Aircraft de-icing and anti-icing fluid thickened by super-long-chain polyoxyethylene ether surfactant and preparation method of aircraft de-icing and anti-icing fluid

Abstract

The invention discloses airplane deicing and anti-icing fluid thickened by a super-long chain (the number of carbon atoms in a hydrophobic tail chain is greater than or equal to 18) polyoxyethylene ether surfactant and a preparation method of the airplane deicing and anti-icing fluid. The airplane deicing and anti-icing fluid thickened by the super-long-chain polyoxyethylene ether surfactant comprises the following components in percentage by mass: 40%-69% of alcohol, 30%-59% of deionized water and 0.2%-2.0% of a surfactant, the surfactant is docosanoic acid polyoxyethylene monomethyl ether ester (C22-350), and the super-long-chain polyoxyethylene ether surfactant is sodium dodecyl benzene sulfonate. The de-icing and anti-icing fluid which is good in de-icing and anti-icing performance and environmentally friendly is obtained, and on the premise that the de-icing and anti-icing effect is guaranteed, the problems that a polymer-based de-icing and anti-icing fluid is prone to being rehydrated on the surface of an airplane to form hydrated gel, and the surface of the airplane is corroded by a surface active agent or other additives are solved.

Description

Technical Field

[0001] The invention belongs to the field of deicing and anti-icing of object surfaces, and in particular relates to a deicing and anti-icing fluid and a preparation method thereof. Background Art

[0002] When an aircraft stops or spends the night at a high-altitude airport, ice, frost or snow is very likely to accumulate on the leading edges of its wings and tail, around the engine air intakes, and on various probes and antennas. This not only increases the weight of the aircraft, but also makes the aircraft surface rough, changes its flatness and shape, destroys the smooth flow of air around the wing surface, causes the aircraft's lift-to-drag ratio and lift coefficient to decrease, makes the flight attitude difficult to control, changes in flight characteristics, and may even cause the aircraft to stall and cause serious flight accidents. Therefore, de-icing is a key link in ensuring the safe flight of aircraft.

[0003] The most effective ground deicing method at present is to use non-Newtonian aircraft deicing fluid. The international aviation industry generally adopts water-soluble polymer thickeners as rheology modifiers to be added to alcohol-water mixed solvents to form shear-thinning non-Newtonian fluids for aircraft deicing. After the deicing fluid is sprayed on the aircraft surface, it can not only remove the ice accumulation on the aircraft surface, but also inhibit the icing of the aircraft surface. Most of these deicing fluids sprayed on the aircraft surface will be blown off during the takeoff process of the aircraft, but there will still be a small amount of residue in some more hidden places (such as wings, elevators, etc.). These residual polymers are very likely to form hydrated gels after encountering water vapor in the air, blocking the elevators and causing hidden dangers to flight safety.

[0004] Avoiding the use of polymers in aircraft de-icing and anti-icing fluids is an effective solution to the above problems. The patent application with publication number CN112094624A discloses "Surfactant / hydrophobically associating polymer viscoelastic fluid with de-icing and anti-icing functions and its preparation method", and obtains a de-icing and anti-icing viscoelastic fluid based on a surfactant and a hydrophobically associating polymer. Although the amount of polymer used has been reduced, the small amount of polymer present may still cause the problem of hydrated gel caused by the polymer thickener. The patent application with publication number CN105199671A discloses "An anti-icing fluid thickened by oligomeric cationic surfactants and its preparation method", and obtains a de-icing and anti-icing fluid based on oligomeric cationic surfactants. However, the surfactant used needs to be added with inorganic salts or organic salts to obtain a non-Newtonian de-icing and anti-icing fluid. The addition of salt greatly increases the risk of corrosion to the aircraft surface, affecting the safety of use. The patent application with publication number CN106883819A discloses "a de-icing fluid based on ultra-long chain viscoelastic surfactants and a preparation method thereof", and obtains an aircraft de-icing fluid that uses ultra-long chain surfactants to increase viscosity. However, the preparation process of the surfactant used is complicated, and the concentration used is still relatively high, which increases the cost of the de-icing fluid. Summary of the invention

[0005] The purpose of the present invention is to provide an aircraft de-icing fluid thickened with an ultra-long chain (the number of carbon atoms in the hydrophobic tail chain is ≥18) polyoxyethylene ether surfactant and a preparation method thereof, so as to obtain a de-icing fluid with good de-icing performance and relatively environmentally friendly, and to solve the problems that the polymer-based de-icing fluid is easy to rehydrate on the aircraft surface to form a hydrated gel, and the surfactant itself or other additives cause corrosion to the aircraft surface while ensuring the de-icing and anti-icing effect.

[0006] The aircraft deicing fluid thickened with a super-long-chain polyoxyethylene ether surfactant provided by the present invention comprises the following components and the mass percentage of each component: 40% to 69% of alcohol, 30% to 59% of deionized water, and 0.2% to 2.0% of a surfactant, wherein the surfactant is polyoxyethylene monomethyl ether behenate (C 22 -350), the structural formula is as follows:

[0007]

[0008] In the above technical solution of the present invention, further, the alcohol is a dihydric alkyl alcohol having 2 to 5 carbon atoms; the dihydric alkyl alcohol is preferably 1,2-propylene glycol.

[0009] In the above technical solution of the present invention, further, the aircraft de-icing fluid thickened with the polyoxyethylene ether surfactant has its components and the mass percentage of each component preferably as follows: 48% to 49% alcohol, 49% to 51% deionized water, and 0.3% to 2.0% surfactant.

[0010] The preparation method of the aircraft deicing and anti-icing fluid thickened with a super-long chain polyoxyethylene ether surfactant provided by the present invention is as follows:

[0011] The preparation method of the aircraft deicing and anti-icing fluid thickened with the polyoxyethylene ether surfactant provided by the present invention is as follows: deionized water and alcohol are mixed and stirred evenly, and C 22 -350 surfactant, heat and stir until it is completely dissolved.

[0012] In the above technical solution of the present invention, further, the alcohol is a dihydric alkyl alcohol having 2 to 5 carbon atoms, preferably 1,2-propylene glycol.

[0013] The present invention also provides the use of the ultra-long chain polyoxyethylene ether in aircraft deicing fluid.

[0014] Compared with the prior art, the present invention has the following beneficial effects:

[0015] 1. The ultra-long chain polyoxyethylene ether surfactant of the present invention is soluble in an alcohol / water mixed solvent for viscosity enhancement, but is insoluble in water, and can replace a polymer as a thickener for use in deicing fluids, thereby solving the problem of residual polymers absorbing water again to form hydrated gels that block elevators and cause safety hazards.

[0016] 2. The polyoxyethylene ether surfactant of the present invention uses an ultra-long carbon chain as a hydrophobic tail chain, so that the surfactant has the effects of increasing viscosity and shear thinning at a relatively low concentration, and has a cost advantage.

[0017] 3. The polyoxyethylene ether surfactant of the present invention can form a viscoelastic fluid as a single component, does not contain other organic salts or inorganic salts, and the surfactant itself does not ionize and has little corrosiveness to the surface of objects. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 It is 0.3wt.% of C in Example 2 22 Viscosity-shear rate relationship of -350 in water / 1,2-propylene glycol at different temperatures.

[0019] Figure 2 0.4 wt.% of C in Example 3 22 Viscosity-shear rate relationship of -350 in water / 1,2-propylene glycol at different temperatures.

[0020] Figure 3 0.5 wt.% of C in Example 4 22 Viscosity-shear rate relationship of -350 in water / 1,2-propylene glycol at different temperatures.

[0021] Figure 4 is 1.0wt.% of C in Example 5 22 Viscosity-shear rate relationship of -350 in water / 1,2-propylene glycol at different temperatures.

[0022] Figure 5 2.0 wt.% of C in Example 6 22 Viscosity-shear rate relationship of -350 in water / 1,2-propylene glycol at different temperatures.

[0023] Figure 6 0.5 wt.% of C in Example 7 22 Figure 2. Anti-icing effect of de-icing fluid composed of -350 and water / 1,2-propylene glycol on aluminum alloy substrate.

[0024] Figure 7 The 0.5wt.% C 22The results of the compatibility test of the de-icing fluid composed of -350 and water / 1,2-propylene glycol with the aircraft fuselage material. (a) is a physical comparison photo of the aluminum alloy test piece before and after being fully immersed in the de-icing fluid, (b) and (c) are microscopic morphology photos of the aluminum alloy test piece before and after being immersed in the de-icing fluid.

[0025] Figure 8 It is 0.5wt.% of C in Example 9 22 -350 aqueous solution in the range of 0 ~ 90 ℃ solution permeability changes with temperature. DETAILED DESCRIPTION

[0026] The aircraft de-icing fluid thickened with a super-long chain polyoxyethylene ether surfactant and the preparation method thereof are further described below by way of examples. The following examples are only used to more clearly illustrate the technical solution of the present invention and are not intended to limit the scope of protection of the present invention. In the following examples, the surfactant is a laboratory-made C 22 -350. In the above technical solution of the present invention, the ultra-long chain polyoxyethylene ether surfactant is prepared by the following method:

[0027] (1) 5.00 g of a molecular weight of 350 g·mol -1 The polyoxyethylene monomethyl ether MPEG was added to 250 g of dichloromethane solution and stirred in a 25°C water bath until the compound was dissolved.

[0028] (2) Weigh 0.35 g of catalyst 4-dimethylaminopyridine and 0.84 g of dimethylaminopyridine toluenesulfonate, add them to the above reaction solution, and stir until the catalyst is completely dissolved.

[0029] (3) Then add 5.80 g of docosanoic acid C 22 FA, stirring to dissolve.

[0030] (4) Add 5.88 g of condensing agent N,N'-dicyclohexylcarboximide to the above solution and continue stirring to carry out esterification reaction. The reaction stops after 48 hours.

[0031] (5) After the reaction is completed, the product is evaporated and then filtered out with a pinhole filter to remove the condensing agent to obtain a crude product.

[0032] (6) The crude product was separated and purified by column chromatography, and finally vacuum dried to obtain surfactant polyoxyethylene monomethyl ether behenate C 22 -350.

[0033] Example 1

[0034] In this embodiment, the formula of the de-icing fluid is as follows:

[0035]

[0036] Preparation: Add the formulated amount of 1,2-propylene glycol to deionized water at room temperature and stir thoroughly to mix. Then add different formulated amounts of C 22 -350, heat to 50℃ and stir until the surfactant is completely dissolved to obtain the deicing fluid.

[0037] The freezing points of the deicing and anti-icing fluid measured according to the petrochemical industry standard SH / T 0090-91 of the People's Republic of China are -37.2°C, -37.0°C, -37.1°C, -36.9°C, and -37.1°C, respectively, indicating that the deicing and anti-icing fluid of the present invention has a lower freezing point and can be used in most extremely cold environments.

[0038] Example 2

[0039] In this embodiment, the formula of the de-icing fluid is as follows:

[0040] Components Mass percentage (wt.%) Deionized water 50.78 Alcohol: 1,2-propylene glycol 48.92 <![CDATA[Surfactant: C 22 -350]]> 0.30

[0041] Preparation: Add the formulated amount of 1,2-propylene glycol to deionized water at room temperature and stir thoroughly to mix. Then add the above formulated amount of C 22 -350, 50℃ stirring until it is completely dissolved to obtain deicing fluid.

[0042] The relationship between the apparent viscosity and shear rate of the de-icing fluid was tested using a rotational rheometer (Anto Paar, MCR 302). The test temperatures were -20°C, -10°C, 0°C, and 10°C. The results are as follows: Figure 1 As shown. Figure 1 It can be seen that at low shear rates, the de-icing fluid exhibits a higher apparent viscosity. As the shear rate increases, the viscosity decreases significantly, that is, it exhibits obvious shear thinning characteristics, which meets the rheological performance requirements of non-Newtonian fluid de-icing fluid. In addition, the maximum shear viscosity of the de-icing fluid changes with temperature, and the viscosity is the largest at low temperatures, which is suitable for low temperature environments.

[0043] Example 3

[0044] In this embodiment, the formula of the de-icing fluid is as follows:

[0045] Components Mass percentage (wt.%) Deionized water 50.73 Alcohol: 1,2-propylene glycol 48.87 <![CDATA[Surfactant: C 22 -350]]> 0.40

[0046] Preparation: Add the formulated amount of 1,2-propylene glycol to deionized water at room temperature and stir thoroughly to mix. Then add the above formulated amount of C 22 -350, 50℃ stirring until it is completely dissolved to obtain deicing fluid.

[0047] The relationship between the apparent viscosity and shear rate of the de-icing fluid was tested using a rotational rheometer (Anto Paar, MCR 302). The test temperatures were -20°C, -10°C, 0°C, and 10°C. The results are as follows: Figure 2 As shown. Figure 2 It can be seen that at low shear rates, the de-icing fluid exhibits a higher apparent viscosity. As the shear rate increases, the viscosity decreases significantly, that is, it exhibits obvious shear thinning characteristics, which meets the rheological performance requirements of non-Newtonian fluid de-icing fluid. In addition, the maximum shear viscosity of the de-icing fluid changes with temperature, and the viscosity is the largest at low temperatures, which is suitable for low temperature environments.

[0048] Example 4

[0049] In this embodiment, the formula of the de-icing fluid is as follows:

[0050] Components Mass percentage (wt.%) Deionized water 50.68 Alcohol: 1,2-propylene glycol 48.82 <![CDATA[Surfactant: C 22 -350]]> 0.50

[0051] Preparation: Add the formulated amount of 1,2-propylene glycol to deionized water at room temperature and stir thoroughly to mix. Then add the above formulated amount of C 22 -350, 50℃ stirring until it is completely dissolved to obtain deicing fluid.

[0052] The relationship between the apparent viscosity and shear rate of the de-icing fluid was tested using a rotational rheometer (Anto Paar, MCR 302). The test temperatures were -20°C, -10°C, 0°C, and 10°C. The results are as follows: Figure 3 As shown. Figure 3 It can be seen that at low shear rates, the de-icing fluid exhibits a higher apparent viscosity. As the shear rate increases, the viscosity decreases significantly, that is, it exhibits obvious shear thinning characteristics, which meets the rheological performance requirements of non-Newtonian fluid de-icing fluid. In addition, the maximum shear viscosity of the de-icing fluid changes with temperature, and the viscosity is the largest at low temperatures, which is suitable for low temperature environments.

[0053] Example 5

[0054] In this embodiment, the formula of the de-icing fluid is as follows:

[0055] Components Mass percentage (wt.%) Deionized water 50.43 Alcohol: 1,2-propylene glycol 48.57 <![CDATA[Surfactant: C 22 -350]]> 1.00

[0056] Preparation: Add the formulated amount of 1,2-propylene glycol to deionized water at room temperature and stir thoroughly to mix. Then add the above formulated amount of C 22 -350, 50℃ stirring until it is completely dissolved to obtain deicing fluid.

[0057] The relationship between the apparent viscosity and shear rate of the de-icing fluid was tested using a rotational rheometer (Anto Paar, MCR 302). The test temperatures were -20°C, -10°C, 0°C, and 10°C. The results are as follows: Figure 4 As shown. Figure 4 It can be seen that at low shear rates, the de-icing fluid exhibits a higher apparent viscosity. As the shear rate increases, the viscosity decreases significantly, that is, it exhibits obvious shear thinning characteristics, which meets the rheological performance requirements of non-Newtonian fluid de-icing fluid. In addition, the maximum shear viscosity of the de-icing fluid changes with temperature, and the viscosity is the largest at low temperatures, which is suitable for low temperature environments.

[0058] Example 6

[0059] In this embodiment, the formula of the de-icing fluid is as follows:

[0060] Components Mass percentage (wt.%) Deionized water 49.92 Alcohol: 1,2-propylene glycol 48.08 <![CDATA[Surfactant: C 22 -350]]> 2.00

[0061] Preparation: Add the formulated amount of 1,2-propylene glycol to deionized water at room temperature and stir thoroughly to mix. Then add the above formulated amount of C 22 -350, 50℃ stirring until it is completely dissolved to obtain deicing fluid.

[0062] The relationship between the apparent viscosity and shear rate of the de-icing fluid was tested using a rotational rheometer (Anto Paar, MCR 302). The test temperatures were -20°C, -10°C, 0°C, and 10°C. The results are as follows: Figure 5 As shown. Figure 5 It can be seen that at low shear rates, the de-icing fluid exhibits a higher apparent viscosity. As the shear rate increases, the viscosity decreases significantly, that is, it exhibits obvious shear thinning characteristics, which meets the rheological performance requirements of non-Newtonian fluid de-icing fluid. In addition, the maximum shear viscosity of the de-icing fluid changes with temperature, and the viscosity is the largest at low temperatures, which is suitable for low temperature environments.

[0063] Example 7

[0064] The components of the deicing fluid in this embodiment, the content of each component and the preparation method are the same as those in Example 4.

[0065] The lower half of an aluminum alloy sheet with a width of 2.5 cm and a length of 7.5 cm was immersed in the above deicing liquid, so that the lower half of the aluminum alloy sheet was adhered to the deicing liquid. The above sheets were then placed in an environment with a temperature of -20°C and a relative humidity of 40%.

[0066] After 5 hours of storage, it was found that the part of the aluminum alloy sheet that did not adhere to the de-icing fluid was almost completely frozen, while the part that adhered to the de-icing fluid was almost unchanged, showing good anti-icing performance. Figure 6 shown.

[0067] Example 8

[0068] The components of the deicing fluid in this embodiment, the content of each component and the preparation method are the same as those in Example 4.

[0069] The de-icing fluid was tested for compatibility with fuselage materials according to "GB / T 20857-2012" issued by the Standardization Administration of China. Three identical aluminum alloy test pieces were immersed in the de-icing fluid for 24 hours, and their appearance changes were observed and their quality changes before and after were tested.

[0070] The results are as follows Figure 7 As shown. By observing the test pieces before and after immersion with the naked eye and further observing them under a microscope, no obvious corrosion phenomenon was found. The three test pieces before and after immersion were weighed, and the mass of the test pieces decreased by 0.02, 0.14, and 0.14 mg / cm respectively. 2 The maximum mass change allowed for the specimen per 24h of infiltration is ≤0.3mg / cm 2 The requirements indicate that the system will basically not be corrosive to the fuselage materials and has good compatibility with the fuselage materials.

[0071] Example 9

[0072] C 22 0.03 g of -350 surfactant was placed in 5.97 g of deionized water and heated to 90°C to disperse the surfactant evenly in the water. The solution was then placed in a UV-visible spectrophotometer and the temperature was reduced from 90°C to 0°C at a rate of 1°C / min. The change in transmittance with temperature was recorded.

[0073] Depend on Figure 8 It can be seen that within the temperature range of 0-90°C, the transmittance of the surfactant is close to 0, and the solution is white and opaque, indicating that the surfactant is insoluble in water. This helps to reduce the risk of the surfactant combining with water again to form a viscoelastic fluid (similar to the formation of a hydrated gel when a polymer meets water).

Claims

1. An aircraft deicing fluid thickened with a super-long chain polyoxyethylene ether surfactant, characterized in that: The composition and mass percentage of each component are as follows: 40% to 69% alcohol, 30% to 59% deionized water, 0.2% to 2.0% surfactant, wherein the surfactant is polyoxyethylene monomethyl ether behenate, and its structural formula is as follows:

2. The aircraft deicing fluid thickened with the ultra-long chain polyoxyethylene ether surfactant according to claim 1, characterized in that: The alcohol is a divalent alkyl alcohol having 2 to 5 carbon atoms.

3. The aircraft deicing fluid thickened with the ultra-long chain polyoxyethylene ether surfactant according to claim 2, characterized in that: It is characterized in that The dihydric alkyl alcohol is preferably 1,2-propylene glycol.

4. The aircraft deicing fluid thickened with the ultra-long chain polyoxyethylene ether surfactant according to claim 2, characterized in that: The components and the mass percentage of each component are as follows: 48% to 49% of alcohol, 49% to 51% of deionized water, and 0.3% to 2.0% of surfactant.

5. A method for preparing an aircraft deicing and anti-icing fluid thickened with a super-long chain polyoxyethylene ether surfactant as claimed in any one of claims 1 to 3, characterized in that Includes the following: After mixing deionized water and alcohol and stirring evenly, add C 22 -350 surfactant, heat and stir until it is completely dissolved.

6. Application of ultra-long chain polyoxyethylene ether in aircraft deicing fluid, wherein the ultra-long chain polyoxyethylene ether is polyoxyethylene monomethyl ether of behenic acid, and its structural formula is as follows:

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