Kerosene phase change material based on amino acid C3 type curing factor and preparation method of kerosene phase change material

Abstract

The invention discloses a kerosene phase change material based on an amino acid C3 type curing factor and a preparation method of the kerosene phase change material. According to the method, the C3 type curing factor and low-polarity energetic liquid such as kerosene and aviation kerosene are heated, blended and then cooled, the energetic liquid can be cured into a solid gel state with stable mechanical properties, and the gel-state sample has no flowing phenomenon when inverted; meanwhile, a gel curing sample has a solid-liquid state reversible transformation characteristic, and solid-liquid state reversible transformation can be achieved under the action of external specific conditions (shearing force, temperature and the like). The preparation method provided by the invention is low in raw material cost, simple in process steps and high in operation controllability, and has remarkable practicability and industrial application value in the field of energetic materials.

Description

Technical Field

[0001] The present invention relates to a kerosene phase change material based on an amino acid C3 type curing factor and a preparation method thereof, belonging to the technical field of phase change of energetic liquid materials. Background Art

[0002] Liquid energetic materials have attracted considerable attention due to their unique physicochemical and energetic properties. While traditional liquid energetic materials offer high energy density and are easy to produce, store, and transport, their liquid fluidity presents safety risks such as leakage and poor stability. Furthermore, the liquid form limits structural construction and precise molding, hindering performance. Furthermore, the development of aerospace is placing higher demands on the energy density, safety, stability, and compatibility of energetic materials. Against this backdrop, the solidification technology for energetic liquid materials has emerged, aiming to convert liquid energetic materials into a solid state while retaining their high energy properties while overcoming the shortcomings of traditional liquid materials. Traditional liquid solidification technologies are often irreversible, limiting material reuse and performance control. Solidification technologies with reversible solid-liquid transition properties overcome this limitation, enabling on-demand changes in material phase, improving efficiency and flexibility, and reducing costs and resource waste. Reversible solid-liquid transition technology for energetic materials can advance the development of efficient, reliable, and safe energetic materials, expanding their potential for application in high-tech fields such as aerospace.

[0003] In supramolecular gel-based phase change material systems, gelling agents and solvent molecules self-assemble through supramolecular forces (such as coordination bonds, hydrogen bonds, and van der Waals forces) to form a three-dimensional interpenetrating network. The dynamic reversibility of supramolecular interactions confers dual advantages on these materials. First, the microstructure can be precisely engineered to adapt to phase transition requirements in diverse scenarios by manipulating the supramolecular system's composition, ratio parameters, and reaction conditions. Second, the material exhibits responsiveness to environmental factors such as temperature, pH, electric fields, and magnetic fields, enabling reversible phase transitions. Amino acid motifs, with their structural diversity, synergistic effects of multiple forces, biocompatibility, modifiability, and low cost, demonstrate broad potential for supramolecular gel construction. Molecular design and functionalization can further expand their application areas, promoting the transition of supramolecular gels from basic research to practical applications. For example, the self-assembly behavior of these typical assembly motifs, such as the C3 molecule, is highly controllable: their self-assembly pathways can be precisely tuned by varying parameters such as peripheral modification groups, the solvent environment, and temperature. For example, when different side chain groups are introduced to the periphery of the C3 molecule, the strength and type of intermolecular interactions change accordingly, thereby regulating the self-assembly mode and aggregate morphology, realizing the transition from a simple collaborative assembly mechanism to a complex self-assembly process, fully meeting the customized requirements of material structure and performance in diverse application scenarios. Summary of the Invention

[0004] The present invention aims to provide a phase change factor capable of reversibly solidifying low-polarity energetic materials such as kerosene and aviation kerosene (JP-10). The present invention provides a variety of chiral C3-type amino acid derivatives as phase change factors, including chiral leucine C3-type derivatives, chiral valine C3-type derivatives, chiral methionine C3-type derivatives, chiral aspartic acid C3-type derivatives, chiral phenylglycine C3-type derivatives, chiral phenylalanine C3-type derivatives, chiral isoleucine C3-type derivatives, and chiral glutamic acid C3-type derivatives. A simple and convenient curing process involves adding a low amount of phase change factor, then thermally blending with the corresponding liquid energetic material to be solidified, and then cooling to form a gel. This allows for the solidification of low-polarity hydrocarbon energetic liquid materials such as kerosene and aviation kerosene (JP-10), thereby completing the preparation of a solid gel energetic material. The solidified material exhibits a gel state that does not flow when inverted and exhibits reversible solid-liquid transition properties.

[0005] The kerosene-based phase change material with solid-liquid thixotropic and reversible transformation provided by the present invention can not only avoid the hidden dangers faced by liquid energetic materials in storage, transportation and use, but also overcome the difficulties in precise molding and complex structure construction of liquid materials, meet the preparation of materials with complex shapes and high dimensional precision, and improve the safety, use efficiency and flexibility of liquid energetic materials.

[0006] The phase change material provided by the present invention has unique reversible solid-liquid transition characteristics. On the one hand, it can avoid the potential risks of liquid energetic materials during storage, transportation and use, and improve the safety of liquid energetic materials during use; on the other hand, it can break through the technical bottlenecks of liquid materials in precise molding and complex structure preparation, and can meet the preparation requirements of high-dimensional precision materials and complex shapes, significantly improving the scope of use and application flexibility of liquid energetic materials.

[0007] In the present invention, the phase change factor comprises a plurality of C3-type chiral amino acid derivatives; for example, at least one of a chiral leucine C3-type derivative, a chiral valine C3-type derivative, a chiral methionine C3-type derivative, a chiral aspartic acid C3-type derivative, a chiral phenylglycine C3-type derivative, a chiral phenylalanine C3-type derivative, a chiral isoleucine C3-type derivative and a chiral glutamate C3-type derivative.

[0008] As a preferred technical solution of the present invention, the phase change factor uses chiral (Leu)3, chiral (Val)3, chiral (Met)3, chiral (Asp)3, chiral (Phe)3 and chiral (Glu)3 as the preferred C3 type phase change factors of the present invention. The above C3 type phase change factors are all products of organic synthesis, and their structural formulas are as follows, including:

[0009] (a) C3-type derivative molecules based on chiral leucine: (Leu)3;

[0010] (b) C3-type derivative molecules based on chiral valine: (Val)3;

[0011] (c) C3-type derivative molecules based on chiral methionine: (Met)3;

[0012] (d) C3-type derivative molecules based on chiral aspartic acid: (Asp)3.

[0013] (e) C3-type derivative molecule based on chiral phenylglycine: (Phg)3.

[0014] (f) C3-type derivative molecules based on chiral glutamic acid: (Glu)3 and other molecules;

[0015]

[0016] In the phase change factor structural formula, the amino acids used are all chirally pure compounds, and the red asterisk represents the location of the chiral carbon center.

[0017] Specifically, the kerosene-based phase change material with solid-liquid thixotropic reversible transformation performance provided by the present invention is a liquid energetic material and a phase change factor that are heated and blended, and after cooling, a gel-state solidified sample that does not flow when inverted is obtained;

[0018] The liquid energetic material is a low-polarity organic liquid energetic hydrocarbon, including kerosene and aviation kerosene;

[0019] The liquid energetic material kerosene was purchased from Aladdin Chemical Reagent Company, and aviation kerosene (JP-10) was purchased from Peterson Chemical Reagent Company. The purchased kerosene-based raw materials and reagents to be solidified can be used for scientific research.

[0020] In the kerosene-based phase change material, the added amount of the phase change factor is 15-60 mg / mL of liquid energetic material.

[0021] The present invention preferably adopts a heating blending method to mix the phase change factor with the corresponding liquid energetic material, the heating temperature is 60-100°C, and the heating time is 5-15 minutes, to ensure that the phase change factor is fully dissolved in the corresponding solidified solvent, and the sample presents a clear and transparent solution state during heating;

[0022] The cooling time is 15-40° C. After the sample is fully cooled, a gel-like solidified material is formed which does not flow when inverted.

[0023] The microstructure of the gel-like kerosene solidified material of the present invention is a regular nanofiber structure observed by a scanning electron microscope (SEM), and the fiber diameter is several hundred nanometers.

[0024] The gel-like kerosene solidified material of the present invention has been shown through rheological tests to exhibit unique thixotropic "solid-liquid" transition characteristics under the action of shear force; the liquid state after shearing can be restored to an inverted, non-flowing solid gel state after standing, realizing a reversible solid-liquid thixotropic process, and can achieve repeated reversible thixotropic solid-liquid transitions.

[0025] The gel-like kerosene solidified material of the present invention, when observed in the sample phase, shows that: when heated, the solid gel sample transforms into a transparent liquid state; and after cooling, it returns to the initial solid gel state; it realizes reversible "solid-liquid" transformation characteristics during the thermal cycle process, and can realize multiple repeated thermal cycle solid-liquid transformations.

[0026] The C3 kerosene-based phase change factor provided by the present invention has a solid-liquid reversible phase change property after solidification. It has a simple operation process and low preparation cost, showing significant practical value. It can not only expand the application scenarios of kerosene-based liquid energetic materials, but also has the following outstanding advantages:

[0027] (1) The present invention prepares a C3-type amino acid derivative phase change factor through a one-step reaction. The synthesis process of the phase change factor has significant advantages such as mild reaction conditions, low raw material cost, simple experimental operation and purification process, and high yield, and can easily achieve industrial-grade mass production.

[0028] (2) The phase change factor provided by the present invention has the remarkable characteristic of low addition amount, which not only helps to control costs, but also ensures that the combustion characteristics of the liquid energetic material itself are not changed; at the same time, the supporting solidification process is simple and convenient, providing a feasible path for large-scale and large-scale preparation of kerosene-based solid energetic materials.

[0029] (3) The kerosene-based phase change material provided by the present invention has the property of reversible solid-liquid transformation, which can not only avoid the safety hazards of liquid energetic materials during storage and use; but also meet the preparation requirements of materials with complex shapes and high dimensional precision, and promote the upgrading and development of liquid energetic materials in a safer, more reliable, efficient and convenient direction. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 The chemical structure and NMR spectrum (NMR solvent: deuterated chloroform) of the C3 chiral leucine derivative molecule (Leu)3.

[0031] Figure 2 The chemical structure and NMR spectrum (NMR solvent: deuterated chloroform) of the C3-type chiral valine derivative molecule (Val)3.

[0032] Figure 3 The chemical structure and NMR spectrum (NMR solvent: deuterated chloroform) of the C3 chiral methionine derivative molecule (Met)3.

[0033] Figure 4 The chemical structure and NMR spectrum (NMR solvent: deuterated chloroform) of the C3-type chiral aspartic acid derivative molecule (Asp)3.

[0034] Figure 5 The chemical structure and NMR spectrum (NMR solvent: deuterated chloroform) of the C3-type chiral phenylglycine derivative molecule (Phg)3.

[0035] Figure 6 The chemical structure and NMR spectrum of the C3-type chiral glutamic acid derivative molecule (Glu)3 (NMR solvent: deuterated chloroform).

[0036] Figure 7 This is a physical picture of the C3-type chiral leucine derivative (Leu)3 solidification sample of Inventive Example 1, kerosene (left), JP-10 (right), and the amount of solidification factor added: 20 mg / mL.

[0037] Figure 8 This is a physical picture of the solidified sample of the C3-type chiral valine derivative (Val) 3 of Inventive Example 1, kerosene (left), JP-10 (right), and the amount of solidification factor added: 20 mg / mL.

[0038] Figure 9 This is a physical picture of the C3-type chiral methionine derivative (Met)3 solidified sample of Inventive Example 1, kerosene (left), JP-10 (right), and the amount of solidification factor added: 20 mg / mL.

[0039] Figure 10 This is a physical picture of the C3-type chiral aspartic acid derivative (Asp)3 solidification sample of Inventive Example 1, kerosene (left), JP-10 (right), and the amount of solidification factor added: 20 mg / mL.

[0040] Figure 11 This is a physical picture of the C3-type chiral phenylglycine derivative (Phg)3 solidification sample of Inventive Example 1, kerosene (left), JP-10 (right), and the amount of solidification factor added: 20 mg / mL.

[0041] Figure 12 This is a physical picture of the C3-type chiral glutamic acid derivative (Glu)3 solidified sample of Inventive Example 1, kerosene (left), JP-10 (right), and the amount of solidification factor added: 20 mg / mL.

[0042] Figure 13 These are SEM microstructure characterization spectra of the phase change material in different to-be-cured solvents according to Inventive Example 2, (a) kerosene, (b) JP-10.

[0043] Figure 143. A physical diagram of the reversible shear-thixotropic solid-liquid transition process shown in Example 3 of the invention, (a) the initial solid gel state of the phase change material; (b) the liquid state of the phase change material after shear thixotropy; (c) the solid gel state of the phase change material after standing and recovering.

[0044] Figure 15 These are rheological test diagrams of the samples shown in Inventive Example 4, (a) kerosene, (b) JP-10.

[0045] Figure 16 Schematic diagram of the thermal cycle reversible solid-liquid transition process shown in Example 5 of the invention, (a) the initial solid gel state of the phase change material; (b) the liquid state of the phase change material after heating; (c) the solid gel state of the phase change material after cooling and recovery.

[0046] Figure 17 Schematic diagram of the curing effect shown in Comparative Example 1 of the invention, (a) kerosene, (b) JP-10.

[0047] Figure 18 Schematic diagram of the curing effect shown in Comparative Example 2 of the invention, (a) kerosene, (b) JP-10. DETAILED DESCRIPTION

[0048] The present invention will be further described in detail below in conjunction with specific embodiments. The examples provided are only intended to illustrate the present invention in detail and are not intended to limit the scope of the present invention. The examples provided below can serve as a guide for further improvements by those of ordinary skill in the art and are not intended to limit the present invention in any way.

[0049] Unless otherwise specified, the experimental methods in the following examples are conventional methods and were performed according to the technical conditions described in the literature in this field or in accordance with the corresponding product instructions. The raw materials and reagents used in the following examples, unless otherwise specified, were all commercially available.

[0050] In the following examples, multiple types of phase change factors added in specific proportions were dispersed into corresponding kerosene-based liquid energetic materials. The samples were heated sufficiently to form a transparent solution state in the heated state. After cooling to room temperature, an inverted, non-flowing solid gel state was formed. The solid-liquid thixotropic properties of the samples under shear thixotropic and thermal cycling stimulations were further studied.

[0051] Preparation of various chiral amino acid derivatives in the following examples:

[0052] 1. The synthesis method of the C3-type phase transition factor (Leu) 3 of the chiral leucine derivative is as follows:

[0053] 1,3,5-Benzenetricarboxylic acid chloride (1.33 g, 5 mmol) was dissolved in 150 mL of tetrahydrofuran (THF). 5 mL of triethylamine was added as an acid binder, and the mixture was stirred at 0°C in an ice bath for 10 min. Chiral leucine ethyl ester hydrochloride (Leu, 3.52 g, 18 mmol) was then added dropwise in an ice bath. After addition, the ice bath was removed and the reaction was continued at 25°C for 16 h. After the reaction, the solvent was rotary evaporated to a residual volume of 30-60 mL. The resulting residue was slowly poured into 1000 mL of acidic aqueous buffer and filtered under reduced pressure to obtain a crude white precipitate. The crude product was dried and recrystallized from a mixed solvent of hexane (Hex) and ethanol (EtOH) (Hex / EtOH). Filtered to obtain a white powder, the pure product (Leu)3 (2.57 g, 81% yield).

[0054] The synthetic route of C3-type phase change factor (Leu) 3 based on chiral leucine derivatives is as follows:

[0055]

[0056] 2. The synthesis method of the C3-type phase transition factor (Val) 3 of the chiral valine derivative is as follows:

[0057] 1,3,5-Benzenetricarboxylic acid chloride (1.33 g, 5 mmol) was dissolved in 150 mL of tetrahydrofuran (THF). 5 mL of triethylamine was added as an acid binder, and the mixture was stirred in an ice bath at 0°C for 10 min. Chiral valine ethyl ester hydrochloride (Val, 3.27 g, 18 mmol) was then added dropwise in an ice bath. After addition, the ice bath was removed and the reaction was continued at 25°C for 16 h. After the reaction, the solvent was rotary evaporated to a residual volume of 30-60 mL. The resulting residue was slowly poured into 1000 mL of acidic aqueous buffer and filtered under reduced pressure to obtain a crude white precipitate. The crude product was dried and recrystallized from a mixed solvent of hexane (Hex) and ethanol (EtOH) (Hex / EtOH). Filtered to obtain a white powder, the pure product (Val)3 (2.43 g, 82% yield).

[0058] The synthetic route of C3-type phase change factor (Val) 3 based on chiral valine derivatives is as follows:

[0059]

[0060] 3. The synthesis method of the C3-type phase transition factor (Met)3 of the chiral methionine derivative is as follows:

[0061] 1,3,5-Benzenetricarboxylic acid chloride (1.33 g, 5 mmol) was dissolved in 150 mL of tetrahydrofuran (THF). 5 mL of triethylamine was added as an acid-binding agent, and the mixture was stirred at 0°C in an ice bath for 10 min. Chiral methionine ethyl ester hydrochloride (Met, 3.85 g, 18 mmol) was then added dropwise in an ice bath. After addition, the ice bath was removed and the reaction was continued at 25°C for 16 h. After the reaction, the solvent was rotary evaporated to a residual volume of 30-60 mL. The resulting residue was slowly poured into 1000 mL of acidic aqueous buffer and filtered under reduced pressure to obtain a crude white precipitate. The crude product was dried and recrystallized from a mixed solvent of hexane (Hex) and ethanol (EtOH) (Hex / EtOH). Filtered to obtain a white powder, the pure product (Met)3 (2.68 g, 78% yield).

[0062] The synthetic route of C3-type phase change factor (Met)3 based on chiral methionine derivatives is as follows:

[0063]

[0064] 4. The synthesis method of the C3-type phase change factor (Asp)3 of the chiral aspartic acid derivative is as follows:

[0065] 1,3,5-Benzenetricarboxylic acid chloride (1.33 g, 5 mmol) was dissolved in 150 mL of tetrahydrofuran (THF). 5 mL of triethylamine was added as an acid-binding agent, and the mixture was stirred in an ice bath at 0°C for 10 min. Chiral aspartic acid diethyl ester hydrochloride (Asp, 4.06 g, 18 mmol) was then added dropwise in an ice bath. After addition, the ice bath was removed and the reaction was continued at 25°C for 16 h. After the reaction, the solvent was rotary evaporated to a residual volume of 30-60 mL. The resulting residue was slowly poured into 1000 mL of acidic aqueous buffer and filtered under reduced pressure to obtain a crude white precipitate. The crude product was dried and recrystallized from a mixed solvent of hexane (Hex) and ethanol (EtOH) (Hex / EtOH). Filtered to obtain a white powder, the pure product (Asp)3 (2.75 g, 76% yield).

[0066] The synthetic route of C3-type phase change factor (Asp)3 based on chiral methionine derivatives is as follows:

[0067]

[0068] 5. The synthesis method of the C3-type phase transition factor (Phg) 3 of the chiral phenylglycine derivative is as follows:

[0069] 1,3,5-Benzenetricarboxylic acid chloride (1.33 g, 5 mmol) was dissolved in 150 mL of tetrahydrofuran (THF). 5 mL of triethylamine was added as an acid binder, and the mixture was stirred in an ice bath at 0°C for 10 min. Chiral phenylglycine ethyl ester hydrochloride (Phg, 3.88 g, 18 mmol) was then added dropwise in an ice bath. After addition, the ice bath was removed and the reaction was continued at 25°C for 16 h. After the reaction, the solvent was rotary evaporated to a residual volume of 30-60 mL. The resulting residue was slowly poured into 1000 mL of acidic aqueous buffer and filtered under reduced pressure to obtain a crude white precipitate. The crude product was dried and recrystallized from a mixed solvent of hexane (Hex) and ethanol (EtOH) (Hex / EtOH). Filtered to obtain a white powder, the pure product (Phe)3 (2.78 g, 80% yield).

[0070] The synthetic route of C3-type phase change factor (Phg) 3 based on chiral phenylglycine derivatives is as follows:

[0071]

[0072] 6. The synthesis method of the C3-type phase transition factor (Glu)3 of the chiral glutamic acid derivative is as follows:

[0073] 1,3,5-Benzenetricarboxylic acid chloride (1.33 g, 5 mmol) was dissolved in 150 mL of tetrahydrofuran (THF). 5 mL of triethylamine was added as an acid-binding agent, and the mixture was stirred in an ice bath at 0°C for 10 min. Chiral glutamic acid diethyl ester hydrochloride (Glu, 4.31 g, 18 mmol) was then added dropwise in an ice bath. After addition, the ice bath was removed and the reaction was continued at 25°C for 16 h. After the reaction, the solvent was rotary evaporated to a residual volume of 30-60 mL. The resulting residue was slowly poured into 1000 mL of acidic aqueous buffer and filtered under reduced pressure to obtain a crude white precipitate. The crude product was dried and recrystallized from a mixed solvent of hexane (Hex) and ethanol (EtOH) (Hex / EtOH). Filtered to obtain a white powder, the pure product (Glu)3 (3.18 g, 83% yield).

[0074] The synthesis route of C3-type phase change factor (Glu)3 based on chiral glutamic acid derivatives is as follows:

[0075]

[0076] During the synthesis of the phase change factor, raw materials and reagents such as 1,3,5-benzenetricarboxylic acid chloride, chiral leucine ethyl ester, chiral valine ethyl ester, chiral methionine ethyl ester, chiral aspartic acid diethyl ester, chiral phenylglycine ethyl ester, chiral glutamic acid diethyl ester, and triethylamine were purchased from Inotech Reagents. Organic solvents used in the reaction, such as tetrahydrofuran, n-hexane, and ethanol, were purchased from Concord Reagents.

[0077] During the above-mentioned phase change factor synthesis process, the acidic aqueous buffer solution, including at least one of acetate buffer solution, citric acid buffer solution, phosphate buffer solution, hydrochloric acid / ammonium chloride buffer solution, hydrochloric acid / disodium hydrogen phosphate buffer solution, and sodium dihydrogen phosphate / ammonium chloride buffer solution, ensures that the pH value is within the range of 3.0-6.0.

[0078] The purity of the above phase change factors was determined by nuclear magnetic hydrogen spectrum and high resolution mass spectrometry. The nuclear magnetic spectrum is shown in Figures 1 to 6 As shown; the mass spectrum information of the phase change factor is shown below:

[0079] The structural formula of (Leu)3 is: C 33 H 51 N3O9, theoretical molecular weight: 633.3625; high-resolution mass spectrometry yielded [M+H] + : The corresponding molecular ion peak of m / z = 634.3694;

[0080] The structural formula of (Val)3 is: C 30 H 45 N3O9, theoretical molecular weight: 591.3156; high-resolution mass spectrometry yielded [M+H] + : The corresponding molecular ion peak of m / z = 592.3228;

[0081] The structural formula of (Met)3 is: C 30 H 45 N3O9S3, theoretical molecular weight: 687.2318; [M+H] was obtained in high-resolution mass spectrometry + : corresponding molecular ion peak of m / z = 688.2390;

[0082] The structural formula of (Asp)3 is: C 39 H 39 N3O9, theoretical molecular weight: 723.2851; high-resolution mass spectrometry yields [M+H] + :m / z=724.2926, [M+Na] + : corresponding molecular ion peak of m / z = 746.2744;

[0083] The structural formula of (Phg)3 is: C 39 H 39N3O9, theoretical molecular weight: 693.2686; [M+H] was obtained in high-resolution mass spectrometry. + :m / z=694.2759, [M+Na] + : corresponding molecular ion peak of m / z = 716.2578;

[0084] The structural formula of (Glu)3 is: C 36 H 51 N3O 15 , theoretical molecular weight: 765.3320; high-resolution mass spectrometry yielded [M+H] + :m / z=766.3391,[M+Na] + : The corresponding molecular ion peak is m / z=788.3208.

[0085] Example 1: Preparation of kerosene-based phase change material based on amino acid C3 curing factor

[0086] Weigh 20mg, 30mg, and 40mg of amino acid C3-based curing factors (Leu)3, (Val)3, (Met)3, (Asp)3, (Phg)3, and (Glu)3 into sample bottles, respectively. Then, add 1mL of the corresponding curing energetic solvent (kerosene, JP-10) to the sample bottles. The resulting dispersion was heated on a heating plate at 80°C for 10 minutes and then cooled to room temperature. Figures 7 to 12 As shown, after the sample is fully cooled, gel-state phase change materials with different addition amounts are obtained, and the solidified sample does not flow when inverted.

[0087] Example 2: Microstructural Characterization of Kerosene-Based Phase Change Materials Based on Amino Acid C3 Curing Factors

[0088] Scanning electron microscopy (SEM) was used to characterize the microstructure of the phase change material. When preparing the SEM test sample, a small amount of the kerosene phase change material sample prepared by the C3-type chiral aspartic acid derivative molecule (Asp)3 phase change factor in Example 1 was taken with a pipette and dropped onto the surface of the single crystal silicon wafer, which was then placed in a vacuum drying environment to allow the solvent to fully evaporate. After the solvent was completely evaporated, the sample surface was subjected to gold spraying to complete the preparation of the SEM test sample. During the test, the acceleration voltage of the scanning electron microscope was set to 8-10 kV to observe and record the microscopic morphology of the sample. Figure 13 As shown, the cured sample presents a regular fiber structure with a fiber diameter of hundreds of nanometers.

[0089] Example 3: Study on the solid-liquid thixotropic properties of kerosene-based phase change materials based on amino acid C3 curing factors

[0090] The kerosene-based phase change material prepared from the C3-type chiral aspartic acid derivative molecule (Asp)3 phase change factor in Example 1 was placed in a sample bottle, which was then fixed in a shaker, and shearing action was applied to the sample, and the state change process of the sample was observed in real time. Figure 14 The experimental results show that: under the action of shear force, the phase change material undergoes a phase transition from the solid state to the initial solid gel state ( Figure 14 Figure a) changes to a liquid flow state with good fluidity ( Figure 14 b); and after standing, it returns to the initial solid gel state ( Figure 14 This experimental phenomenon fully demonstrates that the kerosene-based phase change material of the present invention has excellent solid-liquid thixotropic phase-state reversible transformation performance.

[0091] Example 4: Study on the solid-liquid thixotropic properties of kerosene-based phase change materials based on amino acid C3 type curing factors

[0092] The kerosene-based phase change material prepared from the C3-type chiral aspartic acid derivative molecule (Asp)3 phase change factor in Example 1 was subjected to rheological testing to study its solid-liquid transition properties. The rheometer was set to oscillation scanning mode with a scanning range of 0.001 to 100%. Figure 15 Rheological tests show that under low oscillation strain, the storage modulus (G') of the kerosene-based phase change material is greater than the dissipation modulus (G"), and the phase change material exhibits solid elastic behavior; as the oscillation strain gradually increases, the storage modulus (G') and dissipation modulus (G") curves intersect, proving that the solidified sample undergoes solid-liquid transition under the action of shear force; further, as the oscillation strain increases, the storage modulus (G') is less than the dissipation modulus (G"), proving that the material begins to form a fluid liquid state and can no longer maintain its original solid state.

[0093] Example 5: Study on the thermal cycling solid-liquid transition performance of kerosene-based phase change materials based on amino acid C3 type curing factors

[0094] The kerosene-based phase change material sample prepared by the C3-type chiral aspartic acid derivative molecule (Asp)3 phase change factor in Example 1 was placed in a sample bottle, and then the sample was heated on an 80°C heating table for 10 minutes, and the state change process of the sample was observed in real time. Figure 16 The experimental results show that during the heating process, the phase change material undergoes a phase transition from the solid state to the initial solid gel state ( Figure 16 Figure a) changes to a liquid flow state with good fluidity ( Figure 16 b); and after cooling at 25 ° C, it returned to the initial solid gel state ( Figure 16(Figure c in the middle). This experimental phenomenon fully demonstrates that the kerosene-based phase change material has reversible "solid-liquid" transformation characteristics during thermal cycling.

[0095] Comparative Example 1: Preparation of kerosene-based phase change materials with solid-liquid thixotropic and reversible transition properties

[0096] Weigh 10 mg of C3-type chiral phase transition factors (Leu)3, (Val)3, (Met)3, (Asp)3, (Phg)3, (Glu)3, etc. and place them in sample bottles. Add 1 mL of the corresponding solidified energetic solvent (kerosene, JP-10) to the sample bottles. Heat the resulting dispersion on a heating plate at 80°C for 10 minutes and then cool it to room temperature. Figure 17 As shown in the figure, after the sample is fully cooled, it is still in a flowable liquid state and cannot be completely solidified. This shows that the kerosene energetic material cannot be completely solidified at a low addition amount of 10 mg / mL.

[0097] Comparative Example 2: Preparation of kerosene-based phase change materials with solid-liquid thixotropic and reversible transition properties

[0098] Weigh 20 mg of C3-type chiral phase transition factors (Leu)3, (Val)3, (Met)3, (Asp)3, (Phg)3, (Glu)3, etc. and place them in sample bottles. Add 1 mL of the corresponding solidified energetic solvent (kerosene, JP-10) to the sample bottles. Heat the resulting dispersion on a heating plate at 50°C for 10 minutes and then cool it to room temperature. Figure 18 As shown in the figure, under the heating condition of 50°C, the sample cannot be completely dissolved. After the sample is fully cooled, it is still in a flowable liquid state and cannot be completely solidified. This shows that when the phase change factor is heated and blended, it should be completely dissolved in the solvent to be solidified at an appropriate temperature to ensure a good curing effect.

[0099] In summary, the technical solution of the present invention has been elaborated in detail. For those skilled in the art, without departing from the inventive concept and protection scope of the present invention, the present invention can be implemented in a wider range based on equivalent parameters, concentrations, temperatures and other conditions without creative work. Although the present invention discloses specific embodiments, it should be understood that those skilled in the art can make further improvements thereto based on the principles of the present invention. In general, based on the technical solution of the present invention, this application is intended to cover any changes, applications or improvements based on the present invention, including equivalent substitutions or adaptive modifications that are beyond the scope of the present invention but are achieved by conventional technical means in the art.

Claims

1. Application of C3 amino acid derivatives as phase change factors in the preparation of kerosene-based phase change materials with reversible solid-liquid thixotropic transition properties; The C3 amino acid derivative is a compound with a benzene ring as the core and three amino acid ethyl esters or amino acid methyl esters as outer arms linked by amide bonds.

2. The use according to claim 1, characterized in that: The C3-type amino acid derivative is at least one of a chiral leucine C3-type derivative, a chiral valine C3-type derivative, a chiral methionine C3-type derivative, a chiral aspartic acid C3-type derivative, a chiral phenylglycine C3-type derivative, a chiral phenylalanine C3-type derivative, a chiral isoleucine C3-type derivative and a chiral glutamate C3-type derivative.

3. The use according to claim 2, characterized in that: The chiral leucine C3 derivative is (Leu)3; The chiral valine C3 derivative is (Val)3; The chiral methionine C3 derivative is (Met)3; The chiral aspartic acid C3 derivative is (Asp)3; The chiral phenylglycine C3 derivative is (Phg)3; The chiral glutamic acid C3 type derivative is (Glu)3; 4. A kerosene-based phase change material with reversible solid-liquid thixotropic properties, wherein a liquid energetic material and a phase change factor are heated and blended, and upon cooling, a gel-like solidified sample is obtained that does not flow when inverted; The phase change factor is the C3 type amino acid derivative involved in the application according to any one of claims 1 to 3.

5. The kerosene-based phase change material according to claim 4, characterized in that: The liquid energetic material is a low-polarity organic liquid energetic hydrocarbon, including kerosene and aviation kerosene.

6. The kerosene-based phase change material according to claim 4 or 5, characterized in that: In the kerosene-based phase change material, the added amount of the phase change factor is 15-60 mg / mL of liquid energetic material.

7. The kerosene-based phase change material according to any one of claims 4 to 6, characterized in that: The kerosene-based phase change material exhibits unique "solid-liquid" transition characteristics under heating or shear force.

8. The kerosene-based phase change material according to claim 7, wherein: The "solid-liquid" transition characteristics are specifically manifested as follows: the liquid state after heating or shearing can return to the initial solid gel state that does not flow when inverted after standing, realizing a solid-liquid thixotropic transition process, and reversible thixotropy can be achieved repeatedly.

9. A method for preparing the kerosene-based phase change material according to any one of claims 4 to 8, comprising the steps of: mixing the liquid energetic material with the phase change factor by a heating blending method, and then cooling to obtain the corresponding gel-solid phase change material.

10. The preparation method according to claim 9, characterized in that: The conditions of the heating blending method are as follows: The heating temperature is 60-100°C and the heating time is 5-15 minutes; The cooling time is 15-40°C.

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