chloride and an amine compound are dissolved and subjected to a substitution reaction to obtain the gelator;

[0011] The structure of the amine compound is NH2-R.

[0012] Preferably, the temperature of the substitution reaction is 70 °C and the time is 18 h.

[0013] The present invention also provides the application of the above-mentioned gelator or a homolog of the above-mentioned gelator in detecting trace metal ions. The homolog of the gelator has the structure shown in Formula II;

[0014]

[0015] In Formula II, R1 is an alkyl group with 11 or 13 carbon atoms.

[0016] Preferably, the metal ion is Cu 2+ , Mn 2+ and Cr 2+ or one or more of them.

[0017] The present invention also provides a hydrocarbon fuel gel, which comprises a hydrocarbon fuel and a gelator compound;

[0018] The gelator compound comprises a gelator or a homolog of the gelator;

[0019] The gelator is the gelator shown in Formula I.

[0020] The homolog of the gelator has the structure shown in Formula II;

[0021]

[0022] In Formula II, R1 is an alkyl group with 11 or 13 carbon atoms.

[0023] Preferably, the mass of the hydrocarbon fuel is 95-98% of the mass of the hydrocarbon fuel gel.

[0024] Preferably, the mass of the gelator compound is 2%-5% of the mass of the hydrocarbon fuel gel.

[0025] The present invention also provides a preparation method of the above-mentioned hydrocarbon fuel gel, which comprises the following steps: mixing the hydrocarbon fuel and the gelator compound and then heating to obtain the hydrocarbon fuel gel.

[0026] Preferably, the temperature of the heating is 100 °C and the time is 5-10 min.

[0027] The present invention provides a gelator; the gelator has the structure shown in Formula I. Due to the presence of amide bonds, the gelator provided by the present invention can complex with metal ions such as Cu 2+ , Mn 2+ , Cr 2+ , enhancing the fluorescence intensity of the gelator. Therefore, it can produce a fluorescence response to trace metal elements present in hydrocarbon fuels and can detect the presence of trace metal elements (Cu 2+ , Mn 2+ and Cr 2+ ) in hydrocarbon fuels. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 1H NMR spectrum of the gelator N,N',N”-tri-n-hexylisophthalamide in Example 1; 1 ;

[0029] Figure 2 1H NMR spectrum of the gelator N,N',N”-tri-n-dodecylisophthalamide in Example 2; 1 ;

[0030] Figure 3 Fluorescence excitation spectrum in Test Example 1;

[0031] Figure 4 Fluorescence excitation spectrum in Test Example 2;

[0032] Figure 5 Fluorescence excitation spectrum in Test Example 3;

[0033] Figure 6 Fluorescence excitation spectrum in Test Example 4. DETAILED DESCRIPTION OF THE INVENTION

[0034] The present invention provides a gelator having the structure shown in Formula I:

[0035]

[0036] In Formula I, R is an alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, or 14 carbon atoms;

[0037] In the present invention, the dissolution reagent is preferably N-methylpyrrolidone. In the present invention, the dissolution is preferably carried out by first dissolving the basic catalyst and the amine compound in N-methylpyrrolidone, and then dropwise adding the N-methylpyrrolidone solution of 1,3,5-benzenetricarbonyl chloride to the above mixture.

[0038] In the present invention, the structure of the amine compound is NH2-R.

[0039] In the present invention, the temperature of the substitution reaction is preferably 70 °C, and the time is preferably 18 h.

[0040] In the present invention, after the substitution reaction, it preferably further includes subjecting the system obtained from the substitution reaction to crystallization treatment and suction filtration in sequence, and subjecting the crude product obtained by suction filtration to first drying, recrystallization, and second drying to obtain the gelator.

[0041] In the present invention, the crystallization treatment is preferably to place the system obtained from the substitution reaction in an ice-water bath and let it stand for 20 min. In the present invention, the temperature of the first drying and the second drying is independently preferably 40 °C, and the time is independently preferably 18 h.

[0042] The present invention also provides the application of the above-mentioned gelator or the homolog of the above-mentioned gelator in detecting trace metal ions. The homolog of the gelator has the structure shown in Formula II;

[0043]

[0044] In Formula II, R1 is an alkyl group with 11 or 13 carbon atoms.

[0045] In the present invention, the metal ion is preferably Cu 2+ , Mn 2+ and Cr 2+ or one or more of them.

[0046] The present invention also provides a hydrocarbon fuel gel, which includes a hydrocarbon fuel and a gelator compound;

[0047] The gelator compound includes a gelator or a homolog of the gelator;

[0048] The gelator is the above-mentioned gelator;

[0049] The homolog of the gelator has the structure shown in Formula II;

[0050]

[0051] In Formula II, R1 is an alkyl group with 11 or 13 carbon atoms.

[0052] In the present invention, the hydrocarbon fuel is preferably one or more of norbornane, n-dodecane, tetralin, and decalin, and more preferably norbornane (JP-10), tetralin, or decalin.

[0053] In the present invention, the mass of the hydrocarbon fuel is preferably 95-98% of the mass of the hydrocarbon fuel gel, and more preferably 96-97%.

[0054] In the present invention, the mass of the gelator compound is preferably 2% to 5% of the mass of the hydrocarbon fuel gel, and more preferably 3% to 4%.

[0055] The present invention also provides a method for preparing the above-mentioned hydrocarbon fuel gel, comprising the following steps: mixing the hydrocarbon fuel and the gelator compound, and then heating to obtain the hydrocarbon fuel gel.

[0056] Preferably, the heating temperature is preferably 100 °C, and the time is preferably 5 to 10 min.

[0057] The present invention also provides a method for preparing a hydrocarbon fuel gel, comprising the following steps:

[0058] Mixing the hydrocarbon fuel and the gelator, and then heating to obtain the hydrocarbon fuel gel.

[0059] In the present invention, the heating temperature is preferably 80 to 120 °C, more preferably 100 °C; the time is preferably 5 to 10 min, more preferably 7 to 8 min.

[0060] In the present invention, after heating, it is preferably further included to cool the product obtained by heating. In the present invention, no specific limitation is made on the cooling, and it can be cooled to room temperature.

[0061] To further illustrate the present invention, the following examples are used to describe the solution of the present invention in detail, but they should not be construed as limiting the protection scope of the present invention.

[0062] Example 1

[0063] 9.9 g of JP-10 and 0.1 g of the gelator N,N',N''-tri-n-hexylisophthalamide (R is n-hexyl in formula I) were added to a culture flask, heated at 100 °C for 5 min until the gelator was completely dissolved to form a transparent liquid, and then allowed to stand and cool to room temperature to form a hydrocarbon fuel gel.

[0064] Figure 1 For the 1H NMR spectrum of the gelator N,N',N''-tri-n-hexylisophthalamide in Example 1 1 From Figure 1 it can be seen that the spectral information is: 1H NMR (400 MHz, CDCl3) δ 8.32 (d, J = 10.0 Hz, 1H), 6.89 (s, 1H), 2.03 (s, 2H), 3.43 (s, 2H), 1.64–1.58 (m, 2H), 1.32 (dt, J = 7.9, 3.3 Hz, 4H), 0.90 (qd, J = 5.6, 4.7, 2.1 Hz, 3H).

[0065] Example 2

[0066] 9.7 g of JP-10 and 0.3 g of the gelator N,N',N”-tridodecylbenzene-1,3,5-tricarboxamide (R is dodecyl in Formula I) were added to a culture flask, heated at 100 °C for 5 min until the gelator was completely dissolved to form a transparent liquid, and then allowed to stand and cool to form a hydrocarbon fuel gel.

[0067] Figure 2 For the gelator N,N',N”-tridodecylbenzene-1,3,5-tricarboxamide in Example 2 1 1H NMR spectrum. It can be seen from Figure 1 that the spectral information is as follows: 1H NMR (400 MHz, CDCl3) δ 8.35 (s, 1H), 6.77 (s, 1H), 3.45 (q, J = 6.5 Hz, 2H), 2.45 (s, 2H), 1.63 (q, J = 7.1 Hz, 2H), 1.42–1.36 (m, 1H), 1.35 (s, 2H), 1.29 (d, J = 8.9 Hz, 4H), 1.26 (s, 9H), 0.88 (t, J = 6.7 Hz, 3H).

[0068] Example 3

[0069] 9.85 g of RP3 and 0.15 g of the gelator N,N',N”-tridodecylbenzene-1,3,5-tricarboxamide (R is dodecyl in Formula I) were added to a culture flask, heated at 100 °C for 5 min until the gelator was completely dissolved to form a transparent liquid, and then allowed to stand and cool to form a hydrocarbon fuel gel.

[0070] Example 4

[0071] 9.85 g of decalin and 0.15 g of the gelator N,N',N”-tridodecylbenzene-1,3,5-tricarboxamide (R is dodecyl in Formula I) were added to a culture flask, heated at 100 °C for 5 min until the gelator was completely dissolved to form a transparent liquid, and then allowed to stand and cool to form a hydrocarbon fuel gel.

[0072] Example 5

[0073] 9.85 g of tetralin and 0.15 g of the gelator N,N',N”-tridodecylbenzene-1,3,5-tricarboxamide (R is dodecyl in Formula I) were added to a culture flask, heated at 100 °C for 5 min until the gelator was completely dissolved to form a transparent liquid, and then allowed to stand and cool to form a hydrocarbon fuel gel.

[0074] Test 1:

[0075] 9.9 g of JP-10 and copper naphthenate were mixed, and the resulting mixture was mixed with 0.1 g of the gelator N,N',N”-trihexylbenzene-1,3,5-tricarboxamide to obtain a mixture containing 200 ppm of Cu2+ Hydrocarbon fuel gel;

[0076] The hydrocarbon fuel gel prepared in Example 1 and the hydrocarbon fuel gel containing 200 ppm Cu 2+ were subjected to fluorescence spectroscopy. The detection method was as follows: The prepared hydrocarbon fuel gel and the hydrocarbon fuel gel containing 200 ppm Cu 2+ were heated at 70 °C for 5 min until they returned to the solution state. They were respectively placed in 1 cm cuvettes and scanned with 600 nm emission light to obtain the fluorescence excitation spectra of the hydrocarbon fuel gel and the hydrocarbon fuel gel containing 200 ppm Cu 2+ respectively. The detection results are shown in Figure 3 , and it can be seen from Figure 3 that: The fluorescence excitation spectrum intensity of the hydrocarbon fuel gel containing 200 ppm Cu 2+ is significantly higher than that of the hydrocarbon fuel gel without Cu 2+ , indicating that copper ions can complex with the hydrocarbon fuel gel factor, enhancing its fluorescence intensity.

[0077] Test two:

[0078] 9.9 g of JP-10 and manganese naphthenate were mixed, and the resulting mixture was mixed with 0.1 g of the gelator N,N',N”-tri-n-hexylbenzene-1,3,5-tricarboxamide to obtain a hydrocarbon fuel gel containing 200 ppm Mn 2+ ;

[0079] The hydrocarbon fuel gel prepared in Example 1 and the hydrocarbon fuel gel containing 200 ppm Mn 2+ were subjected to fluorescence spectroscopy. The detection method was as follows: The prepared hydrocarbon fuel gel and the hydrocarbon fuel gel containing 200 ppm Mn 2+ were heated at 70 °C for 5 min until they returned to the solution state. They were respectively placed in 1 cm cuvettes and scanned with 600 nm emission light to obtain the fluorescence excitation spectra of the hydrocarbon fuel gel and the hydrocarbon fuel gel containing 200 ppm Mn 2+ respectively. The detection results are shown in Figure 4 , and it can be seen from Figure 4 that: The fluorescence excitation spectrum intensity of the hydrocarbon fuel gel containing 200 ppm Mn 2+ is significantly higher than that of the hydrocarbon fuel gel without Mn 2+ , indicating that manganese ions can complex with the hydrocarbon fuel gel factor, enhancing its fluorescence intensity.

[0080] Test three:

[0081] Mix 9.9 g of JP-10 with chromium naphthenate, and mix the resulting mixture with 0.1 g of the gelator N,N',N”-tri-n-hexylisophthalamide to obtain a hydrocarbon fuel gel containing 200 ppm of Cr 2+ ;

[0082] Perform fluorescence spectroscopy on the hydrocarbon fuel gel prepared in Example 1 and the hydrocarbon fuel gel containing 200 ppm of Cr 2+ . The detection method is as follows: Heat the prepared hydrocarbon fuel gel and the hydrocarbon fuel gel containing 200 ppm of Cr 2+ at 70 °C for 5 min until they return to the solution state. Place them in 1-cm cuvettes respectively, and scan with 600-nm emission light to obtain the fluorescence excitation spectra of the hydrocarbon fuel gel and the hydrocarbon fuel gel containing 200 ppm of Cr 2+ respectively. The detection results are shown in Figure 5 . It can be seen from Figure 5 that the fluorescence excitation spectrum intensity of the hydrocarbon fuel gel containing 200 ppm of Cr 2+ is significantly higher than that of the hydrocarbon fuel gel without Cr 2+ , indicating that chromium ions can complex with the hydrocarbon fuel gelator, enhancing its fluorescence intensity.

[0083] Test Example 4

[0084] Mix 9.9 g of JP-10 with chromium naphthenate, and mix the resulting mixture with 0.1 g of the gelator N,N',N”-tri-n-hexylisophthalamide to obtain hydrocarbon fuel gels containing 10 ppm, 20 ppm, 50 ppm, 100 ppm, and 150 ppm of Cu 2+ respectively;

[0085] Perform fluorescence spectroscopy on the hydrocarbon fuel gel prepared in Example 1 and the hydrocarbon fuel gel containing Cu 2+ . The detection method is as follows: Heat the prepared hydrocarbon fuel gels containing 10 ppm, 20 ppm, 50 ppm, 100 ppm, and 150 ppm of Cu 2+ at 70 °C for 5 min until they return to the solution state. Place them in 1-cm cuvettes respectively, and scan with 600-nm emission light to obtain the corresponding fluorescence excitation spectra. The detection results are shown in Figure 6 . It can be seen from Figure 6 that as the amount of copper ions added gradually increases, the fluorescence intensity of the hydrocarbon fuel gel gradually increases, and there is a positive correlation between the content of copper ions and the fluorescence intensity of the hydrocarbon fuel gel.

[0086] Although the above embodiments have described the present invention in detail, they are only some embodiments of the present invention, rather than all embodiments. Other embodiments can also be obtained based on these embodiments without creative efforts, and these embodiments all fall within the protection scope of the present invention.

Claims

1. Application of hydrocarbon fuel gel in detecting trace metal ions, characterized in that, The hydrocarbon fuel gel is obtained by mixing a gelator having the structure shown in Formula I with hydrocarbon fuel JP-10 and then heating; In the formula I, R is n-hexyl; The metal ion is Cu 2+ , Cr 2+ and Mn 2+ ; The mass ratio of the hydrocarbon fuel JP-10 to the gelator is 99:

1.

2. The application according to claim 1, wherein The heating temperature is 100 °C and the time is 5 to 10 min.

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