A cleaning agent for electric tea boiler of motor vehicle and preparation method thereof

Abstract

The present invention proposes a cleaning agent for electric tea boilers for motor vehicles and a preparation method thereof, and belongs to the technical field of cleaning agents. The cleaning agent is prepared by the following raw materials by weight: 4-7 parts of bio-based surfactants, 2-3 parts of co-surfactants, 100-120 parts of water, 3-5 parts of citric acid, 2-5 parts of acetic acid, 2-3 parts of disodium EDTA, and 20-30 parts of ethanol. The cleaning agent for electric tea boilers for motor vehicles prepared by the present invention has strong cleaning power, good descaling effect, low toxicity, low sensitivity, degradability, no stimulation and other characteristics, high safety, environmental friendliness, and will not pollute water quality when used for washing tableware, and has broad application prospects.

Description

Technical Field

[0001] The invention relates to the technical field of cleaning agents, and in particular to a cleaning agent for a motor vehicle electric tea boiler and a preparation method thereof. Background Art

[0002] With the continuous development of the economy and society, rail transit trains have become the main means of transportation in today's society. As the operating speed of trains continues to increase, higher requirements will inevitably be placed on train services and safety performance. Electric heating electric tea boilers are a new generation of water supply equipment developed to meet the water supply needs of railway passenger cars. They use the centralized power supply of trains and have the characteristics of high efficiency and energy saving, high thermal efficiency, stable water production, cleanliness and hygiene, and high degree of automation, providing passengers with safe drinking water. In order to facilitate passengers to drink water, the normal operation of electric tea boilers is particularly important.

[0003] Scale is a major problem of electric tea stoves. The main reason for scaling is that the water quality is poor. The electric tea stove separates the calcium and magnesium ions in the water when heating. In addition, the heating chamber and water storage chamber of the furnace body are made of stainless steel, which will cause scale to adhere to its surface with strong adhesion, causing scale accumulation. When the scale accumulates too much, it will affect the water output, and it is easy to make the control electrode fail, causing a large number of faults in the electric tea stove. When descaling the electric tea stove, it is necessary to add a cleaning agent to remove the scale in the electric tea stove.

[0004] In the current production process of cleaning agents, additives, surfactants, and solvents are added into a reaction pot in a certain ratio and mixed and stirred evenly to achieve the effect of dissolving scale and cleaning. However, residues are easily left and affect water quality during use. Therefore, a green, healthy, and safe cleaning agent is needed. Summary of the invention

[0005] The purpose of the present invention is to provide a cleaning agent for electric tea boilers on motor vehicles and a preparation method thereof, which has strong cleaning power, good descaling effect, low toxicity, low sensitivity, biodegradability, no irritation and the like, high safety, environmental friendliness, and will not pollute water quality when used for washing tableware, and has broad application prospects.

[0006] The technical solution of the present invention is achieved in this way:

[0007] The present invention provides a cleaning agent for electric tea boilers of motor vehicles, which is prepared from the following raw materials by weight: 4-7 parts of bio-based surfactants, 2-3 parts of co-surfactants, 100-120 parts of water, 3-5 parts of citric acid, 2-5 parts of acetic acid, 2-3 parts of disodium EDTA, and 20-30 parts of ethanol; wherein the structural formula of the bio-based surfactant is as shown in Formula I:

[0008]

[0009] As a further improvement of the present invention, the preparation method of the bio-based surfactant is as follows:

[0010] S1. Add saponin to water, add NHS and EDC·HCl, stir to activate, add lysine, stir to react, recrystallize, and obtain intermediate 1, the structure of which is as follows:

[0011] S2. The intermediate 1, ionic liquid, base and acetyl bromide-α-D-glucose are mixed and stirred for reaction, concentrated, and separated and purified by column chromatography to obtain the intermediate 2, the structure of which is as follows:

[0012] S3. Add intermediate 2 and sodium methoxide to methanol, stir the mixture at room temperature, and separate and purify the mixture by column chromatography to obtain the product.

[0013] As a further improvement of the present invention, the molar ratio of saponin, NHS, EDC·HCl and lysine in step S1 is 2:4-6:5-7:0.9-1, the stirring activation temperature is 0-4°C, the time is 30-40min, and the stirring reaction time is 4-6h.

[0014] As a further improvement of the present invention, the molar ratio of the intermediate 1, the ionic liquid, the base and acetyl bromide-α-D-glucose in step S2 is 1:1-1.2:3-4:0.9-1, the ionic liquid is an imidazolyl ionic liquid, selected from at least one of 1-butyl-3-methyl-imidazolium bromide, 1-hexyl-3-methyl-imidazolium bromide, 1-ethyl-3-methyl-imidazolium bromide, and 1-methyl-3-n-octyl-imidazolium bromide, the base is NaOH or KOH, and the stirring reaction time is 3-5h.

[0015] As a further improvement of the present invention, the molar ratio of the intermediate 2 to sodium methoxide in step S3 is 1:1-2, and the reaction time under room temperature stirring is 7-9 hours.

[0016] As a further improvement of the present invention, the preparation method of the bio-based surfactant is specifically as follows:

[0017] S1. Add 2 molar equivalents of saponin to water, add 4-6 molar equivalents of NHS and 5-7 molar equivalents of EDC·HCl, stir and activate at 0-4°C for 30-40 min, add 0.9-1 molar equivalents of lysine, stir and react for 4-6 h, and recrystallize to obtain intermediate 1;

[0018] S2. 1 molar equivalent of intermediate 1, 1-1.2 molar equivalent of ionic liquid, 3-4 molar equivalent of NaOH or KOH and 0.9-1 molar equivalent of acetyl bromide-α-D-glucose were mixed and added to dichloromethane, stirred for 3-5h, concentrated, and purified by column chromatography to obtain intermediate 2;

[0019] S3. Add 1 molar equivalent of intermediate 2 and 1-2 molar equivalents of sodium methoxide to methanol, stir and react at room temperature for 7-9 hours, separate and purify by column chromatography to obtain the product.

[0020] As a further improvement of the present invention, the co-surfactant is lecithin.

[0021] The present invention further protects a method for preparing the above-mentioned cleaning agent for electric train boilers, comprising the following steps: dissolving a bio-based surfactant and a co-surfactant in water, adding disodium EDTA, citric acid and acetic acid, heating and stirring to dissolve, adding ethanol, stirring and mixing evenly, and preparing a cleaning agent for electric train boilers.

[0022] As a further improvement of the present invention, the temperature of the heating, stirring and dissolving is 40-60° C. and the time is 20-40 min.

[0023] The present invention further protects the use of the cleaning agent for electric tea boiler on a motor vehicle in cleaning kitchenware, tableware and teaware.

[0024] The present invention has the following beneficial effects:

[0025] Saponin is a bio-based compound that can form an aqueous solution or a colloidal solution and can form soap-like foam. It comes from soapberries, is safe, has low toxicity, and has good surface activity, but its detergency is limited.

[0026] After the activation, the present invention performs a condensation reaction with an amino acid lysine having two amino groups, thereby preparing a Gemini surfactant, greatly improving the surfactant, and significantly improving the detergency. Further, the intermediate reacts with acetyl bromide-α-D-glucose to form a glycoside structure, which greatly improves the thermal stability of the product, and at the same time, the water solubility is significantly improved. At the same time, it has the characteristics of low toxicity, low sensitivity, degradability, no stimulation, high safety, environmental friendliness, and will not pollute water quality when used for washing tableware. In addition, the glycoside structure of the bio-based surfactant also has a broad-spectrum antibacterial property, can increase the permeability of the Pseudomonas cell wall, and reduce its metabolic activity.

[0027] In addition, the present invention also adds citric acid and acetic acid, which are highly acidic and have a pH buffering effect, while being less corrosive to metals. They are compounded with the above-mentioned bio-based surfactant and disodium EDTA to remove calcium and magnesium scale, thereby greatly improving the scale removal rate.

[0028] The cleaning agent for the electric tea boiler on a motor vehicle prepared by the invention has strong cleaning power, good descaling effect, low toxicity, low sensitivity, degradability, no irritation and the like, high safety, environmental friendliness, and will not pollute water quality when used for washing tableware, and has broad application prospects. DETAILED DESCRIPTION

[0029] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0030] Preparation Example 1 Preparation of bio-based surfactant

[0031] The synthetic route is as follows:

[0032]

[0033] The specific method is as follows:

[0034] S1. Add 2 mmol of saponin to 50 mL of water, add 5 mmol of NHS and 6 mmol of EDC·HCl, stir and activate at 0°C for 35 min, add 1 mmol of lysine, stir and react for 5 h, and recrystallize to obtain intermediate 1; ESI-MS calculated value: C 32 H 43 N2O6(M+H) + 551.69, found: 551.7, yield: 67%.

[0035] NMR results: 1 H NMR (300MHz, CDCl3) δ11.0 (br, 1H), 8.05 (br, 2H), 7.84 (m, 4H), 6.92 (m, 4H), 5.7 (m, 2H), 4.96-5.02 (m, 4H), 4.45 (t, 1H), 3.94 (t, 4H), 3.20 (t, 2H), 1.97 (m, 4H), 1.69-1.82 (m, 8H), 1.30-1.33 (m, 6H).

[0036] S2. 1 mmol of intermediate 1, 1.2 mmol of 1-hexyl-3-methyl-imidazolium bromide, 3.5 mmol of NaOH and 1 mmol of acetyl bromide-α-D-glucose were mixed and added into 50 mL of dichloromethane, stirred for 4 h, concentrated, and separated and purified by silica gel column chromatography (the eluent was petroleum ether and ethyl acetate in a volume ratio of 3:1) to obtain intermediate 2; ESI-MS calculated value: C 47 H 63 N2O14 (M+H) + 879.42, found: 879.4, yield: 52%.

[0037] NMR results: 1 H NMR (300MHz, CDCl3) δ8.0 (br, 2H), 7.82 (m, 4H), 6.95 (m, 4H), 5.75 (m, 2H), 4.92-5.00 (m, 4H), 4.42-4.59 (m, 4H), 3.92 -4.2(m, 8H), 3.22(t, 2H), 2.05(s, 12H), 1.95(m, 4H), 1.68-1.80(m, 8H), 1.57(m, 1H), 1.31-1.34(m, 6H), 0.82(s, 1H).

[0038] S3. Add 1 mmol of intermediate 2 and 1.5 mmol of sodium methoxide to 50 mL of methanol, stir at room temperature for 8 h, separate and purify by silica gel column chromatography (the eluent is chloroform and ethanol in a volume ratio of 4:1) to obtain the product. ESI-MS calculated value: C 39 H 55 N2O 10 (M+H) + 711.38, found: 711.4, yield: 82%.

[0039] NMR results: 1 H NMR (300MHz, CDCl3) δ8.0 (br, 2H), 7.84 (m, 4H), 6.92 (m, 4H), 5.7 (m, 2H), 4.96-5.02 (m, 4H), 4.54 (m, 1H), 4.45 (t, 1 H), 3.94 (t, 4H), 3.2-3.7 (m, 7H), 3.20 (t, 2H), 1.97-2.0 (m, 8H), 1.69-1.82 (m, 8H), 1.30-1.33 (m, 6H), 0.96 (m, 1H).

[0040] Test Example 1

[0041] The equilibrium surface tension of the aqueous solution of the bio-based surfactant prepared in Preparation Example 1 at different concentrations at (25±0.1)°C was tested by the platinum ring method. Each concentration was measured 10 times and the average value was taken. After the test, a γ-c curve was drawn with concentration (c) as the horizontal axis and surface tension (γ) as the vertical axis. The cmc was determined according to the turning point of the curve, and the surface tension at this time was recorded. The results are shown in Table 1.

[0042] Table 1

[0043] Group <![CDATA[cmc(×10 -6 mol / L)]]> <![CDATA[γ cmc (mN / m)]]> Preparation Example 1 5.2 27.9

[0044] It can be seen from the above table that the bio-based surfactant prepared in Preparation Example 1 of the present invention has a lower critical micelle concentration and a lower surface tension at this time.

[0045] Example 1

[0046] This embodiment provides a cleaning agent for a motor vehicle electric tea boiler.

[0047] The preparation method comprises the following steps: dissolving 4 g of the bio-based surfactant prepared in Preparation Example 1 and 2 g of lecithin in 100 mL of water, adding 2 g of disodium EDTA, 3 g of citric acid and 2 g of acetic acid, heating to 40° C., stirring for 20 min, adding 20 g of ethanol, stirring and mixing for 20 min, and preparing a cleaning agent for an electric tea boiler for a motor vehicle.

[0048] Example 2

[0049] This embodiment provides a cleaning agent for a motor vehicle electric tea boiler.

[0050] The preparation method comprises the following steps: dissolving 7 g of the bio-based surfactant prepared in Preparation Example 1 and 3 g of lecithin in 120 mL of water, adding 3 g of disodium EDTA, 5 g of citric acid and 5 g of acetic acid, heating to 60° C., stirring for 40 min, adding 30 g of ethanol, stirring and mixing for 20 min, and preparing a cleaning agent for an electric tea boiler for a motor vehicle.

[0051] Example 3

[0052] This embodiment provides a cleaning agent for a motor vehicle electric tea boiler.

[0053] The preparation method comprises the following steps: dissolving 5.5 g of the bio-based surfactant prepared in Preparation Example 1 and 2.5 g of lecithin in 110 mL of water, adding 2.5 g of disodium EDTA, 4 g of citric acid and 3.5 g of acetic acid, heating to 50° C., stirring for 30 min, adding 25 g of ethanol, stirring and mixing for 20 min, and preparing a cleaning agent for an electric tea boiler for a motor vehicle.

[0054] Comparative Example 1

[0055] Compared with Example 3, the difference is that the bio-based surfactant prepared in Preparation Example 1 is replaced by saponin of equal mass.

[0056] The preparation method comprises the following steps: dissolving 5.5 g of saponin and 2.5 g of lecithin in 110 mL of water, adding 2.5 g of disodium EDTA, 4 g of citric acid and 3.5 g of acetic acid, heating to 50° C., stirring for 30 minutes, adding 25 g of ethanol, stirring and mixing for 20 minutes, and preparing a cleaning agent for a motor vehicle electric tea boiler.

[0057] Comparative Example 2

[0058] Compared with Example 3, the difference is that the bio-based surfactant prepared in Preparation Example 1 is not added.

[0059] The preparation method comprises the following steps: dissolving 8 g of lecithin in 110 mL of water, adding 2.5 g of disodium EDTA, 4 g of citric acid and 3.5 g of acetic acid, heating to 50° C., stirring for 30 minutes, adding 25 g of ethanol, stirring and mixing for 20 minutes, and preparing a cleaning agent for a motor vehicle electric tea boiler.

[0060] Comparative Example 3

[0061] The difference compared with Example 3 is that lecithin is not added.

[0062] The preparation method comprises the following steps: dissolving 8 g of the bio-based surfactant prepared in Preparation Example 1 in 110 mL of water, adding 2.5 g of disodium EDTA, 4 g of citric acid and 3.5 g of acetic acid, heating to 50° C., stirring for 30 min, adding 25 g of ethanol, stirring and mixing for 20 min, and preparing a cleaning agent for an electric tea boiler for a motor vehicle.

[0063] Comparative Example 4

[0064] Compared with Example 3, the difference is that citric acid and acetic acid are not added.

[0065] The preparation method comprises the following steps: dissolving 5.5 g of the bio-based surfactant prepared in Preparation Example 1 and 2.5 g of lecithin in 110 mL of water, adding 2.5 g of disodium EDTA, heating to 50° C., stirring for 30 min, adding 25 g of ethanol, stirring and mixing for 20 min, and preparing a cleaning agent for an electric tea boiler for a motor vehicle.

[0066] Test Example 2

[0067] The cleaning agents for electric train electric tea boilers prepared in Examples 1-3 and Comparative Examples 1-4 and similar products on the market were prepared into 5 wt % aqueous solutions for performance testing.

[0068] The cleaning power (%) of the sample by swing washing was tested according to the method of GB / T 35759-2017 "Metal Cleaners".

[0069] Foaming test: The Roche foam meter was set to 25°C, the sample solution of the present invention was placed in the bottom of the foam meter, the scale was aligned to 50 mL, and the test solution was then drawn with a 200 mL quantitative funnel, the center of the funnel was fixed, the test solution was placed, and the foam height (mm) was recorded, retaining the integer.

[0070] Stable foam test: Set the Roche foam meter to 25°C, place the sample solution at the bottom of the foam meter, align the scale to 50mL, then use a 200mL quantitative funnel to absorb the test solution, fix the center position of the funnel, put down the test solution, and record the foam height (mm) after 30 minutes, retaining the integer.

[0071] The results are shown in Table 2.

[0072] Table 2

[0073] Group Cleaning power (%) Foam height (mm) Foam height after 30 minutes (mm) Example 1 90 245 210 Example 2 92 249 214 Example 3 94 252 220 Comparative Example 1 86 212 167 Comparative Example 2 52 152 78 Comparative Example 3 73 177 92 Comparative Example 4 80 224 173 Commercially available 78 194 115

[0074] It can be seen from the above table that the cleaning agents for electric tea boilers on motor vehicles prepared in Examples 1-3 have good detergency, foaming properties and foam stability.

[0075] Test Example 3

[0076] The cleaning agents for electric tea boilers on motor vehicles prepared in Examples 1-3 of the present invention and Comparative Examples 1-4 were prepared into 1 wt % aqueous solutions for experiments.

[0077] Stimulus test:

[0078] A 9-day-old fertilized egg was selected, and the air chamber end of the egg was found with a light source. A hole was punched from the air chamber end of the egg to reduce pressure, and then the eggshell at the air chamber end was cut open; a few drops of distilled water were dripped on the eggshell membrane to separate the chorionic follicle membrane from the eggshell membrane, and the egg membrane was carefully peeled off to expose the vascularized CAM, and the undamaged CAM was selected for the test. 0.1 mL of sample was dripped on the CAM, and after 30 seconds, it was rinsed with 0.75wt% saline, and the initial time of vascular congestion, bleeding and coagulation within 5 minutes was observed and recorded, and the stimulation score was calculated.

[0079] The calculation formula of the stimulation score is as follows:

[0080] IS=[(301-secH)×5+(301-secL)×7+(301-secC)×9] / 300

[0081] Wherein, secH is the initial time of congestion (s); secL is the initial time of bleeding (s); secC is the initial time of coagulation (s).

[0082] Safety toxicology experiments:

[0083] According to GB15193-2003 "Food Safety Toxicology Evaluation Procedures and Methods", the maximum tolerated dose method was used. Kunming mice were selected, half male and half female, and fasted for 16 hours before the test. Drinking water was not limited. The sample solution was given by gavage at 0.4mL / 20g body weight. After gavage, the poisoning symptoms and death of the animals were observed. The animals were weighed once a week and observed for 14 days.

[0084] The results are shown in Table 3.

[0085] Table 3

[0086] Group Stimulation score LD50(mg / kgBW), ≧ Example 1 3.4 20000 Example 2 3.3 20000 Example 3 3.1 20000 Comparative Example 1 7.5 5000 Comparative Example 2 4.7 10000 Comparative Example 3 4.2 10000 Comparative Example 4 3.9 20000

[0087] It can be seen from the above table that the cleaning agents for electric train electric tea boilers prepared in Examples 1-3 of the present invention have low irritation and are non-toxic.

[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 in the protection scope of the present invention.

Claims

1. A cleaning agent for electric tea boilers on motor vehicles, characterized in that: The bio-based surfactant is prepared from the following raw materials in parts by weight: 4-7 parts of bio-based surfactant, 2-3 parts of co-surfactant, 100-120 parts of water, 3-5 parts of citric acid, 2-5 parts of acetic acid, 2-3 parts of disodium EDTA, and 20-30 parts of ethanol; wherein the bio-based surfactant has a structural formula as shown in Formula I: Formula I; The preparation method of the bio-based surfactant is as follows: S1. Add saponin to water, add NHS and EDC·HCl, stir to activate, add lysine, stir to react, recrystallize, and obtain intermediate 1, the structure of which is as follows: ; S2. The intermediate 1, ionic liquid, base and acetyl bromide-α-D-glucose are mixed and stirred for reaction, concentrated, and separated and purified by column chromatography to obtain the intermediate 2, the structure of which is as follows: ; S3. The intermediate 2 and sodium methoxide were added to methanol, the reaction was stirred at room temperature, and the product was separated and purified by column chromatography to obtain the product.

2. The cleaning agent for electric tea boiler for motor vehicles according to claim 1, characterized in that: In step S1, the molar ratio of saponin, NHS, EDC·HCl and lysine is 2:4-6:5-7:0.9-1, the stirring activation temperature is 0-4°C, the time is 30-40min, and the stirring reaction time is 4-6h.

3. The cleaning agent for electric tea boiler for motor vehicles according to claim 1, characterized in that: In step S2, the molar ratio of the intermediate 1, the ionic liquid, the base and acetyl bromide-α-D-glucose is 1:1-1.2:3-4:0.9-1, the ionic liquid is an imidazolyl ionic liquid, selected from at least one of 1-butyl-3-methyl-imidazolium bromide, 1-hexyl-3-methyl-imidazolium bromide, 1-ethyl-3-methyl-imidazolium bromide, and 1-methyl-3-n-octyl-imidazolium bromide, the base is NaOH or KOH, and the stirring reaction time is 3-5h.

4. The cleaning agent for electric tea boiler for motor vehicles according to claim 1, characterized in that: In step S3, the molar ratio of the intermediate 2 to sodium methoxide is 1:1-2, and the reaction time under room temperature stirring is 7-9 hours.

5. The cleaning agent for electric tea boiler for motor vehicles according to claim 1, characterized in that: The preparation method of the bio-based surfactant is specifically as follows: S1. Add 2 molar equivalents of saponin to water, add 4-6 molar equivalents of NHS and 5-7 molar equivalents of EDC·HCl, stir and activate at 0-4°C for 30-40 min, add 0.9-1 molar equivalent of lysine, stir and react for 4-6 h, and recrystallize to obtain intermediate 1; S2. 1 molar equivalent of intermediate 1, 1-1.2 molar equivalent of ionic liquid, 3-4 molar equivalent of NaOH or KOH and 0.9-1 molar equivalent of acetyl bromide-α-D-glucose were mixed and added to dichloromethane, stirred for 3-5h, concentrated, and separated and purified by column chromatography to obtain intermediate 2; S3. 1 molar equivalent of intermediate 2 and 1-2 molar equivalents of sodium methoxide were added to methanol, and the mixture was stirred at room temperature for 7-9 hours. The mixture was separated and purified by column chromatography to obtain the product.

6. The cleaning agent for electric tea boiler for motor vehicles according to claim 1, characterized in that: The co-surfactant is lecithin.

7. A method for preparing a cleaning agent for a motor vehicle electric tea boiler as claimed in any one of claims 1 to 6, characterized in that: The method comprises the following steps: dissolving a bio-based surfactant and a co-surfactant in water, adding disodium EDTA, citric acid and acetic acid, heating and stirring to dissolve, adding ethanol, stirring and mixing evenly, and preparing a cleaning agent for electric tea boilers of electric trains.

8. The preparation method according to claim 7, characterized in that: The temperature of the heating, stirring and dissolving is 40-60° C. and the time is 20-40 min.

9. Use of the cleaning agent for electric tea boiler on motor vehicles as claimed in any one of claims 1 to 6 in cleaning tableware and tea sets.

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