Rare earth composite temperature-sensitive supramolecular gel deicing material for railway and preparation method thereof

Abstract

This invention provides a rare-earth composite thermosensitive supramolecular gel de-icing material for railways and its preparation method. This gel de-icing material utilizes the photothermal effect of rare-earth nano-borides, such as lanthanum hexaboride, to accelerate ice melting. It also utilizes a thermosensitive supramolecular polymer, which undergoes a gel-sol transition at a specific temperature. In cold weather, its temperature is far below the transition temperature, so it remains in a gel state. However, as the rare-earth nano-borides continuously absorb heat and gradually reach the transition temperature, it becomes a sol state and detaches with the ice layer, thereby solving the railway anti-icing problem.

Description

Technical Field

[0001] This invention belongs to the field of railway de-icing technology, and in particular relates to a rare earth composite thermosensitive supramolecular gel de-icing material for railways and its preparation method. Background Technology

[0002] Currently, most existing technologies utilize inorganic hydrophobic materials for de-icing. However, research shows that inorganic materials suffer from poor flexibility and coating cracking during construction. Furthermore, the continuous penetration of ice increases the adhesion between the hydrophobic material and the ice surface, thus reducing its anti-icing effect. Low temperatures can also cause coating cracking in inorganic materials. Additionally, because inorganic hydrophobic materials are typically blended mixtures with weak intermolecular interactions, their lifespan is easily shortened under the continuous sunlight and wind pressure of railway operation, potentially leading to coating peeling. Moreover, the production cost of inorganic hydrophobic materials is high, and because the solvent is usually water-based, they are either non-volatile or evaporate slowly, producing a strong, pungent odor. Summary of the Invention

[0003] In view of this, the present invention aims to propose a rare earth composite thermosensitive supramolecular gel de-icing material for railways and its preparation method, which combines the advantages of inorganic materials such as strong weather resistance, good acid and alkali resistance, flame retardancy, wear resistance and strong stability with organic materials such as strong flexibility and good film-forming properties, to solve the problem of ice formation on the bottom plate of high-speed trains during high-speed operation and difficulty in removal.

[0004] To achieve the above objectives, the technical solution of the present invention is implemented as follows:

[0005] A rare-earth composite thermosensitive supramolecular gel de-icing material for railways is prepared from raw materials comprising the following weight percentages: 83.72-85.68% of the main component, 14.1-15.74% of the guest component, and 0.22-0.54% of the solvent. The main component comprises the following raw materials in weight percentages: 78.64%-86.36% of hexacarbon bromine columnar aromatic hydrocarbons, 4.8%-13.31% of rare-earth nano-borides, 3.27%-3.59% of the reaction solvent, and 4.78%-5.25% of the catalyst. The guest component is a bispyridine-modified alkyl compound, and the rare-earth nano-borides are rare-earth borides with active hydroxyl groups on their surface.

[0006] The six-carbon bromine-chain columnar aromatic hydrocarbon not only has a large cavity that can interact with the guest, but also has reduced steric hindrance after modification with a long alkyl chain, enabling it to better undergo substitution reactions with rare earth nano-borides.

[0007] Furthermore, the rare earth nano-borides are one or more of lanthanum hexaboride, samarium hexaboride, or cerium hexaboride; preferably, the rare earth nano-borides are lanthanum hexaboride; the particle size D50 of the rare earth nano-borides is <90 nm. Lanthanum hexaboride is a preferred material in this invention due to its low price, high yield, and excellent endothermic effect, making it a high-performance material with a high cost-effectiveness. Although hexaborides such as samarium hexaboride also exhibit the LSPR effect, their cost is very high and they are not easy to separate from rare earth minerals.

[0008] The rare earth nano-borides are rare earth nanocompounds with photothermal effects. The preparation method of the rare earth nano-borides requires that their surface have active hydroxyl groups. These hydroxyl groups will undergo a substitution reaction with bromine, thereby connecting the rare earth nano-borides to the polymer chain. The main function is to rapidly raise the temperature of the polymer through endothermic absorption to achieve the effect of melting and de-icing.

[0009] Furthermore, the solvent in the raw materials for the de-icing material is dimethyl sulfoxide and / or tetrahydrofuran; the main reaction solvent is one or more of acetonitrile, tetrahydrofuran, or dichloromethane.

[0010] Furthermore, the catalyst is one or more of potassium carbonate, potassium iodide, or sodium carbonate.

[0011] Furthermore, the catalyst is potassium carbonate powder that has undergone anhydrous drying treatment.

[0012] These catalysts were chosen because a weakly alkaline environment is conducive to the removal of halogen atoms, thereby causing a substitution reaction. At the same time, it is best to use anhydrous and dried potassium carbonate powder so that it can absorb trace amounts of moisture in the reaction environment.

[0013] Furthermore, six-carbon bromine-chain columnar aromatics are prepared by the following method:

[0014] a) A monobromo-modified anisole was obtained by reacting 1,6-dibromohexane and p-hydroxyphenol in acetonitrile under the catalysis of potassium carbonate and potassium iodide.

[0015] b) The monobromine-modified anisole was reacted with terephthalic acid dimethyl ether and paraformaldehyde in dichloromethane in an ice bath under the catalysis of boron trifluoride diethyl ether.

[0016] Furthermore, the bispyridine-modified alkyl compound was prepared by refluxing 1,10-dibromodecane and 4,4'-bipyridine in acetonitrile at 85°C, followed by filtration and drying.

[0017] The present invention also provides a method for preparing a rare earth composite temperature-sensitive supramolecular gel de-icing material for railways as described above, the method comprising the following steps:

[0018] 1) Preparation of six-carbon bromine-chain columnar aromatic hydrocarbons;

[0019] 2) Preparation of the main body: Hexacarbon bromine-chain columnar aromatic hydrocarbons, rare earth nano-borides and catalyst powders are mixed in a reaction solvent, heated under reflux and stirred for 36-48 hours, and then separated by phase to obtain the main body;

[0020] 3) Preparation of alkyl compounds modified with guest bispyridine;

[0021] 4) The alkyl compound modified with bispyridine as the host and guest are ultrasonically mixed evenly in a solvent, and then stabilized at 20-30°C for 2-5 minutes. If the sol does not drip down the wall when the vial is removed, it is considered to have formed a gel.

[0022] The present invention also provides an application of the rare earth composite thermosensitive supramolecular gel de-icing material for railways as described above, wherein the de-icing material is coated on the surface of the object to be de-iced.

[0023] Compared with existing technologies, the rare earth composite thermosensitive supramolecular gel de-icing material and its preparation method for railways described in this invention have the following advantages:

[0024] (1) The rare earth composite thermosensitive supramolecular gel de-icing material for railways described in this invention comprises two parts: inorganic rare earth nanoparticles (D50 < 90 nm) and thermosensitive organic supramolecular gel. This is also the first time that the heat absorption effect of rare earth has been used to enable the thermosensitive polymer to achieve sol-gel transformation and be used in the field of de-icing.

[0025] (2) The rare-earth composite thermosensitive supramolecular gel de-icing material for railways described in this invention utilizes the photothermal effect of rare-earth nano-borides, such as lanthanum hexaboride, to accelerate ice melting. It also utilizes a thermosensitive supramolecular polymer, which undergoes a gel-sol transition at a specific temperature. In cold weather, its temperature is far below the transition temperature, resulting in a gel state. As the rare-earth nano-borides continuously absorb heat and gradually reach the transition temperature, they transform into a sol state and detach with the ice layer, thus solving the railway anti-icing problem. Furthermore, comparisons show that the heating rate of the rare-earth composite thermosensitive supramolecular gel de-icing material prepared in this invention far exceeds that of ordinary thermosensitive supramolecular polymers.

[0026] (3) The rare earth composite thermosensitive supramolecular gel de-icing material for railways described in this invention has a high initial preparation yield, and subsequent gel formation only requires low temperature, making the process simple. During use, the absorption of sunlight by rare earth nano-borides allows for rapid temperature rise within approximately 10 minutes to achieve ice layer shedding. Furthermore, if the critical gel transition temperature of 32-37°C is not reached, it can be reused multiple times, significantly reducing costs.

[0027] (4) The rare-earth composite thermosensitive supramolecular gel de-icing material for railways described in this invention utilizes host-guest chemistry to average the internal stress of the ice layer. This allows the ice layer to detach as a whole along with the structural transformation of the thermosensitive polymer, thus achieving the de-icing effect. Host-guest chemistry differs from traditional covalent chemistry; it relies on non-covalent interactions between molecules to form different systems. When the size, characteristics, and outline of the guest molecule match the size of the cavity provided by the host molecule, the guest molecule is constrained and fixed. This constraint on the guest molecule generally depends on the desorption of solvent molecules by the host molecule. Typically, guest molecules have a higher adsorption capacity than solvent molecules, thus giving host-guest complexes broad application prospects. This thermosensitive supramolecular gel formed by host-guest chemistry can average the internal stress of the ice layer during temperature-induced structural changes, thereby causing the ice layer to detach as a whole.

[0028] (5) The rare-earth composite thermosensitive supramolecular gel de-icing material for railways described in this invention utilizes six-carbon chain modified columnar aromatics, which endows the polymer monomer with good flexibility. In addition, the guest monomer is also a long-chain monomer with moderate binding ability to the columnar aromatic cavity, forming a highly flexible supramolecular structure under the interaction of host and guest. This invention imparts a lower gel transition temperature than the prior art, which is beneficial to the synergistic effect of rare-earth endothermic effect and temperature isomerism.

[0029] (6) The rare earth composite thermosensitive supramolecular gel de-icing material for railways described in this invention uses rare earth nano-borides as compounds for rare earth heat absorption, especially lanthanum hexaboride, which is a cathode emission material. This gives it excellent localized surface plasmon resonance (LSPR) effect. Moreover, among the existing rare earth nano-borides, lanthanum hexaboride is inexpensive, has a large production volume, and has excellent heat absorption effect. Attached Figure Description

[0030] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings:

[0031] Figure 1 This is a schematic diagram of the structure of the rare earth nanoparticle composite temperature-sensitive supramolecular gel de-icing material prepared in Example 1 of the present invention;

[0032] Figure 2 The heating rate graphs are shown for coating the gel prepared in Example 1 and the gel prepared in Comparative Example 1 onto an iron plate under 100W simulated light source irradiation.

[0033] Figure 3 The graphs show the heating rate of rare earth borides with different particle sizes in Example 1 and Comparative Example 3, and their effect on endothermic melting and de-icing. Detailed Implementation

[0034] It should be noted that, unless otherwise specified, the embodiments and features described in the present invention can be combined with each other.

[0035] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0036] Example 1

[0037] The preparation method of rare earth nanoparticle composite temperature-sensitive supramolecular gel de-icing material includes the following steps:

[0038] 1) Preparation of six-carbon bromine-chain aromatic hydrocarbons:

[0039] Using 1,6-dibromohexane (4.00 g, 16.40 mmol) and p-hydroxyphenol

[0040] (1.81 g, 16.40 mmol) was reacted in acetonitrile (100 mL) under the catalysis of potassium carbonate (0.66 g, 4.80 mmol) and potassium iodide (0.27 g, 1.64 mmol) to give monobromo-modified anisole. Then, using it as a starting material, it was reacted with terephthalic acid dimethyl ether (18 g, 0.13 mol) and paraformaldehyde (2.35 g, 26.06 mmol) in dichloromethane (200 mL) in an ice bath under the catalysis of boron trifluoride diethyl ether (5 mL) to give the product.

[0041] 2) Preparation of the main body:

[0042] First, rare earth nano-boron lanthanum hexaboride (0.21 g, 1.05 mmol, particle size D50 < 90 nm) with active hydroxyl groups on its surface and potassium carbonate powder (0.23 g, 1.68 mmol) were stirred and activated in acetonitrile (100 mL) for a period of time. Then, hexacarbon bromide columnar aromatic hydrocarbon (3.78 g, 4.2 mmol) was completely dissolved in acetonitrile (100 mL) and added to the previously activated solution system. The mixture was then heated under reflux and stirred for 48 hours. After the reaction was completed, the temperature was lowered and the solid was filtered out using a vacuum filtration device. The filtrate in the vacuum filtration flask was evaporated at 36 °C using a rotary evaporator to remove the solvent.

[0043] The crude product was dissolved in dichloromethane (300 mL) and washed three times with water (140 mL). After separation using a separatory funnel, anhydrous magnesium sulfate was added and the mixture was dried over silica gel. The product was then purified by column chromatography using petroleum ether and ethyl acetate in a volume ratio of 2:1. The final product was a white powder (0.41 g, yield 21%).

[0044] 3) Preparation of bispyridine-modified alkyl compounds (guests):

[0045] First, 4,4'-bipyridine (5.56 g, 35.7 mmol) was dissolved in acetonitrile (50 mL) in a round-bottom flask. Then, 1,10-dibromodecane (3.78 g, 12.6 mmol) and acetonitrile (60 mL) were mixed thoroughly in a dropping funnel and placed above the round-bottom flask. The solution was added dropwise to the flask at a constant rate, stirred, and refluxed at 85 °C. After 12 hours, the mixture was cooled to room temperature, and a suspended solid was formed in the solution. The solid and liquid were then separated using a vacuum filtration flask and a funnel and washed with acetonitrile. The solid was then dried in a vacuum oven at 60 °C overnight under vacuum, finally yielding a light green bispyridine-modified alkyl compound (guest) product (7 g, 90% yield).

[0046] 4) Dissolve the main component and the bispyridine-modified alkyl compound in 10 mL of dimethyl sulfoxide at a molar ratio of 2:1 and at 40 °C (above the critical gelation temperature). After the system is homogeneous, let it stand for 5 minutes to form a gel.

[0047] The structure of this rare-earth composite temperature-sensitive supramolecular gel de-icing material is as follows: Figure 1 As shown in the figure. Observation shows that the critical transition temperature of the gel de-icing material is approximately 33℃.

[0048] from Figure 2 The data shows that the transition temperature was not reached at 9 minutes, but it was reached at 10 minutes. However, by this time, the ice had almost completely melted, indicating that the process before 9 minutes was primarily ice-melting. Once the transition temperature was reached, the structural transformation likely played a synergistic role in the ice-melting process. Therefore, the main reason for the coating peeling off is that the rare earth elements absorbed heat, causing the ice layer to melt.

[0049] Example 2

[0050] The preparation method of rare earth nanoparticle composite temperature-sensitive supramolecular gel de-icing material includes the following steps:

[0051] 1) Preparation of six-carbon bromine-chain columnar aromatic hydrocarbons as in step 1 of Example 1).

[0052] 2) Preparation of the main body

[0053] First, rare earth nano-boron lanthanum hexaboride (0.34 g, 1.68 mmol, particle size D50 < 90 nm) with active hydroxyl groups on its surface and potassium carbonate powder (0.23 g, 1.68 mmol) were stirred and activated in acetonitrile (100 mL) for a period of time. Then, hexacarbon bromide columnar aromatic hydrocarbon (3.78 g, 4.2 mmol) was completely dissolved in acetonitrile (100 mL) and added to the previously activated solution system. The mixture was then heated under reflux and stirred for 48 hours. The post-treatment was the same as in Example 1. Finally, a white powdery main product (0.94 g, yield 30%) was obtained.

[0054] 3) Preparation of the bispyridine-modified alkyl compound (guest) is as described in step 3 of Example 1.

[0055] 4) Dissolve the main component and the bispyridine-modified alkyl compound in 10 mL of dimethyl sulfoxide at a molar ratio of 2:1 at 40 °C (above the critical gelation temperature). After the system is homogeneous, let it stand for 5 minutes to form a gel.

[0056] The structure of this rare-earth composite temperature-sensitive supramolecular gel de-icing material is as follows: Figure 1 As shown in the figure. Observation shows that the critical transition temperature of the gel de-icing material is approximately 34℃.

[0057] Example 3

[0058] The preparation method of rare earth nanoparticle composite temperature-sensitive supramolecular gel de-icing material includes the following steps:

[0059] 1) Preparation of six-carbon bromine-chain columnar aromatic hydrocarbons as in step 1 of Example 1).

[0060] 2) Preparation of the main body

[0061] First, rare earth nano-boron lanthanum hexaboride (0.43 g, 2.1 mmol, particle size D50 < 90 nm) with active hydroxyl groups on its surface and potassium carbonate powder (0.23 g, 1.68 mmol) were stirred and activated in acetonitrile (100 mL) for a period of time. Then, monobromo-chain columnar aromatic hydrocarbon (3.78 g, 4.2 mmol) was completely dissolved in acetonitrile (100 mL) and added to the previously activated solution system. The mixture was then heated under reflux and stirred for 48 hours. The post-treatment was the same as in Example 1. Finally, a white powdery main product (0.71 g, yield 18%) was obtained.

[0062] 3) Preparation of the bispyridine-modified alkyl compound (guest) is as described in step 3 of Example 1.

[0063] 4) Dissolve the main component and the bispyridine-modified alkyl compound in 10 mL of dimethyl sulfoxide at a molar ratio of 2:1 at 40 °C (above the critical gelation temperature). After the system is homogeneous, let it stand for 5 minutes to form a gel.

[0064] The structure of this rare-earth composite temperature-sensitive supramolecular gel de-icing material is as follows: Figure 1 As shown in the figure. Observation shows that the critical transition temperature of the gel de-icing material is approximately 36℃.

[0065] Example 4

[0066] The preparation method of rare earth nanoparticle composite temperature-sensitive supramolecular gel de-icing material includes the following steps:

[0067] 1) Preparation of six-carbon bromine-chain columnar aromatic hydrocarbons as in step 1 of Example 1).

[0068] 2) Preparation of the main body

[0069] First, rare earth nano-boron lanthanum hexaboride (0.64 g, 3.15 mmol, particle size D50 < 90 nm) with active hydroxyl groups on its surface and potassium carbonate powder (0.23 g, 1.68 mmol) were stirred and activated in acetonitrile (100 mL) for a period of time. Then, hexacarbon bromide columnar aromatic hydrocarbon (3.78 g, 4.2 mmol) was completely dissolved in acetonitrile (100 mL) and added to the previously activated solution system. The mixture was then heated under reflux and stirred for 48 hours. The post-treatment was the same as in Example 1. Finally, a white powdery main product (0.47 g, yield 12%) was obtained.

[0070] 3) Preparation of the bispyridine-modified alkyl compound (guest) is as described in step 3 of Example 1.

[0071] 4) The dimer and the bispyridine-modified alkyl compound were dissolved in 10 mL of dimethyl sulfoxide at a molar ratio of 2:1 at 40 °C (above the critical gelation temperature). After the system was homogeneous, it was allowed to stand for 5 minutes to form a gel.

[0072] The structure of this rare-earth composite temperature-sensitive supramolecular gel de-icing material is as follows: Figure 1 As shown in the figure. Observation shows that the critical transition temperature of the gel de-icing material is approximately 37℃.

[0073] Comparative Example 1

[0074] The preparation method of rare earth-free thermosensitive supramolecular gel includes the following steps:

[0075] 1) A mixture of hexacarbon bromide columnar aromatic hydrocarbon (3.78 g, 4.2 mmol), bis(4-hydroxyphenyl) disulfide (0.42 g, 1.68 mmol), and potassium carbonate powder (0.23 g, 1.68 mmol) in acetonitrile (100 mL) was heated under reflux and stirred for 48 hours. The mixture was then cooled and the solid was filtered off using a vacuum filtration device. The solvent was concentrated by rotary evaporation. The crude product was dissolved in dichloromethane (300 mL) and washed three times with water (140 mL). After separation, the mixture was stirred, dried, filtered, and purified by column chromatography to obtain a white powdery product (P5)2.

[0076] 2) Dissolve 1,10-dibromodecane (3.78 g, 12.6 mmol) in a dropping funnel containing acetonitrile (50 mL), and add the solution dropwise to a solution of 4,4'-bipyridine (5.56 g, 35.7 mmol) in acetonitrile (60 mL). Stir and heat to 85 °C under reflux overnight. After cooling, filter, wash and dry to obtain a light green solid, product G.

[0077] 3) Dissolve (P5)2 and G in 10 mL of dimethyl sulfoxide at a molar ratio of 2:1 at 50 °C using ultrasonication. After the system is homogeneous, let it stand for 5 minutes to form a gel.

[0078] Observations reveal that the transition temperature of the above-mentioned rare earth-free thermosensitive supramolecular gel is 28-32℃, while the transition temperature of the de-icing material obtained in Example 1 of this application is 32-37℃. This indicates that the composite of rare earth nanoparticles in this application lowers the original thermosensitive polymer gel-sol transition temperature, which is more conducive to reaching the phase transition temperature during rare earth photothermal action, thus making de-icing easier to achieve.

[0079] like Figure 2 As shown, the heating rate graphs of Comparative Example 1 (without rare earth) and Example 1 (with rare earth) are shown. It can be seen that the data of Example 1 stops at 10 minutes, indicating that the temperature reaches more than 30 degrees Celsius at 10 minutes, and the ice layer falls off. This shows that rare earth doping can achieve rapid heating to a large extent and play a role in rapid ice melting.

[0080] Comparative Example 2

[0081] A method for preparing a thermosensitive organic supramolecular gel with rare earth nanoparticles and no hydroxyl groups on its surface includes the following steps:

[0082] 1) Potassium carbonate powder (0.23 g, 1.68 mmol) was activated in acetonitrile (100 mL) by stirring for a period of time. Then, hexacarbon bromide columnar aromatic hydrocarbon (3.78 g, 4.2 mmol) was completely dissolved in acetonitrile (100 mL) and added to the previously activated solution system. The mixture was then heated under reflux and stirred for 48 hours. The post-treatment was the same as in the above example. Finally, a white powdery main product was obtained.

[0083] 2) The preparation steps of the bispyridine-modified alkyl compound (guest) are the same as those described above.

[0084] 3) The dimer and the bispyridine-modified alkyl compound were ultrasonically dissolved in 10 mL of dimethyl sulfoxide at a molar ratio of 2:1 (above the critical gel temperature). Then, rare earth nano-borides (0.64 g, 3.15 mmol) without active hydroxyl groups on the surface were added and physically mixed with the sol system. After the system was homogeneous, it was allowed to stand.

[0085] In this method, rare earth nano-borides cannot react with columnar aromatics because they lack surface hydroxyl groups. They can only be mixed with the gel system through physical blending. This causes the rare earth nano-borides to detach when the gel undergoes a gel-sol transition due to temperature changes, because there are no chemical bonds between them and the host and guest polymers. As a result, the anti-icing and de-icing coating is not reusable.

[0086] Comparative Example 3 Particle Size

[0087] The experimental steps in Comparative Example 3 are the same as in Example 1, except for the particle size of the rare earth boride. Here, the D50 particle size of the rare earth boride is in the micrometer range, and it does not possess the LSPR effect. Therefore, the melting rate is far inferior to the melting effect in Example 1. The melting effect is as follows: Figure 3 As shown.

[0088] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A rare earth composite temperature sensitive supramolecular gel de-icing material for railway characterized in that: This material is prepared from raw materials comprising the following weight percentages: main component 83.72-85.68%, guest component 14.1-15.74%, and solvent 0.22-0.54%; wherein the main component comprises the following raw materials comprising the following weight percentages: hexacarbon bromine-chain columnar aromatic hydrocarbons 78.64%-86.36%, rare earth nano-borides 4.8%-13.31%, reaction solvent 3.27%-3.59%, and catalyst 4.78%-5.25%; the guest component is a bispyridine-modified alkyl compound, and the rare earth nano-borides are rare earth nano-borides with active hydroxyl groups on their surface; the particle size D50 of the rare earth nano-borides is <90 nm; This material is prepared by a method including the following steps: 1) Preparation of six-carbon bromine-chain columnar aromatic hydrocarbons; 2) Preparation of the main body: Hexacarbon bromine-chain columnar aromatic hydrocarbons, rare earth nano-borides and catalyst powders are mixed in a reaction solvent, heated under reflux and stirred for 36-48 hours, and then separated by phase to obtain the main body; 3) Preparation of alkyl compounds modified with guest bispyridine; 4) The alkyl compound modified with bispyridine as the host and guest are ultrasonically mixed in a solvent and stabilized at 20-30°C for 2-5 minutes. If the sol does not drip down the wall when the vial is removed, it is considered to have formed a gel.

2. The rare-earth composite thermosensitive supramolecular gel de-icing material for railways according to claim 1, characterized in that: Rare earth nano-borides are one or more of lanthanum hexaboride, samarium hexaboride, or cerium hexaboride.

3. The rare-earth composite thermosensitive supramolecular gel de-icing material for railways according to claim 1, characterized in that: The solvent in the raw materials for the de-icing material is dimethyl sulfoxide and / or tetrahydrofuran; the main reaction solvent is one or more of acetonitrile, tetrahydrofuran, or dichloromethane.

4. The rare-earth composite thermosensitive supramolecular gel de-icing material for railways according to claim 1, characterized in that: The catalyst is one or more of potassium carbonate, potassium iodide, or sodium carbonate.

5. The rare-earth composite thermosensitive supramolecular gel de-icing material for railways according to claim 4, characterized in that: The catalyst is potassium carbonate powder that has been dried anhydrous.

6. The rare-earth composite thermosensitive supramolecular gel de-icing material for railways according to claim 1, characterized in that: Hexacarbon bromine-chain columnar aromatics are prepared by the following method: a) A monobromo-modified anisole was obtained by reacting 1,6-dibromohexane and p-hydroxyphenol in acetonitrile under the catalysis of potassium carbonate and potassium iodide. b) The monobromine-modified anisole was reacted with terephthalic acid dimethyl ether and paraformaldehyde in dichloromethane in an ice bath under the catalysis of boron trifluoride diethyl ether.

7. The rare-earth composite thermosensitive supramolecular gel de-icing material for railways according to claim 1, characterized in that: The bispyridine-modified alkyl compound was prepared by refluxing 1,10-dibromodecane and 4,4'-bipyridine in acetonitrile at 85°C, followed by filtration and drying.

8. A method for preparing a rare-earth composite thermosensitive supramolecular gel de-icing material for railways as described in any one of claims 1-7, characterized in that: The method includes the following steps: 1) Preparation of six-carbon bromine-chain columnar aromatic hydrocarbons; 2) Preparation of the main body: Hexacarbon bromine-chain columnar aromatic hydrocarbons, rare earth nano-borides and catalyst powders are mixed in a reaction solvent, heated under reflux and stirred for 36-48 hours, and then separated by phase to obtain the main body; 3) Preparation of alkyl compounds modified with guest bispyridine; 4) The alkyl compound modified with bispyridine as the host and guest are ultrasonically mixed in a solvent and stabilized at 20-30°C for 2-5 minutes. If the sol does not drip down the wall when the vial is removed, it is considered to have formed a gel.

9. An application of the rare earth composite temperature-sensitive supramolecular gel de-icing material for railways as described in any one of claims 1-7, characterized in that: Apply the de-icing material to the surface of the object that needs de-icing.

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