Organic gel as well as preparation method and application thereof

Abstract

The invention relates to organic gel as well as a preparation method and application thereof. The organic gel comprises an organic gelling agent and a solvent A. The preparation method comprises the following steps: mixing the organic gelling agent with the solvent A to prepare the organic gel. A stable gel system with a three-dimensional network structure is formed through non-covalent interaction of intermolecular hydrogen bonds, Van der Waals force and the like, the gel system is endowed with thermodynamic reversibility, self-repairing capability and environmental adaptability, the solvent A is wide in application range, and absolute configuration of chiral carbon atoms has no obvious influence on the property of the organic gel.

Description

Technical Field

[0001] The present invention relates to the technical field of supramolecular chemistry, and in particular to an organic gel and a preparation method and application thereof. Background Art

[0002] Some small-molecule organic compounds possess the unique property of causing organic solvents to gel, forming organogels (oranogels), even at extremely low concentrations. These small-molecule compounds are called low-molecular-weight organogels. Unlike polymer gels, these gels are physical gels with thermal reversibility, making them currently attracting considerable attention as soft matter materials.

[0003] In the prior art, research on low molecular weight organogels has primarily focused on the design of gelling agent molecules and the optimization of solvent systems. However, the gelling agents reported so far generally have the following problems: (1) the gelling agent molecular structure is complex and the synthesis steps are cumbersome; (2) the applicable solvent range is narrow and the compatibility with polar or non-polar solvents is insufficient; (3) the gel stability is significantly affected by environmental factors (such as temperature and pH), which limits its practical application; and (4) the properties of the gel are easily affected by the chiral carbon configuration in the gel molecules. In addition, traditional preparation methods often rely on high-temperature dissolution and quenching processes, which consume high energy and are difficult to achieve large-scale production.

[0004] WO2015128178A1 discloses a gelling agent based on a glutamic acid derivative, but its solvent compatibility is narrow. CN106366789A synthesizes a gelling agent containing a diamide group, but its solvent compatibility is limited to non-polar systems. CN108218256A uses diethyl glutamate to synthesize a gelling agent that can gel ethanol and ethyl acetate, but the gelling concentration is relatively high.

[0005] Therefore, how to provide an organic gel with excellent thermal stability and solvent compatibility has become an urgent problem to be solved. Summary of the Invention

[0006] To solve the above technical problems, the present invention provides an organogel, a preparation method thereof, and an application thereof. The present invention uses a specific organogel to form a stable gel system with a three-dimensional network structure through intermolecular hydrogen bonds, van der Waals forces, and other non-covalent interactions between the organogel and solvent A. The gel system is endowed with thermodynamic reversibility, self-healing ability, and environmental adaptability. Furthermore, solvent A has a wide range of applications, and the absolute configuration (R or S) of the chiral carbon atoms in the organogel has no significant effect on the properties of the organogel.

[0007] To achieve this object, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides an organogel, comprising at least one organogelator and a solvent A; the organogelator has a structure as shown in the following formula I:

[0009]

[0010] wherein n can be selected from an integer between 6 and 20 (e.g., 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20), and X can be selected from NH or O.

[0011] The organogel provided by the present invention forms a stable gel system with a three-dimensional network structure through non-covalent forces such as intermolecular hydrogen bonds and van der Waals forces between the organogel and solvent A, and endows the gel system with thermodynamic reversibility, self-repairing ability and environmental adaptability. n CH3) significantly enhances the intermolecular attraction through the action of van der Waals forces, thereby promoting the formation and stability of organogels. The presence of three amide bonds (-NH-CO-) in the organogel molecule enables the formation of hydrogen bonds between molecules. Hydrogen bonds can serve as reversible cross-linking points, connecting the long alkyl carbon chain with the glutamic acid main chain, forming a stable three-dimensional network structure, giving the organogel excellent self-healing ability and adaptability under different environmental conditions. The presence of amide groups and ester groups in the organogel molecule gives the organogel self-healing ability through intermolecular hydrogen bonds and dynamic ester bonds, and enhances the interaction between molecules through van der Waals forces and dipole-dipole effects to form a stable gel system.

[0012] It should be noted that the organogel provided by the present invention may be composed of one organogelator having a structure of Formula I and solvent A, or may be composed of two or more organogelators having a structure of Formula I and solvent A; at the same time, it may be composed of at least one R-configuration organogelator having a structure of Formula I and solvent A, or may be composed of at least one S-configuration organogelator having a structure of Formula I and solvent A, or may be composed of at least one R-configuration organogelator having a structure of Formula I, at least one S-configuration organogelator having a structure of Formula I, and solvent A.

[0013] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved and realized.

[0014] Preferably, the organogel comprises a composition of Formula I-1 and Formula I-2:

[0015]

[0016] Here, n has the same definition as above.

[0017] Preferably, the mass ratio of Formula I-1 to Formula I-2 in the organogel is 1:(0.5:2), for example, it can be 1:0.5, 1:0.7, 1:0.9, 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8 or 1:2, etc.

[0018] Preferably, the organogelator is a compound of formula I having an R configuration or a compound of formula I having an S configuration.

[0019] Preferably, the organogel has an optically pure R-configuration structure as shown in Formula I or an optically pure S-configuration structure as shown in Formula I.

[0020] It should be noted that the organogel provided by the present invention has an optically pure R-configuration structure shown in Formula I or an optically pure S-configuration structure shown in Formula I, wherein optical purity refers to the optical purity of the structure shown in Formula I, optically pure R configuration means that the structure shown in Formula I contains only R-configuration enantiomers, and optically pure S configuration means that the structure shown in Formula I contains only S-configuration enantiomers.

[0021] There is no significant difference in the gelling properties of the organogels with R and S configurations in the present invention. This is because the intermolecular forces play a dominant role in the organogel system prepared by the present invention, weakening the effect of the absolute configuration of the chiral carbon atoms on the organogel properties.

[0022] Preferably, the concentration of the organogelling agent in the organogel is 1-20 mg / mL, for example, 1 mg / mL, 2 mg / mL, 4 mg / mL, 6 mg / mL, 8 mg / mL, 10 mg / mL, 12 mg / mL, 14 mg / mL, 16 mg / mL, 18 mg / mL or 20 mg / mL.

[0023] Preferably, the solvent A comprises any one or a combination of at least two of a halogenated hydrocarbon solvent, a hydrocarbon solvent, an alcohol solvent, an ether solvent, a ketone solvent, an ester solvent, a nitrile solvent, an amide solvent, a thioether solvent, a sulfone solvent or pyridine.

[0024] Preferably, the halogenated hydrocarbon solvent includes any one or a combination of at least two of dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, bromoform, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, bromoethane, 1,2-dibromoethane, bromobenzene, chlorofluorocarbons or trifluorotoluene.

[0025] Preferably, the hydrocarbon solvent includes any one of cyclohexane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, cyclopentane, methylcyclohexane, ethylbenzene, o-xylene, m-xylene, p-xylene, naphthalene, anthracene, petroleum ether, benzene, toluene, hexene, heptene, styrene or exo-tetrahydrodicyclopentadiene, or a combination of at least two thereof.

[0026] Preferably, the alcohol solvent includes any one or a combination of at least two of methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, ethylene glycol, propylene glycol, glycerol, butanediol, octanol, decanol, dodecanol or benzyl alcohol.

[0027] Preferably, the ether solvent includes any one or a combination of at least two of diethyl ether, tetrahydrofuran, dioxane, butyl ether, ethylene oxide, propylene oxide, anisole, diphenyl ether, methyl tert-butyl ether or diisopropyl ether.

[0028] Preferably, the ester solvent includes any one of ethyl acetate, methyl acetate, diethyl oxalate, butyl acetate, amyl acetate, ethyl butyrate, methyl benzoate or ethyl benzoate, or a combination of at least two thereof.

[0029] Preferably, the nitrile solvent includes any one of acetonitrile, propionitrile, butyronitrile, benzonitrile or acrylonitrile, or a combination of at least two thereof.

[0030] Preferably, the amide solvent includes any one of N,N-dimethylformamide, N,N-dimethylacetamide, N-ethylpyrrolidone, formamide or acetamide, or a combination of at least two thereof.

[0031] Preferably, the sulfide solvent includes dimethyl sulfide.

[0032] Preferably, the sulfone solvent includes sulfolane and / or dimethyl sulfoxide.

[0033] Preferably, the organogel is prepared by EDC condensation method.

[0034] Preferably, the EDC condensation method comprises the following steps: mixing glutamic acid monomer, reactive monomer, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, 1-hydroxybenzotriazole and solvent B, and reacting to obtain the organic gel; the reactive monomer is selected from a long-chain primary amine or a long-chain alcohol; and the glutamic acid monomer is selected from N-acetyl-L-glutamic acid or N-acetyl-D-glutamic acid.

[0035] It should be noted that when the glutamic acid monomer is selected as N-acetyl-L-glutamic acid, the obtained organogel is of R configuration; when the glutamic acid monomer is selected as N-acetyl-D-glutamic acid, the obtained organogel is of S configuration.

[0036] Preferably, the long-chain primary amine includes a C8-C22 (for example, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21 or C22) alkyl primary amine, more preferably any one of dodecylamine, octadecylamine or eicosylamine.

[0037] Preferably, the long-chain alcohol comprises an alkyl alcohol of C8-C22 (for example, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21 or C22), preferably any one of dodecanol, octadecanol or eicosanol.

[0038] Preferably, the molar ratio of the glutamic acid monomer, the reactive monomer, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 1-hydroxybenzotriazole is 1:(1.5-2.5):(1.5-2.5):(1.5-2.5).

[0039] Among them, "1.5-2.5" can be 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4 or 2.5, etc.

[0040] Preferably, the reaction temperature is 20-30°C (for example, 20°C, 22°C, 24°C, 26°C, 28°C or 30°C), and the reaction time is 60-80h (for example, 60h, 62h, 64h, 68h, 70h, 72h, 74h, 76h, 78h or 80h, etc.).

[0041] Preferably, the solvent B comprises dichloromethane.

[0042] In a second aspect, the present invention provides a method for preparing the organogel according to the first aspect, the method comprising the following steps: mixing an organogelator with a solvent A to prepare the organogel.

[0043] Preferably, the mixing is performed under heating conditions.

[0044] Preferably, the heating temperature is less than or equal to the boiling point of the solvent A.

[0045] Preferably, the mixing further includes a post-processing step, and the post-processing method includes cooling.

[0046] Preferably, the temperature of the cooled system is -5 to 25°C, for example, -5°C, 0°C, 5°C, 15°C, 20°C or 25°C.

[0047] In a third aspect, the present invention provides a use of the organogel as described in the first aspect in aerospace fuel propellant.

[0048] Compared with the prior art, the present invention has at least the following beneficial effects:

[0049] (1) The organic gel prepared by the present invention forms a stable gel system with a three-dimensional network structure through non-covalent interactions such as intermolecular hydrogen bonds and van der Waals forces, and endows the gel system with thermodynamic reversibility, self-repairing ability and environmental adaptability.

[0050] (2) The organic gel solvent A prepared by the present invention has a wide range of applications, covering almost all common organic solvents from low-polarity cyclohexane and n-decane to high-polarity dimethyl sulfoxide, N,N-dimethylformamide, etc., and can even successfully construct low-molecular-weight organic gels in special organic solvents such as pyrrolidone and N-methylpyrrolidone.

[0051] (3) The absolute configuration of the chiral carbon atoms in the organogel prepared by the present invention has no significant effect on the gelation properties, that is, there is no significant difference in the gelation properties between the R-configuration and the S-configuration gels. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 This is a physical picture of the organogel prepared in some embodiments of the present invention;

[0053] Among them, 1-organogel prepared in Example 2, 2-organogel prepared in Example 3, 3-organogel prepared in Example 4, 4-organogel prepared in Example 5, 5-organogel prepared in Example 6, 6-organogel prepared in Example 7, 7-organogel prepared in Example 8, 8-organogel prepared in Example 9, 9-organogel prepared in Example 10, 10-organogel prepared in Example 11;

[0054] Figure 2 This is an AFM test image of the organogel prepared in Example 1 of the present invention, with a scale of 2.0 μm;

[0055] Figure 3 This is a SEM test image of the organogel prepared in Example 20 of the present invention, with a scale of 5.00 μm;

[0056] Figure 4 This is a comparison chart of the viscosity test of the organogels prepared in Example 1 of the present invention and Comparative Example 1;

[0057] Figure 5 Graph showing the viscoelasticity test results of the organogel prepared in Example 1 of the present invention;

[0058] Figure 6 This is a graph showing the viscoelasticity test results of the organogel prepared in Comparative Example 1 of the present invention;

[0059] Figure 7 This is a comparison chart of the yield stress test of the organogels prepared in Example 1 of the present invention and Comparative Example 1;

[0060] Figure 8 This is a comparison chart of the thixotropy test of the organogels prepared in Example 1 of the present invention and Comparative Example 1. DETAILED DESCRIPTION

[0061] The technical solution of the present invention will be further described below with reference to the accompanying drawings and through specific embodiments. However, the following examples are merely simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims.

[0062] The organogel used in the following examples and comparative examples was prepared by the following method: glutamic acid monomer (1 mol, N-acetyl-L-glutamic acid or N-acetyl-D-glutamic acid), reaction monomer (2.1 mol, wherein, when X is selected from NH, n is 4, 6, 10, 12, 16, 18, 20, 22, the reaction monomer is n-hexane, octane, dodecylamine, tetradecylamine, octadecylamine, eicosylamine, docosylamine, tetracosylamine; .... When n is 10, 16, or 20, the reaction monomers are dodecanol, octadecanol, or docosanol), 1-ethyl-(3-dimethylaminopropyl), 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (2.1 mol), 1-hydroxybenzotriazole (2.1 mol), and dichloromethane (1 L). The mixture is reacted at 25° C. for 72 hours. After the reaction is completed, the mixture is cooled, filtered, washed, dried, and purified to obtain the organogel.

[0063] The following are the H NMR spectra or mass spectrometry data of the organogels used in the examples and comparative examples:

[0064] (1) When X is selected from NH and n is 4, Formula I is the structure shown in Compound M1:

[0065]

[0066] 1 H NMR(400MHz, CDCl3)δ7.18(s,1H),6.88(s,1H),6.41(s,1H),4.44-4.25(m,1H),3.31-3.19(m,4H), 2.40(ddt,J=53.3,14.6,7.9Hz,2H),2.03(s,5H),1.50(s,4H),1.25(s,12H),0.88(t,J=6.7Hz,6H).

[0067] (2) When X is selected from NH, n is 6, Formula I is the structure of compound M2:

[0068]

[0069] 1 H NMR(400MHz, CDCl3)δ7.18(s,1H),6.88(s,1H),6.41(s,1H),4.44-4.25(m,1H),3.31-3.19(m,4H), 2.40(ddt,J=53.3,14.6,7.9Hz,2H),2.03(s,5H),1.50(s,4H),1.25(s,20H),0.88(t,J=6.7Hz,6H).

[0070] (3) When X is selected from NH, n is 10, Formula I is the structure shown in Compound M3:

[0071]

[0072] 1 H NMR(400MHz, CDCl3)δ7.18(s,1H),6.88(s,1H),6.41(s,1H),4.44-4.25(m,1H),3.31-3.19(m,4H), 2.40(ddt,J=53.3,14.6,7.9Hz,2H),2.03(s,5H),1.50(s,4H),1.25(s,36H),0.88(t,J=6.7Hz,6H).

[0073] (4) When X is selected from NH, n is 12, Formula I is the structure shown in Compound M4:

[0074]

[0075] 1 H NMR(400MHz, CDCl3)δ7.18(s,1H),6.88(s,1H),6.41(s,1H),4.44-4.25(m,1H),3.31-3.19(m,4H), 2.40(ddt,J=53.3,14.6,7.9Hz,2H),2.03(s,5H),1.50(s,4H),1.25(s,44H),0.88(t,J=6.7Hz,6H).

[0076] (5) When X is selected from NH, n is 16, Formula I is the structure shown in Compound M5:

[0077]

[0078] 1 H NMR(400MHz, CDCl3)δ7.18(s,1H),6.88(s,1H),6.41(s,1H),4.44-4.25(m,1H),3.31-3.19(m,4H), 2.40(ddt,J=53.3,14.6,7.9Hz,2H),2.03(s,5H),1.50(s,4H),1.25(s,60H),0.88(t,J=6.7Hz,6H).

[0079] (6) When X is selected from NH, n is 18, Formula I is the structure shown in Compound M6:

[0080]

[0081] 1 H NMR(400MHz, CDCl3)δ7.18(s,1H),6.88(s,1H),6.41(s,1H),4.44-4.25(m,1H),3.31-3.19(m,4H), 2.40(ddt,J=53.3,14.6,7.9Hz,2H),2.03(s,5H),1.50(s,4H),1.25(s,68H),0.88(t,J=6.7Hz,6H).

[0082] (7) When X is selected from NH, n is 20, Formula I is the structure shown in Compound M7:

[0083]

[0084] 1 H NMR(400MHz, CDCl3)δ7.18(s,1H),6.88(s,1H),6.41(s,1H),4.44–4.25(m,1H),3.31–3.19(m,4H), 2.40(ddt,J=53.3,14.6,7.9Hz,2H),2.03(s,5H),1.50(s,4H),1.25(s,76H),0.88(t,J=6.7Hz,6H).

[0085] (8) When X is selected from NH, n is 22, Formula I is the structure shown in Compound M8:

[0086]

[0087] 1H NMR(400MHz, CDCl3)δ7.18(s,1H),6.88(s,1H),6.41(s,1H),4.44-4.25(m,1H),3.31-3.19(m,4H), 2.40(ddt,J=53.3,14.6,7.9Hz,2H),2.03(s,5H),1.50(s,4H),1.25(s,84H),0.88(t,J=6.7Hz,6H).

[0088] (9) When X is selected from O and n is 10, Formula I is the structure of compound M9:

[0089]

[0090] 1 H NMR (400MHz, CDCl3) δ7.18 (s, 1H), 4.65-4.46 (m, 1H), 4.19-4.07 (m, 4H), 2.71 (ddt, J= 53.3, 14.6, 7.9Hz, 2H), 2.03 (s, 5H), 1.81 (s, 4H), 1.25 (s, 36H), 0.88 (t, J = 6.7Hz, 6H).

[0091] (10) When X is selected from O, n is 16, Formula I is the structure shown in Compound M10:

[0092]

[0093] 1 H NMR (400MHz, CDCl3) δ7.18 (s, 1H), 4.65-4.46 (m, 1H), 4.19-4.07 (m, 4H), 2.71 (ddt, J= 53.3, 14.6, 7.9Hz, 2H), 2.03 (s, 5H), 1.81 (s, 4H), 1.25 (s, 60H), 0.88 (t, J = 6.7Hz, 6H).

[0094] (11) When X is selected from O, n is 20, Formula I is the structure shown in Compound M11:

[0095]

[0096] 1H NMR (400MHz, CDCl3) δ7.18 (s, 1H), 4.65-4.46 (m, 1H), 4.19-4.07 (m, 4H), 2.71 (ddt, J= 53.3, 14.6, 7.9Hz, 2H), 2.03 (s, 5H), 1.81 (s, 4H), 1.25 (s, 76H), 0.88 (t, J = 6.7Hz, 6H).

[0097] Example 1

[0098] This embodiment provides an organogel and a preparation method thereof, wherein the organogel comprises an organogel (compound M6, n=18, X is NH, R configuration) and exo-tetrahydrodicyclopentadiene;

[0099] The preparation method of the organogel is as follows:

[0100] An organic gelling agent (compound M6, n=18, X is NH, R configuration) and exo-tetrahydrodicyclopentadiene were heated and mixed at 185° C. to prepare an organic gelling agent with a concentration of 10 mg / mL.

[0101] Example 2-108

[0102] Examples 2-108 each provide an organogel and a preparation method thereof, which differ from Example 1 only in that the types of organogels and solvents and / or the concentrations of the organogels are different, and the heating temperature in the preparation method is the boiling point of the solvent used, as shown in Table 1:

[0103] Table 1

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110] Comparative Example 1

[0111] This comparative example provides an organogel and a preparation method thereof, which differs from Example 1 only in that the organogel has a structure shown in the following formula II:

[0112]

[0113] The organogel is prepared by the following method: N-Boc-L-glutamic acid (1 mol), eicosylamine (2.1 mol), carbodiimide hydrochloride (2.1 mol), 1-hydroxybenzotriazole (2.1 mol) and dichloromethane (1 L) are mixed, reacted at 25° C. for 72 hours, and after the reaction is completed, filtered, washed, dried and purified to obtain the organogel.

[0114] 1 H NMR (400MHz, CDCl3) δ6.71(s,1H),6.07(s,1H),5.71(s,1H),4.14-3.95(m,1H),3.31-3.19(m,4H),2.40 (ddt,J=53.3,14.6,7.9Hz,2H),2.03(s,5H),1.5(s,4H),1.46(s,9H)1.27(s,60H),0.9(t,J=6.7Hz,6H).

[0115] The preparation method of the organogel is the same as that in Example 1.

[0116] Comparative Example 2

[0117] This comparative example provides an organogel and a preparation method thereof, which is different from Example 1 only in that the organogel is compound M1.

[0118] Comparative Example 3

[0119] This comparative example provides an organogel and a preparation method thereof, which is different from Example 1 only in that the organogel is compound M8.

[0120] Figure 1 This is a physical picture of the organogel prepared in some embodiments of the present invention;

[0121] Among them, 1 is the organogel prepared in Example 2, 2 is the organogel prepared in Example 3, 3 is the organogel prepared in Example 4, 4 is the organogel prepared in Example 5, 5 is the organogel prepared in Example 6, 6 is the organogel prepared in Example 7, 7 is the organogel prepared in Example 8, 8 is the organogel prepared in Example 9, 9 is the organogel prepared in Example 10, and 10 is the organogel prepared in Example 11.

[0122] As can be seen from the figure, the organogel solvent A prepared in the present invention has a wide range of applications and is semi-fluid as a whole, meeting the property requirements of the organogel.

[0123] The present invention uses Hitachi S-4800FE-SEM to characterize the microscopic morphology of the organogel provided in Example 1, and its AFM image is as follows: Figure 2As shown, the scale bar is 2.0 μm. Figure 2 It can be seen that the organogel prepared in Example 1 presents a linear structure from a microscopic perspective, has a very high aspect ratio, and the diameter of the microstructure of the organogel is at the nanometer level.

[0124] The present invention uses Dimension FastScan (Bruker Nano)-AFM to characterize the microscopic morphology of the organogel provided in Example 20, and its SEM image is as follows Figure 3 As shown, the scale bar is 5.0μm. Figure 3 It can be seen that the organogel prepared in Example 20 presents a banded structure from a microscopic perspective, and the diameter of the gel's microstructure is at the micron or submicron level.

[0125] Figure 4 The viscosity test comparison chart of the organogel prepared in Example 1 of the present invention and Comparative Example 1 shows that at a low shear rate (10 -1 s -1 ) The organogel provided in Example 1 of the present invention has more excellent viscosity properties and better gelling performance.

[0126] Figure 5 This is a graph showing the viscoelasticity test results of the organogel provided in Example 1 of the present invention. The graph shows G' (storage modulus) and G" (loss modulus) at low strain. The storage modulus is higher than the loss modulus, indicating that the organogel has a solid-like elastic recovery ability and better organogel properties. The loss tangent (tan δ) indicates the ratio of the loss modulus to the elastic modulus. The tan δ value ranges from 0 to 1, i.e., the δ range is 0-90°. The loss tangent value can indicate the relationship between the loss modulus and the elastic modulus.

[0127] Figure 6 This is a graph showing the viscoelasticity test results of the organogel prepared in Comparative Example 1 of the present invention. The graph shows that at low strain, G' (storage modulus) and G" (loss modulus) show that the storage modulus is higher than the loss modulus, indicating that the organogel has elastic recovery ability similar to that of a solid and better organogel properties.

[0128] Figure 7 This is a comparison chart of the yield stress test of the organogel prepared in Example 1 of the present invention and Comparative Example 1. It can be seen from the figure that under low stress, the organogel prepared in Example 1 of the present application has smaller strain, the mutation point withstands greater pressure, and the stress shows periodic changes when the structure is destroyed. Due to the intermolecular hydrogen bonding of the amide bond, the organogel can be reorganized, giving the organogel excellent self-healing ability.

[0129] Figure 8The figure shows a comparison of the thixotropy test results of the organogels prepared in Example 1 of the present invention and Comparative Example 1. The figure shows that under the three-stage thixotropy test, the organogel prepared in Example 1 has a stronger degree of recovery after structural destruction, and has almost the same performance as the organogel before destruction.

[0130] The performance of the organogels provided in the above examples and comparative examples was tested, and the specific test standards are as follows:

[0131] (1) Viscosity (Pa·s): The organogels prepared in Examples 1-11, 27-28, 106-108 and Comparative Examples 1-3 were measured for viscosity using a rheometer at a shear rate of 10 -1 s -1 Testing the viscosity of organogels at low shear rates;

[0132] (2) Viscoelasticity (Pa): The organogels prepared in Examples 1-11, 27-28, 106-108, and Comparative Examples 1-3 were measured for their viscoelasticity using a rheometer. The storage modulus (G'), loss modulus (G"), and loss tangent (tan δ) were measured by applying an oscillating shear force. δ is the tangent angle, representing the modulus at the intersection of the storage modulus and the loss modulus. The modulus corresponding to structural failure, i.e., the maximum modulus that can be sustained, is the viscoelasticity.

[0133] (3) Yield stress (Pa): The yield stress of the organogels prepared in Examples 1-11, 27-28, 106-108, and Comparative Examples 1-3 was measured using a rheometer. The shear stress corresponding to the structural failure is the yield stress point.

[0134] (4) Thixotropy (%): The organogels prepared in Examples 1-11, 27-28, 106-108 and Comparative Examples 1-3 were tested for thixotropy using a rheometer through a three-stage thixotropy test. First, the organogels were placed in a static state and subjected to a shear rate of 0.1s. - 1. Continue for 60 seconds to establish the initial structure of the sample, and then apply a higher shear rate for 100 seconds - 1, lasting 30 s to destroy the structure of the sample, and finally reducing the shear rate to the value of the static stage for 120 s to observe the recovery of the sample structure.

[0135] Test results

[0136] The test results of the organogels prepared in Examples 1-11, 27-28, 106-108 and Comparative Examples 1-3 are shown in Table 2:

[0137] Table 2

[0138]

[0139]

[0140] The test results show that:

[0141] (1) It can be seen from Examples 1 to 108 that the viscosity of the organogel prepared by the present invention can reach 1.16×10 2 -3.41×10 4 Pa·s, and the viscoelasticity can reach 6.17×10 3 -5.72×10 4 Pa, the yield stress can reach 99.3-418.2Pa, and the thixotropy can reach 0.42-0.67%. It has excellent gelling properties, thermodynamic reversibility, self-healing ability and environmental adaptability.

[0142] (2) It can be seen from Example 1 and Comparative Example 1 that the acetyl group exists in the organogel structure provided by the present invention, and the amide group in the group provides a linking site for the formation of a three-dimensional structure. The prepared organogel has good gelling performance and can overcome a large destructive force. However, the Boc group in the organogel structure provided by Comparative Example 1 has a larger steric hindrance than the acetyl group, which destroys the tight stacking in the three-dimensional space and weakens the van der Waals force-driven self-assembly, resulting in poor organogel gelling performance.

[0143] (3) It can be seen from Example 1 and Comparative Examples 2-3 that the longer the hydrophobic carbon chain in the organogel structure, the stronger the anti-destruction ability of the prepared organogel, the greater the viscosity, the better the viscoelasticity, yield stress, and thixotropy; if there is an excessively long hydrophobic carbon chain in the organogel structure, it is difficult for the ultra-long chain molecules to be arranged in a regular and orderly manner. At the same time, the excessive entanglement of the long carbon chain will also destroy the orderly arrangement between molecules, and then destroy the structure of the organogel, resulting in the prepared organogel being brittle, and the structure is easily destroyed under a large shear stress, the yield stress is reduced, and the self-repairing ability of the organogel is deteriorated, and the thixotropy is reduced.

[0144] The applicant declares that the above is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention fall within the scope of protection and disclosure of the present invention.

Claims

1. An organogel, characterized in that The organogel comprises at least one organogel and solvent A; the organogel has a structure shown in the following formula I: wherein n is selected from an integer between 6 and 20, and X is selected from NH or O.

2. The organogel according to claim 1, characterized in that The organogel comprises a composition of formula I-1 and formula I-2: Wherein, n has the same definition as in claim 1; Preferably, the organogelator is a compound of formula I having an R configuration or a compound of formula I having an S configuration.

3. The organogel according to claim 1 or 2, characterized in that The concentration of the organogelator in the organogel is 1-20 mg / mL.

4. The organogel according to any one of claims 1 to 3, characterized in that The solvent A includes any one or a combination of at least two of a halogenated hydrocarbon solvent, a hydrocarbon solvent, an alcohol solvent, an ether solvent, a ketone solvent, an ester solvent, a nitrile solvent, an amide solvent, a thioether solvent, a sulfone solvent or pyridine; Preferably, the halogenated hydrocarbon solvent includes any one or a combination of at least two of dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, bromoform, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, bromoethane, 1,2-dibromoethane, bromobenzene, chlorofluorocarbons or trifluorotoluene; Preferably, the hydrocarbon solvent includes any one or a combination of at least two of cyclohexane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, cyclopentane, methylcyclohexane, ethylbenzene, o-xylene, m-xylene, p-xylene, naphthalene, anthracene, petroleum ether, benzene, toluene, hexene, heptene, styrene or exo-tetrahydrodicyclopentadiene; Preferably, the alcohol solvent includes any one or a combination of at least two of methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, ethylene glycol, propylene glycol, glycerol, butanediol, octanol, decanol, dodecanol or benzyl alcohol; Preferably, the ether solvent includes any one or a combination of at least two of diethyl ether, tetrahydrofuran, dioxane, butyl ether, ethylene oxide, propylene oxide, anisole, diphenyl ether, methyl tert-butyl ether or diisopropyl ether; Preferably, the ester solvent includes any one or a combination of at least two of ethyl acetate, methyl acetate, diethyl oxalate, butyl acetate, amyl acetate, ethyl butyrate, methyl benzoate or ethyl benzoate; Preferably, the nitrile solvent includes any one or a combination of at least two of acetonitrile, propionitrile, butyronitrile, benzonitrile or acrylonitrile; Preferably, the amide solvent includes any one or a combination of at least two of N,N-dimethylformamide, N,N-dimethylacetamide, N-ethylpyrrolidone, formamide or acetamide; Preferably, the sulfide solvent includes dimethyl sulfide; Preferably, the sulfone solvent includes sulfolane and / or dimethyl sulfoxide.

5. The organogel according to any one of claims 1 to 4, characterized in that The organic gel is prepared by adopting EDC condensation method.

6. The organogel according to claim 5, characterized in that The EDC condensation method comprises the following steps: mixing glutamic acid monomer, reaction monomer, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, 1-hydroxybenzotriazole and solvent B, and reacting to obtain the organic gel; The glutamate monomer is selected from N-acetyl-L-glutamate or N-acetyl-D-glutamate; The reactive monomer is selected from long-chain primary amines or long-chain alcohols.

7. The organogel according to claim 6, characterized in that The long-chain primary amine includes a C8-C22 alkyl primary amine, and is further preferably any one of dodecylamine, octadecylamine or eicosylamine; Preferably, the long-chain alcohol includes a C8-C22 alkyl alcohol, more preferably any one of dodecanol, octadecanol or eicosanol; Preferably, the molar ratio of the glutamic acid monomer, the reactive monomer, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 1-hydroxybenzotriazole is 1:(1.5-2.5):(1.5-2.5):(1.5-2.5); Preferably, the reaction temperature is 20-30° C., and the reaction time is 60-80 h.

8. A method for preparing the organogel according to any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: mixing an organic gelling agent with a solvent A to prepare the organic gel.

9. The method for preparing the organogel according to claim 8, characterized in that: The mixing is carried out under heating conditions; Preferably, the heating temperature is less than or equal to the boiling point of the solvent A; Preferably, the mixing further includes a post-processing step, and the post-processing method includes cooling.

10. Use of the organogel according to any one of claims 1 to 7 in aerospace fuel propellant.

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