Supramolecular deicing fluid based on ultralong-chain glucose amide and method for preparing same

Abstract

The application discloses a supermolecular self-assembly deicing and anti-icing liquid based on super-long chain glucose amide and a preparation method thereof, which comprises the following components and mass percentages: alcohol 10-72%; deionized water 20-89%; and surfactant 1-8%. The surfactant is at least one of super-long chain glucose amide nonionic surfactants. The application also provides a preparation method of the deicing and anti-icing liquid. The hydrophilic head group of the surfactant synthetic raw material is a derivative of glucose, namely meglumine and glycolamine; and the hydrophobic head group is a by-product in the processing of rapeseed, namely oleic acid, erucic acid and nervonic acid, which are all biomass raw materials. The surfactant has the advantages of low toxicity and environmental friendliness, and does not contain an ionic head group in the molecular structure, and is not corrosive to metals and plastics. The thickening of the deicing and anti-icing liquid depends on the supermolecular self-assembly aggregate of the nonionic surfactant, and due to the weak interaction and reversibility of the supermolecular self-assembly, the risk of reformation of a hydrogel in the take-off process is greatly reduced.

Description

Technical Field

[0001] This invention belongs to the field of de-icing fluids, specifically a supramolecular non-Newtonian de-icing fluid based on an ultra-long chain glucamide nonionic surfactant and its preparation method. Background Technology

[0002] In cold winters, when aircraft transit or spend the night at airports, ice, snow, frost, and other condensations may accumulate on their outer surfaces. These condensations not only increase the aircraft's weight but also roughen its surface, leading to increased drag and reduced lift during flight, seriously affecting flight safety. Therefore, aviation standard manuals in various countries require that aircraft undergo de-icing and anti-icing treatments before takeoff.

[0003] Currently, although various methods for aircraft surface de-icing have been developed, such as mechanical de-icing, hot air de-icing, ultrasonic de-icing, and the use of anti-icing coatings, chemical de-icing and anti-icing, especially non-Newtonian de-icing and anti-icing fluids, remain the most widely used and effective. Non-Newtonian de-icing and anti-icing fluids rapidly thin under the high shear rate of the nozzle, making them easy to spray from the reservoir onto the aircraft surface and perform de-icing. Upon reaching the aircraft surface, the shear rate returns to zero, and the viscosity of the de-icing and anti-icing fluid reaches its maximum value, allowing it to easily coat the aircraft surface and perform its anti-icing function.

[0004] Non-Newtonian de-icing fluids typically consist of polyols, water, thickeners, and rust inhibitors. The thickener is the key component that imparts the liquid's anti-icing and shear-thinning properties. Currently, non-Newtonian de-icing fluids primarily use water-soluble polymers to thicken the alcohol / water mixture. These polymers are usually synthetic polyacrylic acid and its derivatives, non-renewable petroleum-based compounds. After these thickened liquids are sprayed onto the aircraft surface using high-pressure nozzles, de-icing and anti-icing are achieved when the aircraft is stationary. While most of the de-icing fluid is blown away during takeoff, polymer thickeners may remain in concealed areas such as the wings and elevators. These water-soluble polymers readily absorb moisture from the air at high altitudes and low temperatures, forming hydrogels and freezing. This can lead to blockages in control components such as elevators and landing gear during descent, potentially creating safety hazards. Furthermore, the high shear force of the nozzles during spraying can damage the polymer molecular chains, causing degradation and reducing the thickening effect, thus weakening or even eliminating de-icing and anti-icing performance.

[0005] Therefore, developing a low-corrosion, environmentally friendly, polymer-free de-icing fluid made from renewable raw materials has become an urgent problem to be solved in the industry. Reducing or even eliminating the use of polymers and added salts in aircraft de-icing fluids is a key path to effectively solve the above problems. Patent application CN105199671A discloses "An anti-icing fluid thickened by oligomeric cationic surfactants and its preparation method," resulting in an anti-icing fluid thickened by oligomeric cationic surfactants. This anti-icing fluid successfully achieves excellent thickening effect and forms a non-Newtonian anti-icing fluid by adding oligomeric cationic surfactants to a mixed solution of polyols and water. However, in order to promote the self-assembly of these surfactants into worm-like micelles to increase viscosity, a relatively high concentration of inorganic or organic salts is still required. Although this approach is effective, it also brings two main problems: first, it increases the risk of corrosion of the aircraft surface by the anti-icing fluid; second, it may lead to instability of the anti-icing fluid system, affecting the safety of use. Patent application CN106883819A details a de-icing and anti-icing fluid based on ultra-long-chain viscoelastic surfactants and its preparation method. This technology successfully developed an aircraft de-icing and anti-icing fluid that does not require the addition of external polymers and inorganic or organic salts. The thickening properties of ultra-long-chain surfactants simplify traditional formulations and reduce the product's environmental impact and cost. However, this technology still faces challenges in practical applications. First, the preparation process of the surfactants used is complex, involving high-temperature reactions (165℃) and low-temperature crystallization (-20℃), resulting in high energy consumption. Second, some raw materials may have a significant environmental impact, and the high concentration of surfactants further increases the cost of the de-icing and anti-icing fluid. Patent application CN108441171A discloses "An aircraft de-icing and anti-icing fluid thickened with alkylolamine surfactants and its preparation method," obtaining an aircraft de-icing fluid constructed from alkylolamine surfactants. The raw materials used in the synthesis of the surfactants are mainly petroleum-based and lack renewability. Summary of the Invention

[0006] The present invention aims to overcome the defects in the prior art and provide a supramolecular de-icing and anti-icing fluid based on ultra-long chain glucamide and its preparation method, in order to solve the defects of existing de-icing and anti-icing fluids that easily form hydrogels on aircraft surfaces, cause corrosion, and are prone to shear degradation of polymer thickeners.

[0007] The specific principle of the de-icing fluid described in this invention is as follows: Long-chain glucosamide nonionic surfactants self-assemble into worm-like micelles in an alcohol / water mixture through supramolecular interactions such as hydrophobicity. At high surfactant concentrations, these worm-like micelles intertwine to form supramolecular assemblies, exhibiting strong thickening behavior macroscopically, thus functioning as polymer thickeners. However, unlike polymer thickeners, the supramolecular assembly forces are weaker and reversible. During aircraft takeoff, the worm-like micelle supramolecular assemblies are broken up by shear forces. The disintegrated small-molecule surfactants are easily blown off, preventing the accumulation and recrystallization of hydrogels seen with polymer thickeners, thereby significantly reducing the safety hazards associated with de-icing fluids.

[0008] The supramolecular de-icing and anti-icing fluid based on ultra-long chain glucosamide provided by this invention has the following components and their mass percentages: alcohol, 10%–72%; deionized water, 20%–89%; surfactant, 1%–8%. The surfactant is at least one of ultra-long chain glucosyl alkylamide nonionic surfactants having the following general structural formula.

[0009]

[0010] In the formula, R1 in the hydrophilic head group is CH3 or CH2CH3, and the hydrophobic tail chain is characterized by containing an unsaturated bond, and n is 1, 5 or 7.

[0011] The surfactant used in the de-icing fluid is a nonionic surfactant. The hydrophilic head groups in its synthesis are glucose derivatives meglumine and meglumine, while the hydrophobic head groups are byproducts of rapeseed processing such as oleic acid, erucic acid, or nervonic acid—all biomass raw materials. This surfactant not only possesses advantages such as biorenewability, low toxicity, and environmental friendliness, but also does not contain ionic head groups in its molecular structure, is non-corrosive to metals and plastics, and does not contain polymers, greatly reducing the risk of hydration gel formation.

[0012] In the above technical solution of the present invention, the ultra-long chain glucamide nonionic surfactant is preferably at least one of N-octadecyl glucose formamide, N-octadecyl glucose acetamide, N-dodecyl glucose formamide, N-dodecyl glucose acetamide, N-tetracosyl glucose formamide and N-tetracosyl glucose acetamide.

[0013]

[0014] N-Octadecanoformamide (UC) 18 GMe)

[0015]

[0016] N-Octylglucoseacetamide (UC)18 GEt)

[0017]

[0018] N-Dicosylformamide (UC) 22 GMe)

[0019]

[0020] N-Docosylacetamide (UC) 22 GEt)

[0021]

[0022] N-Tyroformamide (UC) 24 GMe)

[0023]

[0024] N-Tetraglucoseacetamide (UC) 24 GEt)

[0025] The above-mentioned ultra-long chain glucamide nonionic surfactant was prepared by the following method:

[0026] Step 1: Add meglumine or meglumine to the solvent, and add the catalyst DMAP or NaF. Mix and activate the amine groups by high shear stirring at 10-30℃ for 20-40 min to obtain solution A; dissolve oleic acid, erucic acid or nervonic acid in the solvent to obtain solution B.

[0027] Step 2: Mix solution A and solution B by high shear mixing, stir and react at 10-30°C for 8-24 hours, remove the organic solvent after the reaction is completed, and obtain crude product of ultra-long chain glucamide nonionic surfactant.

[0028] Step 3: Dissolve the crude product in dichloromethane, and slowly add acetone dropwise at 15-45°C to crystallize, thereby obtaining the purified ultra-long chain glucamide nonionic surfactant.

[0029] The mass ratio of meglumine or meglumine to its solvent in step 1 is 1:(50-60); the mass ratio of meglumine or meglumine to the catalyst is 1:(0.002-0.003).

[0030] In step 1, the molar ratio of oleic acid, erucic acid, or nervonic acid to meglumine or meglumine is 1:(0.8-0.95); the mass ratio of oleic acid, erucic acid, or nervonic acid to its solvent is 1:(20-30).

[0031] The solvent mentioned in step 1 is at least one of methanol, ethanol, ethylene glycol, and propylene glycol.

[0032] The high-shear method described in step 1 involves mixing the solution A at 8000–12000 rpm and 25°C for 30 minutes using a high-shear mixer.

[0033] In step 2, oleic acid, erucic acid, or nervonic acid are dissolved in a solvent and ultrasonically mixed using an ultrasonic mixer to obtain solution B.

[0034] Step 2: Mix solutions A and B using a high-shear mixer at 25°C and 8000–12000 rpm until fully mixed.

[0035] The method for removing organic solvents described in step 2 is vacuum distillation.

[0036] In step 3, the mass ratio of the crude product to dichloromethane is 1:(45-55); the mass ratio of the added acetone to dichloromethane is 1:(0.5-0.8). In the above technical solution of the present invention, the alcohol is at least one of a dialkyl alcohol with 2-5 carbon atoms and a polyalkyl alcohol with 2-5 carbon atoms. The dialkyl alcohol is preferably at least one of ethylene glycol, 1,2-propanediol, and 1,3-propanediol, and the polyalkyl alcohol is preferably glycerol.

[0037] In the above technical solution of the present invention, the preferred mass percentage content of each component is as follows: alcohol 22% to 70%, deionized water 22% to 70%, and ultra-long chain glucamide nonionic surfactant 1% to 8%.

[0038] The present invention provides a method for preparing the supramolecular anti-icing fluid based on ultralong-chain glucamide: Deionized water and alcohol are mixed and stirred until homogeneous, then ultralong-chain glucamide nonionic surfactant is added at room temperature and stirred until completely dissolved. Compared with the prior art, the present invention has the following beneficial effects:

[0039] 1. Reversibility of supramolecular interactions: Supramolecular interactions can form worm-like micelle assemblies with similar viscosity-enhancing properties to polymer solutions. However, since supramolecular interactions are weak and reversible, the strong shear forces during aircraft takeoff can cause surfactant supramolecular assemblies to break apart and be easily blown off, thereby minimizing safety hazards.

[0040] 2. Environmental friendliness: The surfactant used in this invention is derived from renewable biomass raw materials, has low toxicity and is environmentally friendly, reducing negative impacts on the environment.

[0041] 3. Corrosion resistance: The nonionic surfactant used in this invention does not contain ionic head groups, so it is non-corrosive to AMS 5045 carbon steel and AMS 4041 aluminum alloy, ensuring the safe use of the product on aircraft surfaces.

[0042] 4. Not prone to hydrogel formation after takeoff: The anti-icing fluid of this invention does not contain any polymers, thereby effectively reducing the formation of hydrated gels and avoiding potential performance instability.

[0043] 5. Freezing point adjustment: The freezing point of the anti-icing fluid described in this invention can be flexibly adjusted by adjusting the ratio of alcohol to water, and can be as low as -68.6℃. It has a wide range of applications and meets the needs of use in different environments. Attached Figure Description

[0044] Figure 1 The viscosity-shear rate relationship of 8% N-octadecyl glucose formamide in Example 26 in a water / alcohol (ethylene glycol, 1,2-propanediol or 1,3-propanediol) mixed solvent at -20°C is shown in the figure.

[0045] Figure 2 The viscosity-shear rate relationship of 5% N-dosoglucose acetamide in Example 27 in a water / alcohol (ethylene glycol, 1,2-propanediol or 1,3-propanediol) mixed solvent at -20°C is shown in the figure.

[0046] Figure 3 The viscosity-shear rate relationship of 5% N-dodecylglucoseacetamide in Example 28 in a water / ethylene glycol mixed solvent at different temperatures is shown in the graph.

[0047] Figure 4 The viscosity-shear rate relationship of 1% N-doscoglucose acetamide in Example 29 in a water / glycerol mixed solvent at different temperatures is shown in the graph.

[0048] Figure 5 5% of the UC of Example 30 22 GEt H2O / PG (v / v = 50 / 50) mixed solvent (a), 5% UC 24 GMeH2O / PG (v / v = 50 / 50) mixed solvent (b), 5% UC 24 GEt H2O / GLY (v / v = 50 / 50) mixed solvent (c), 5% UC 22 GMe H2O / EG (v / v = 50 / 50) mixed solvent (d), 5% UC 18 GEt H2O / EG (v / v = 50 / 50) mixed solvent (e) and 5% UC 18Antifreeze performance test of aircraft de-icing fluid (f) in GMe H2O / GLY (v / v=50 / 50) mixed solvent (f) at -30℃;

[0049] Figure 6 This is a comparison image of AMS 5045 carbon steel before and after corrosion in H2O / EG (v / v = 50 / 50) solution in Example 31;

[0050] Figure 7 This is a comparison image of AMS 5045 carbon steel before and after corrosion in H2O / PG (v / v = 50 / 50) solution in Example 31;

[0051] Figure 8 This is a comparison image of AMS 5045 carbon steel before and after anti-icing corrosion treatment with 5% polyether surfactant H2O / PG (v / v = 50 / 50) in Example 31.

[0052] Figure 9 Comparison of AMS 5045 carbon steel before and after anti-icing corrosion treatment with 5% CTAB H2O / PG (v / v = 50 / 50) in Example 31;

[0053] Figure 10 AMS 5045 carbon steel of Example 31 - 5% UC 22 Comparison of GEt H2O / PG (v / v=50 / 50) before and after anti-icing fluid corrosion;

[0054] Figure 11 AMS 5045 carbon steel of Example 31 - 5% UC 18 Comparison of GEt H2O / EG (v / v=50 / 50) before and after anti-icing fluid corrosion treatment;

[0055] Figure 12 AMS 5045 carbon steel of Example 31 - 5% UC 22 Comparison of GMe H2O / EG (v / v=50 / 50) before and after anti-icing fluid corrosion removal;

[0056] Figure 13 AMS 4041 aluminum alloy of Example 31 – 5% UC 24 Comparison of GEt H2O / PG (v / v=50 / 50) before and after anti-icing fluid corrosion;

[0057] Figure 14 AMS 4041 aluminum alloy of Example 31 – 5% UC 22 Comparison of GEt H2O / GLY (v / v=50 / 50) before and after anti-icing fluid corrosion. Detailed Implementation

[0058] The present invention will be further illustrated below through embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Those skilled in the art can make some non-essential improvements and adjustments to the present invention based on the above-described invention, and these improvements and adjustments still fall within the scope of protection of the invention.

[0059] In the following examples, all surfactants used were synthesized in-house, and all alcohols were commercially available reagents.

[0060] Example 1

[0061] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0062] Ultrapure water 46.86 Ethylene glycol 52.14 N-Octylglucosamine 1

[0063] Preparation: Add the prescribed amount of ethylene glycol to deionized water at room temperature, then add N-octadecyl glucose formamide and stir until N-octadecyl glucose formamide is completely dissolved to obtain the anti-icing fluid.

[0064] According to the petrochemical industry standard SH / T0090-91, the freezing point of this de-icing fluid is -40.7℃, indicating that the de-icing fluid of the present invention has a low freezing point and can be used in most extremely cold environments.

[0065] Example 2

[0066] In this embodiment, the formulation of the anti-icing fluid is listed in the table below:

[0067] Ultrapure water 47.28 1,2-Propanediol 49.72 N-Octylglucosamine 3

[0068] Preparation: Add the prescribed amount of 1,2-propanediol to deionized water at room temperature, then add N-octadecyl glucose formamide and stir until N-octadecyl glucose formamide is completely dissolved to obtain the anti-icing fluid.

[0069] According to the petrochemical industry standard SH / T0090-91, the freezing point of this de-icing fluid is -36.1℃, indicating that the de-icing fluid of the present invention has a low freezing point and can be used in most extremely cold environments.

[0070] Example 3

[0071] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0072] Ultrapure water 46.22 1,3-Propanediol 45.78 N-Octylglucosamine 8

[0073] Preparation: Add the prescribed amount of 1,3-propanediol to deionized water at room temperature, then add N-octadecyl glucose formamide and stir until N-octadecyl glucose formamide is completely dissolved to obtain the anti-icing fluid.

[0074] According to the petrochemical industry standard SH / T0090-91, the freezing point of this de-icing fluid is -30.0℃, indicating that the de-icing fluid of the present invention has a low freezing point and can be used in most extremely cold environments.

[0075] Example 4

[0076] The formulation of the de-icing fluid described in this embodiment is listed in the table below:

[0077] Ultrapure water 42.06 Glycerol 52.94 N-Octylglucosamine 5

[0078] Preparation: Add the prescribed amount of glycerol to deionized water at room temperature, then add N-octadecyl glucose formamide and stir until N-octadecyl glucose formamide is completely dissolved to obtain the anti-icing fluid.

[0079] According to the petrochemical industry standard SH / T0090-91, the freezing point of this de-icing fluid is -31.9℃, indicating that the de-icing fluid of the present invention has a low freezing point and can be used in most extremely cold environments.

[0080] Example 5

[0081] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0082]

[0083]

[0084] Preparation: Add the prescribed amount of ethylene glycol to deionized water at room temperature, then add N-octadecylglucose acetamide and stir until N-octadecylglucose acetamide is completely dissolved to obtain the anti-icing fluid.

[0085] According to the petrochemical industry standard SH / T0090-91, the freezing point of this de-icing fluid is -41.2℃, indicating that the de-icing fluid of the present invention has a low freezing point and can be used in most extremely cold environments.

[0086] Example 6

[0087] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0088] Ultrapure water 46.90 1,2-Propanediol 49.10 N-Octagalglucoseacetamide 4

[0089] Preparation: At room temperature, add the prescribed amount of 1,2-propanediol to deionized water, then add N-octadecylglucose acetamide, and stir until N-octadecylglucose acetamide is completely dissolved to obtain the anti-icing fluid.

[0090] According to the petrochemical industry standard SH / T0090-91, the freezing point of this de-icing fluid is -36.5℃, indicating that the de-icing fluid of the present invention has a low freezing point and can be used in most extremely cold environments.

[0091] Example 7

[0092] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0093] Ultrapure water 46.15 1,3-Propanediol 47.85 N-Octagalglucoseacetamide 6

[0094] Preparation: Add the prescribed amount of 1,3-propanediol to deionized water at room temperature, then add N-octadecylglucose acetamide and stir until N-octadecylglucose acetamide is completely dissolved to obtain the anti-icing fluid.

[0095] According to the petrochemical industry standard SH / T0090-91, the freezing point of this de-icing fluid is -29.9℃, indicating that the de-icing fluid of the present invention has a low freezing point and can be used in most extremely cold environments.

[0096] Example 8

[0097] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0098] Ultrapure water 40.67 Glycerol 51.33 N-Octagalglucoseacetamide 8

[0099] Preparation: Add the prescribed amount of glycerol to deionized water at room temperature, then add N-octadecylglucose acetamide and stir until N-octadecylglucose acetamide is completely dissolved to obtain the anti-icing fluid.

[0100] According to the petrochemical industry standard SH / T0090-91, the freezing point of this de-icing fluid is -32.0℃, indicating that the de-icing fluid of the present invention has a low freezing point and can be used in most extremely cold environments.

[0101] Example 9

[0102] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0103] Ultrapure water 46.86 Ethylene glycol 52.14 N-Dicosylformamide 1

[0104] Preparation: Add the prescribed amount of ethylene glycol to deionized water at room temperature, then add N-doscoglucose formamide and stir until N-doscoglucose formamide is completely dissolved to obtain the anti-icing fluid.

[0105] According to the petrochemical industry standard SH / T0090-91, the freezing point of this de-icing fluid is -41.7℃, indicating that the de-icing fluid of the present invention has a low freezing point and can be used in most extremely cold environments.

[0106] Example 10

[0107] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0108] Ultrapure water 47.28 1,2-Propanediol 49.72 N-Dicosylformamide 3

[0109] Preparation: Add the prescribed amount of 1,2-propanediol to deionized water at room temperature, then add N-dosoglucose formamide and stir until N-dosoglucose formamide is completely dissolved to obtain the anti-icing fluid.

[0110] According to the petrochemical industry standard SH / T0090-91, the freezing point of this de-icing fluid is -36.1℃, indicating that the de-icing fluid of the present invention has a low freezing point and can be used in most extremely cold environments.

[0111] Example 11

[0112] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0113] Ultrapure water 47.53 1,3-Propanediol 48.47 N-Dicosylformamide 4

[0114] Preparation: Add the prescribed amount of 1,3-propanediol to deionized water at room temperature, then add N-dosoglucose formamide and stir until N-dosoglucose formamide is completely dissolved to obtain the anti-icing fluid.

[0115] According to the petrochemical industry standard SH / T0090-91, the freezing point of this de-icing fluid is -28.9℃, indicating that the de-icing fluid of the present invention has a low freezing point and can be used in most extremely cold environments.

[0116] Example 12

[0117] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0118] Ultrapure water 42.06 Glycerol 52.94 N-Dicosylformamide 5

[0119] Preparation: Add the prescribed amount of glycerol to deionized water at room temperature, then add N-doscoglucose formamide and stir until N-doscoglucose formamide is completely dissolved to obtain the anti-icing fluid.

[0120] According to the petrochemical industry standard SH / T0090-91, the freezing point of this de-icing fluid is -31.8℃, indicating that the de-icing fluid of the present invention has a low freezing point and can be used in most extremely cold environments.

[0121] Example 13

[0122] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0123] Ultrapure water 46.86 Ethylene glycol 52.14 N-Dicosylacetamide 1

[0124] Preparation: Add the prescribed amount of ethylene glycol to deionized water at room temperature, then add N-dosoglucose acetamide and stir until N-dosoglucose acetamide is completely dissolved to obtain the anti-icing fluid.

[0125] According to the petrochemical industry standard SH / T0090-91, the freezing point of this de-icing fluid is -40.9℃, indicating that the de-icing fluid of the present invention has a low freezing point and can be used in most extremely cold environments.

[0126] Example 14

[0127] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0128] Ultrapure water 47.28 1,2-Propanediol 49.72 N-Dicosylacetamide 3

[0129] Preparation: At room temperature, add the prescribed amount of 1,2-propanediol to deionized water, then add N-dosoglucose acetamide, and stir until N-dosoglucose acetamide is completely dissolved to obtain the anti-icing fluid.

[0130] According to the petrochemical industry standard SH / T0090-91, the freezing point of this de-icing fluid is -36.4℃, indicating that the de-icing fluid of the present invention has a low freezing point and can be used in most extremely cold environments.

[0131] Example 15

[0132] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0133] Ultrapure water 47.53 1,3-Propanediol 48.47 N-Dicosylacetamide 4

[0134] Preparation: At room temperature, add the prescribed amount of 1,3-propanediol to deionized water, then add N-dosoglucoseacetamide, and stir until N-dosoglucoseacetamide is completely dissolved to obtain the anti-icing fluid.

[0135] According to the petrochemical industry standard SH / T0090-91, the freezing point of this de-icing fluid is -30.2℃, indicating that the de-icing fluid of the present invention has a low freezing point and can be used in most extremely cold environments.

[0136] Example 16

[0137] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0138] Ultrapure water 42.06 Glycerol 52.94 N-Dicosylacetamide 5

[0139] Preparation: Add the prescribed amount of glycerol to deionized water at room temperature, then add N-dosoglucose acetamide and stir until N-dosoglucose acetamide is completely dissolved to obtain the anti-icing fluid.

[0140] According to the petrochemical industry standard SH / T0090-91, the freezing point of this de-icing fluid is -32.6℃, indicating that the de-icing fluid of the present invention has a low freezing point and can be used in most extremely cold environments.

[0141] Example 17

[0142] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0143] Ultrapure water 46.86 Ethylene glycol 52.14 N-Tyroformamide 1

[0144] Preparation: Add the prescribed amount of ethylene glycol to deionized water at room temperature, then add N-tetracosamide and stir until N-tetracosamide is completely dissolved to obtain the anti-icing fluid.

[0145] According to the petrochemical industry standard SH / T0090-91, the freezing point of this de-icing fluid is -42.1℃, indicating that the de-icing fluid of the present invention has a low freezing point and can be used in most extremely cold environments.

[0146] Example 18

[0147] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0148]

[0149]

[0150] Preparation: Add the prescribed amount of 1,2-propanediol to deionized water at room temperature, then add N-tetracosamide and stir until N-tetracosamide is completely dissolved to obtain the anti-icing fluid.

[0151] According to the petrochemical industry standard SH / T0090-91, the freezing point of this de-icing fluid is -36.2℃, indicating that the de-icing fluid of the present invention has a low freezing point and can be used in most extremely cold environments.

[0152] Example 19

[0153] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0154] Ultrapure water 47.53 1,3-Propanediol 48.47 N-Tyroformamide 4

[0155] Preparation: Add the prescribed amount of 1,3-propanediol to deionized water at room temperature, then add N-tetracosamide and stir until N-tetracosamide is completely dissolved to obtain the anti-icing fluid.

[0156] According to the petrochemical industry standard SH / T0090-91, the freezing point of this de-icing fluid is -29.1℃, indicating that the de-icing fluid of the present invention has a low freezing point and can be used in most extremely cold environments.

[0157] Example 20

[0158] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0159] Ultrapure water 42.06 Glycerol 52.94 N-Tyroformamide 5

[0160] Preparation: Add the prescribed amount of glycerol to deionized water at room temperature, then add N-tetracosamide and stir until N-tetracosamide is completely dissolved to obtain the anti-icing fluid.

[0161] According to the petrochemical industry standard SH / T0090-91, the freezing point of this de-icing fluid is -32.1℃, indicating that the de-icing fluid of the present invention has a low freezing point and can be used in most extremely cold environments.

[0162] Example 21

[0163] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0164] Ultrapure water 46.86 Ethylene glycol 52.14 N-Tetraglucoseacetamide 1

[0165] Preparation: Add the prescribed amount of ethylene glycol to deionized water at room temperature, then add N-tetracosylglucose acetamide and stir until N-tetracosylglucose acetamide is completely dissolved to obtain the anti-icing fluid.

[0166] According to the petrochemical industry standard SH / T0090-91, the freezing point of this de-icing fluid is -42.0℃, indicating that the de-icing fluid of the present invention has a low freezing point and can be used in most extremely cold environments.

[0167] Example 22

[0168] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0169] Ultrapure water 47.28 1,2-Propanediol 49.72 N-Tetraglucoseacetamide 3

[0170] Preparation: At room temperature, add the prescribed amount of 1,2-propanediol to deionized water, then add N-tetracosylglucose acetamide, and stir until N-tetracosylglucose acetamide is completely dissolved to obtain the anti-icing fluid.

[0171] According to the petrochemical industry standard SH / T0090-91, the freezing point of this de-icing fluid is -36.7℃, indicating that the de-icing fluid of the present invention has a low freezing point and can be used in most extremely cold environments.

[0172] Example 23

[0173] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0174] Ultrapure water 47.53 1,3-Propanediol 48.47 N-Tetraglucoseacetamide 4

[0175] Preparation: At room temperature, add the prescribed amount of 1,3-propanediol to deionized water, then add N-tetracosylglucose acetamide, and stir until N-tetracosylglucose acetamide is completely dissolved to obtain the anti-icing fluid.

[0176] According to the petrochemical industry standard SH / T0090-91, the freezing point of this de-icing fluid is -30.1°C, indicating that the de-icing fluid of this invention has a low freezing point and can be used in most extremely cold environments.

[0177] Example 24

[0178] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0179] Ultrapure water 42.06 Glycerol 52.94 N-Tetraglucoseacetamide 5

[0180] Preparation: Add the prescribed amount of glycerol to deionized water at room temperature, then add N-tetracosylglucose acetamide and stir until N-tetracosylglucose acetamide is completely dissolved to obtain the anti-icing fluid.

[0181] According to the petrochemical industry standard SH / T0090-91, the freezing point of this de-icing fluid is -32.6℃, indicating that the de-icing fluid of the present invention has a low freezing point and can be used in most extremely cold environments.

[0182] Example 25

[0183] This embodiment includes five types of anti-icing fluids, and the formulations of each anti-icing fluid are listed in the table below:

[0184]

[0185] Preparation: At room temperature, different amounts of ethylene glycol were added to deionized water, and then different amounts of N-dosoglucose acetamide were added. The mixture was stirred until the N-dosoglucose acetamide was completely dissolved to obtain the anti-icing fluid.

[0186] According to the petrochemical industry standard SH / T 0090-91, the freezing points of the above five anti-icing fluids were measured to be -9.1℃, -24.7℃, -41.7℃, -54.3℃, and -68.6℃, respectively. This indicates that the freezing point of the anti-icing fluid of the present invention is adjustable and can meet the needs of use in most environments.

[0187] Example 26

[0188] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0189]

[0190]

[0191] Preparation: At room temperature, add the prescribed amounts of ethylene glycol, 1,2-propanediol, or 1,3-propanediol to deionized water and mix thoroughly. Then add the prescribed amounts of N-dodecoglucoseacetamide and stir until completely dissolved to obtain three anti-icing solutions.

[0192] The relationship between the apparent viscosity and shear rate of the de-icing fluid was tested using a rotational rheometer (Anto Paar, MCR 302) at a temperature of -20°C. The results are as follows: Figure 1 As shown. By Figure 1 It can be seen that at low shear rates, the de-icing fluid exhibits high apparent viscosity, and as the shear rate increases, the viscosity decreases significantly, which shows obvious shear-thinning characteristics, meeting the rheological performance requirements of non-Newtonian fluid de-icing fluid.

[0193] Example 27

[0194] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0195]

[0196] Preparation: At room temperature, add the prescribed amounts of ethylene glycol, 1,2-propanediol, or 1,3-propanediol to deionized water and mix thoroughly. Then add the prescribed amounts of N-dodecoglucoseacetamide and stir until completely dissolved to obtain three anti-icing solutions.

[0197] The relationship between the apparent viscosity and shear rate of the de-icing fluid was tested using a rotational rheometer (Anto Paar, MCR 302) at a temperature of -20°C. The results are as follows: Figure 2 As shown. By Figure 2 It can be seen that at low shear rates, the de-icing fluid exhibits high apparent viscosity, and as the shear rate increases, the viscosity decreases significantly, which shows obvious shear-thinning characteristics, meeting the rheological performance requirements of non-Newtonian fluid de-icing fluid.

[0198] Example 28

[0199] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0200] Deionized water 44.92 Ethylene glycol 50.08 N-Tyroformamide 5

[0201] Preparation: Add the prescribed amount of ethylene glycol to deionized water at room temperature and stir thoroughly until homogeneous. Then add the prescribed amount of N-tetracosamide and stir until completely dissolved to obtain the anti-icing solution.

[0202] The relationship between the apparent viscosity and shear rate of the de-icing fluid was tested using a rotational rheometer (Anto Paar, MCR 302) at temperatures of 0℃, -5℃, -10℃, -15℃, -17℃, and -20℃. The results are as follows: Figure 3 As shown. By Figure 3 It can be seen that at low shear rates, the de-icing fluid exhibits high apparent viscosity, and as the shear rate increases, the viscosity decreases significantly, which shows obvious shear-thinning characteristics, meeting the rheological performance requirements of non-Newtonian fluid de-icing fluid.

[0203] Example 29

[0204] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0205] Deionized water 42.06 Glycerol 52.94 N-Tyrodactylglucacetamide 5

[0206] Preparation: Add the prescribed amount of glycerol to deionized water at room temperature and stir thoroughly until homogeneous. Then add the prescribed amount of N-tetracosamide and stir until completely dissolved to obtain the anti-icing solution.

[0207] The relationship between the apparent viscosity and shear rate of the de-icing fluid was tested using a rotational rheometer (Anto Paar, MCR 302) at temperatures of 0℃, -5℃, -10℃, -15℃, -17℃, and -20℃. The results are as follows: Figure 3 As shown. By Figure 3 It can be seen that at low shear rates, the de-icing fluid exhibits high apparent viscosity, and as the shear rate increases, the viscosity decreases significantly, which shows obvious shear-thinning characteristics, meeting the rheological performance requirements of non-Newtonian fluid de-icing fluid.

[0208] Example 30

[0209] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0210]

[0211] Preparation: At room temperature, add the prescribed amounts of ethylene glycol, 1,2-propanediol, or glycerol to deionized water and mix thoroughly. Then add the prescribed amounts of N-octadecylglucoseformamide, N-dodecylglucoseacetamide, N-dodecylglucoseformamide, N-dodecylglucoseacetamide, N-tetracosylglucoseformamide, or N-tetracosylglucoseacetamide, and stir until completely dissolved to obtain six anti-icing solutions.

[0212] Antifreeze performance test: The antifreeze performance of six de-icing fluids was tested using a cryogenic liquid nitrogen cooling-heating stage (Linkam, HFS600E-PB4). The specific method was as follows: ultrapure water and de-icing fluid were sprayed onto the upper and lower sides of a glass slide, respectively, and the slide was placed on the platinum thermally conductive stage of the cryogenic liquid nitrogen cooling-heating stage and stabilized at -30°C for 4 hours. The results were obtained by observing the freezing conditions. Figure 5 As shown. According to Figure 5 The results showed that the side sprayed with water froze, while the side sprayed with the six different anti-icing fluids remained unfrozen. This indicates that the anti-icing fluid composed of six surfactants exhibits excellent antifreeze properties under extreme low-temperature conditions.

[0213] Example 31

[0214] In this embodiment, the formula of the anti-icing fluid is listed in the table below:

[0215]

[0216]

[0217] At room temperature, first add the required amount of ultrapure water (42.06 to 49.11 parts depending on the specific formulation) to a suitable container. Then, according to the formulation requirements, add the appropriate amount of alcohol solvent (such as ethylene glycol (EG), 1,2-propanediol (PG), or glycerol (GLY)). Ensure the alcohol solvent and water are thoroughly mixed. Next, add the surfactant specified in the formulation (such as polyether surfactant, hexadecyltrimethylammonium bromide (CTAB), N-dodecylglucose acetamide, etc.) and continue stirring until the surfactant is completely dissolved in the solution. During stirring, ensure the solution is homogeneous and the surfactant is completely dispersed, avoiding undissolved particles or precipitates. The solution for each formulation should be accurately proportioned and stirred according to the ratios listed in the table to ensure the total mass of the final solution is 100 parts.

[0218] The corrosivity of the above nine anti-icing fluids was determined according to GB / T 20857-2012. The test results are as follows:

[0219]

[0220]

[0221] Anti-icing fluid No. 4 (5wt.% CTAB H2O / PG, v / v = 50 / 50) showed a mass change of 0.892 mg / cm³ before and after treatment. 2 The corrosion rate of the anti-icing fluid on AMS 5045 carbon steel before and after the test, exceeding the national standard, was less than 0.8 mg / cm³. 2 The mass of AMS 4041 aluminum alloy before and after corrosion testing was less than 0.3 mg / cm³. 2 Compared with blank samples 1 and 2, nonionic surfactants (commercial polyether surfactants and ultra-long-chain glucamide nonionic surfactants such as UC) showed improved performance. 18 GEt,UC 22 GMe,UC 22 GEt,UC 24 Both GEt and other nonionic surfactants have certain anti-corrosion properties, and the anti-corrosion performance of ultra-long chain glucamide nonionic surfactants is better than that of commercial polyether surfactants.

[0222] The Fe and Al content in the de-icing fluid after corrosion of AMS 4041 aluminum alloy and AMS 5045 carbon steel was analyzed using X-ray fluorescence spectrometry (XRF). The results are as follows:

[0223]

[0224]

[0225] Sample preparation method: First, take 50 mL of the de-icing solution after corrosion and evaporate it using a rotary evaporator at 80 °C until the solvent is completely evaporated, obtaining a dry solid. Next, add the solid to 5 mL of ethanol solvent and sonicate to ensure uniform dispersion. Then, evenly coat the dispersion onto filter paper with a diameter of 52 mm, ensuring a consistent solid layer thickness. Place the filter paper in a vacuum drying oven at 60 °C, controlling the vacuum degree at 100–200 Pa, and dry for 12–16 hours to ensure complete solvent evaporation and complete sample drying. After drying, remove the filter paper and cool it at room temperature to avoid the influence of hot air on the sample. If particles aggregate, they can be gently scraped off or redispersed. Finally, perform full elemental scanning analysis of the sample using X-ray fluorescence spectrometry (XRF).

[0226] Corrosion Resistance Analysis: For AMS 5045 carbon steel, blank filter paper was used as a control sample, and its corrosion resistance was used as the benchmark. The results showed that De-icing fluid No. 4 (5wt.% CTAB H2O / PG (v / v = 50 / 50)) performed the worst, with the highest Fe content at 3120 mg / L, indicating the weakest corrosion resistance. Following closely were De-icing fluid No. 2 (H2O / PG (v / v = 50 / 50)) and De-icing fluid No. 3 (5wt.% commercial polyether surfactant H2O / PG (v / v = 50 / 50)), with Fe contents of 617 mg / L and 527 mg / L, respectively. In contrast, the De-icing fluids prepared using ultra-long-chain glucamide nonionic surfactants (Nos. 5, 6, and 7) performed excellently, with Fe contents of 31 mg / L (No. 5), 22 mg / L (No. 6), and 34 mg / L (No. 7), respectively, showing strong corrosion resistance. For AMS 4041 aluminum alloy, the de-icing fluids prepared using ultra-long-chain glucamide nonionic surfactants (No. 8 and No. 9) exhibited the best corrosion resistance. Fe contents of 27 mg / L and 27 mg / L, and Al contents of 20 mg / L and 26 mg / L, respectively, all showed good corrosion resistance. Finally, a comparative analysis was conducted on the pre- and post-corrosion photographs and micrographs of the nine de-icing fluids on AMS 5045 carbon steel and AMS 4041 aluminum alloy (see...). Figures 6-14 It was observed that anti-icing fluids No. 4 (5 wt.% CTAB H2O / PG (v / v = 50 / 50)), No. 2 (H2O / PG (v / v = 50 / 50)), and No. 3 (5 wt.% commercial polyether surfactant H2O / PG (v / v = 50 / 50)) caused significant corrosion marks on the surface of AMS 5045 carbon steel. In contrast, anti-icing fluids prepared using ultra-long-chain glucamide nonionic surfactants (Nos. 5, 6, and 7) did not cause corrosion to AMS 5045 carbon steel. Furthermore, anti-icing fluids prepared using ultra-long-chain glucamide nonionic surfactants (Nos. 8 and 9) showed no corrosive effect on AMS 4041 aluminum alloy.

Claims

1. A supramolecular de-icing and anti-icing fluid based on ultralong-chain glucosamide, characterized in that, Its components and the mass percentages of each component are as follows: alcohol 10%~72%; deionized water 20%~89%; surfactant 1%~8%; the surfactant is at least one of the following ultra-long chain glucosamide nonionic surfactants having the following general structural formula: ， In the structural formula, R1 is CH3 or CH2CH3, and n is 1, 5 or 7; The alcohol is at least one of ethylene glycol, 1,2-propanediol, and 1,3-propanediol, and the polyalkyl alcohol is glycerol.

2. The supramolecular de-icing and anti-icing fluid based on ultralong-chain glucosamide according to claim 1, characterized in that, The ultra-long chain glucamide nonionic surfactant is at least one of N-octadecyl glucose formamide, N-octadecyl glucose acetamide, N-dodecyl glucose formamide, N-dodecyl glucose acetamide, N-tetracosyl glucose formamide, and N-tetracosyl glucose acetamide.

3. The method for preparing supramolecular de-icing fluid based on ultralong-chain glucosamide according to claim 1 or 2, characterized in that, Deionized water and alcohol were mixed and stirred to form a mixed solution. Long-chain glucosamide nonionic surfactant was added to the resulting mixed solution and stirred until it was completely dissolved.

Images