CN112458468B - Spray cleaning agent and preparation method thereof - Google Patents

Abstract

The application belongs to the technical field of cleaning agents, and particularly relates to a spraying cleaning agent and a preparation method thereof. The present application provides in a first aspect a spray cleaner comprising: potassium n-heptanoate, PEG400MO phosphate, an alkaline auxiliary agent, an organic solvent, a chelating agent and water; the potassium n-heptanoate has the structure shown in the formula I. The application provides a preparation method of the spray cleaning agent in a second aspect, which comprises the following steps: mixing potassium n-heptanoate, PEG400MO phosphate, an alkaline auxiliary agent, an organic solvent, a chelating agent and water to prepare the spray cleaning agent. The application provides a spraying cleaning agent and a preparation method thereof, which effectively solve the technical defect that the existing spraying cleaning agent cannot simultaneously have cleaning performance and foamless performance.

Description

Spray cleaning agent and preparation method thereof

Technical Field

The application belongs to the technical field of cleaning agents, and particularly relates to a spraying cleaning agent and a preparation method thereof.

Background

The bubble-free spraying is more and more concerned in recent years by comprehensively considering aspects of energy conservation, environmental protection, economic benefit and the like, is applied to various fields such as petroleum, chemical industry, metallurgy, traffic, civil use and the like at present, and has wide development prospect. One important feature of the spray cleaners employed is the requirement for stable low or no foaming. If the system generates foam, the foam can overflow from the spray tank, and the amount of water washing required for the washed material is large, which wastes energy. The low-foam or non-foam system is generally realized by adding a large amount of defoaming agent and compounding a low-foam surfactant. Many defoamers do not survive for long periods of time under strongly alkaline conditions, have poor durability, and can cause problems such as silicon spots, imprint residue, and the like. The low foaming can be realized by selecting proper surfactant, but the prior low foaming surfactant compound agent has the problems of poor oil removal rate, poor alkali resistance and the like.

In summary, the existing spray cleaning agent has the following disadvantages: 1. the water-based spray cleaning agent with low foam generally has the defects of poor cleaning performance, easy precipitation or decomposition in a system containing an alkaline auxiliary agent and reduced cleaning efficiency; 2. the cleaning agent with good cleaning performance mostly has the problems of abundant foam, difficult rinsing during spray cleaning, large water consumption and water resource waste. The invention aims to provide an alkaline spray cleaning degreasing agent which has the characteristics of high degreasing efficiency, no bubbles and the like.

Disclosure of Invention

In view of this, the application provides a spray cleaning agent and a preparation method thereof, which effectively solve the technical defect that the existing spray cleaning agent cannot simultaneously have both cleaning performance and foamless performance.

The application provides in a first aspect a spray cleaner comprising:

potassium n-heptanoate, PEG400MO phosphate, an alkaline auxiliary agent, an organic solvent, a chelating agent and water;

the potassium n-heptanoate has a structure shown in the formula I;

preferably, the spray cleaning agent comprises the following components in percentage by mass:

specifically, in the spray cleaning agent, the proportion of potassium n-heptate and PEG400MO phosphate is very important, and under a specific proportion range, the spray cleaning agent has the performance of no bubbles and high-efficiency oil removal.

Preferably, the preparation method of the potassium n-heptanoate comprises the following steps:

reacting n-heptanoic acid with potassium hydroxide aqueous solution to obtain potassium n-heptanoate.

Preferably, the molar ratio of the n-heptanoic acid to the potassium hydroxide is 1: (1.1-1.3).

Preferably, the mass fraction of the potassium hydroxide aqueous solution is 20% to 30%.

Preferably, when n-heptanoic acid reacts with an aqueous solution of potassium hydroxide, the reaction temperature is 50 ℃ to 60 ℃; the reaction time is 2-3 h.

Preferably, the alkaline auxiliary agent is one or more selected from caustic alkali, sodium carbonate, anhydrous sodium metasilicate, sodium bicarbonate and triethanolamine.

Preferably, the chelating agent is one or more selected from ethylenediaminetetraacetic acid tetrasodium salt, sodium tartrate, sodium alginate, sodium gluconate, sodium tripolyphosphate and potassium pyrophosphate.

Preferably, the organic solvent is selected from one or more of isopropyl alcohol, ethylene glycol monobutyl ether, dipropylene glycol butyl ether, diethylene glycol butyl ether and dipropylene glycol methyl ether.

The application provides a preparation method of the spray cleaning agent in a second aspect, which comprises the following steps:

mixing potassium n-heptanoate, PEG400MO phosphate, an alkaline auxiliary agent, an organic solvent, a chelating agent and water to prepare the spray cleaning agent.

The third aspect of the application provides the application of the spray cleaning agent in metal cleaning.

Preferably, the metal is selected from the group consisting of copper materials, iron materials, aluminum materials, steel materials, zinc materials, titanium materials, and alloys thereof.

The spray cleaning agent can be used in the field of foamless spray cleaning, and can also be used in the situations of cleaning agents in various fields such as petroleum, chemical engineering, metallurgy, traffic, civil use and the like.

The application aims to develop a foamless and efficient oil-removing spray cleaning agent without a defoaming agent. The detergent disclosed by the application is simple in components and comprises potassium n-heptanoate, PEG400MO phosphate, an alkaline auxiliary agent, an organic solvent, a chelating agent and water, and the application finds that the potassium n-heptanoate has excellent performance characteristics: the water-based paint has the advantages of no bubbles, alkali resistance, hard water resistance, good corrosion inhibition and oil removal effects on red copper and brass H62, and the potassium n-heptanoate has stronger wetting, penetrating, dispersing and dirt removing capabilities compared with other metal salts. The application finds that the cleaning agent with high stability, high-efficiency oil removal, high spreadability and no foam is obtained by compounding potassium n-heptanoate, PEG400MO phosphate, an alkaline assistant, an organic solvent, a chelating agent and water.

In the spray cleaning agent, potassium n-heptanoate and PEG400MO phosphate mainly play a role in efficiently removing oil, the alkaline auxiliary agent provides alkalinity for a system, prolongs the service life of a detergent, can neutralize partial fatty acid in oil stains, reduces flocculation and redeposition tendency of the stains, plays a role in cleaning the stains, and also has the functions of a pH buffering agent, a hard water softening agent, a metal corrosion inhibitor and the like. The organic solvent can not only solubilize a part of surfactant and improve the stability of the formula, but also dissolve grease and promote the removal of dirt.

Compared with the prior art, the spray cleaning agent has the following advantages compared with the common spray cleaning agent on the market:

1. the cleaning agent does not contain a defoaming agent, and the defects that the defoaming performance of the cleaning agent is reduced due to the combination of the defoaming agent and oil stains, hydrolysis in an acid or alkali solution and the like are avoided;

2. the washing machine is free of bubbles, secondary rinsing in the spraying and cleaning process can be avoided, and water resources are saved;

3. the coating is alkali-resistant, does not delaminate and hydrolyze under medium and high alkali conditions, and can keep stable for a long time;

4. the spreading performance on the surface of the oil stain is good, and the detergency is strong;

5. the preparation method of the spray cleaning agent is simple and easy to obtain.

Detailed Description

The application provides a spraying cleaning agent and a preparation method thereof, which are used for solving the technical defect that the existing spraying cleaning agent cannot simultaneously have cleaning performance and foamless performance.

The technical solutions in the embodiments of the present application will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

Wherein, the raw materials or reagents used in the following examples are all sold in the market or made by the user;

the preparation method of potassium n-heptate used in the following examples comprises:

1. putting n-heptanoic acid into a reaction kettle, and heating to 50 ℃ for later use;

2. slowly putting the potassium hydroxide aqueous solution into a reaction kettle, and reacting for 2.5h at 55 ℃; wherein the mass fraction of the potassium hydroxide in the potassium hydroxide aqueous solution is 25 percent; wherein the molar ratio of the n-heptanoic acid to the potassium hydroxide is 1: 1.2;

3. and stopping heating after the reaction is finished, naturally cooling to room temperature, and discharging to obtain the potassium n-heptylate.

4. The infrared spectrum and nuclear magnetic spectrum detection of the potassium n-heptanoate disclosed by the application result shows that the infrared spectrum of the potassium n-heptanoate prepared by the application example meets the infrared spectrum of the standard n-heptanoate, and the nuclear magnetic spectrum of the potassium n-heptanoate prepared by the application example meets the nuclear magnetic spectrum of the standard n-heptanoate, so that the potassium n-heptanoate is successfully prepared by the application.

Comparative example 3 is a commercially available hard surface cleaner.

Comparative example 4 is a commercially available spray cleaner.

Example 1

The application provides a first spray cleaning agent, and the specific preparation method comprises the following steps:

according to the total mass of the preset foamless spray cleaning agent, 8% by mass of potassium n-heptate, 6% by mass of PEG400MO phosphate, 1% by mass of sodium hydroxide, 3% by mass of sodium metasilicate pentahydrate, 2% by mass of sodium carbonate, 0.5% by mass of tetrasodium ethylenediaminetetraacetate and 79.5% by mass of deionized water are sequentially added. The mixture was stirred well with a stirrer until well mixed and labeled as example 1.

Example 2

The application provides a second spray cleaning agent, and the specific preparation method comprises the following steps:

according to the total mass of the preset foamless spray cleaning agent, 12% by mass of potassium n-heptate, 4% by mass of PEG400MO phosphate, 1% by mass of sodium hydroxide, 2% by mass of sodium metasilicate pentahydrate, 2% by mass of sodium carbonate, 1% by mass of sodium tartrate and 78% by mass of deionized water are sequentially added. The mixture was stirred well with a stirrer until well mixed and labeled as example 2.

Comparative example 1

The application provides a first control product, which is prepared by a specific method comprising the following steps:

according to the total mass of the preset foamless spray cleaning agent, 15% by mass of PEG400MO phosphate, 1% by mass of sodium hydroxide, 3% by mass of sodium metasilicate pentahydrate, 2% by mass of sodium carbonate, 0.5% by mass of ethylenediaminetetraacetic acid tetrasodium salt and 78.5% by mass of deionized water are sequentially added. The mixture was stirred well with a stirrer until uniform mixing was obtained and the label was comparative example 1.

Comparative example 2

The application provides a second control product, which is specifically prepared by a method comprising the following steps:

according to the total mass of the preset foam spraying cleaning agent, 16% by mass of PEG400MO phosphate, 1% by mass of sodium hydroxide, 2% by mass of sodium metasilicate pentahydrate, 2% by mass of sodium carbonate, 1% by mass of sodium tartrate and 78% by mass of deionized water are sequentially added. The mixture was stirred well with a stirrer until uniform mixing was obtained and the label was comparative example 2.

Comparative example 3

A third control product of the present application is a commercial hard surface cleaner having the composition shown in table 1.

TABLE 1 common hard surface cleaner compositions available commercially

Composition of

AEO-6

AEO-3

Phosphoric acid esters

Anhydrous sodium metasilicate

Ethylenediaminetetraacetic acid

Deionized water

Mass percent

5％

5％

10％

10％

4％

66％

Comparative example 4

A fourth control product of the present application was a commercial spray rinse having the composition shown in Table 2

TABLE 2 commercial spray cleaners

Example 3

The embodiment of the application provides test tests of spreading performance, foaming performance and cleaning power of embodiments 1-2 and comparative examples 1-4, and the test tests comprise the following specific steps:

1. spreading performance test method

The test sample is characterized by the contact angle of the test sample on the surface of the paraffin film. The smaller the contact angle, the better the spreadability of the cleaning agent on the greasy dirt surface, and the better the cleaning and degreasing are.

2. Foaming test method

Foaming power was measured according to the method for measuring foaming power in GB/T7462-94 improved surfactant foaming power in Ross-Miles method, and the foam volume at 30s was recorded, and the average value of the foam volume of 3 parallel experiments was taken as foaming power. The smaller the foaming volume, the lower the foaming power, and the better the low foaming property.

3. Cleaning force testing method

The oil stain cleaning capability of the metal surface is evaluated, and a weighed metal test piece (the weight is M)₁) Immersing into oil stain for 10min, taking out, draining, weighing, and weighing₂Then immersing the test piece into a swinging tank containing 500mL of test solution at 30 ℃, standing for 3min, swinging for 3min, taking out the test piece, swinging for 10 times in 500mL of distilled water at 30 ℃, taking out the test piece, immediately drying in an oven at 70 ℃ for 40min, taking out, cooling to room temperature, weighing, and weighing the test piece with the weight of M₃. The cleaning power is expressed in terms of the oil-washing rate h and is calculated as follows: h ═ M₂-M₃)/(M₂-M₁)]The larger the value of "x 100" and "h" is, the better the cleaning effect is.

The spreading property, foaming property and cleaning power of examples 1 to 2 and comparative examples 1 to 4 were measured in the above manner, respectively, and the results are shown in Table 3.

Table 3 results of performance testing

Index (I)	Example 1	Example 2	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4
							Contact angle °	0	0	34	37	0	33
Foaming power ml	0	0	0	0	184	0
							Cleaning power%	97.84	98.76	81.02	79.34	96.21	83.26

As can be seen from Table 3:

the contact angle of the spray cleaning agent obtained in the embodiment 1 and the embodiment 2 is 0 degrees, which shows that the oil removing effect of the spray cleaning agent is better than that of the spray cleaning agent sold in the market, the spray cleaning agent has good spreadability on oil stains, can be spread on the surface of the oil stains quickly, and is beneficial to cleaning;

the foaming volumes of the spray cleaning agents obtained in the embodiment 1 and the embodiment 2 are both 0, which shows that the foaming capacity of the spray cleaning agent is lower than that of the commercially available cleaning agent, and the spray cleaning agent belongs to a non/low-foaming spray cleaning agent;

third, the cleaning power of the spray cleaning agent obtained in example 1 and example 2 is higher than that of the commercial cleaning agent, and the spray cleaning agent has excellent cleaning power. Therefore, compared with the commercially available cleaning agent, the cleaning agent has the remarkable advantages of low foam and good cleaning power.

And fourthly, compared with the products prepared by the example 1 and the example 2, the products prepared by the comparative example 1 and the comparative example 2 without adding the potassium n-heptanoate serving as the surfactant have the cleaning power which is not as good as that of the products prepared by the example 1 and the example 2 and even lower than that of the products prepared by the comparative example 3. It can be seen that in the foamless spray cleaning system, potassium n-heptanoate plays an important role in cleaning effect.

Example 4

The embodiment of the application provides alkali resistance stability and hydrolysis stability test tests of embodiments 1-2 and comparative examples 1-4, and the specific steps comprise:

1. alkali resistance test:

sodium hydroxide aqueous solutions with different concentrations are prepared, the sodium hydroxide aqueous solutions with different concentrations are used as solvents, the sodium hydroxide aqueous solutions with different concentrations are used for preparing the solutions of examples 1-2 and comparative examples 1-4 with 1% concentration respectively, the appearance state of the sample solution after being stored for 30 days is observed, if the sample solution is layered or floated, the alkali resistance stability is good, otherwise, the alkali resistance stability is poor, and the results are shown in table 4.

Table 4 alkali resistance stability test results

2. And (3) testing the hydrolytic stability:

the sample solutions of examples 1 to 2 and comparative examples 1 to 4 are respectively prepared by taking water as a solvent and water as solutes at concentrations of 1%, the sample solutions of examples 1 and 2, comparative examples 3 and 4 are respectively tested for contact angles when the sample solutions are stored for 7 days, 15 days and 30 days, the change of the contact angles can represent the hydrolytic stability of the sample solutions, if the hydrolytic stability is good, the change of the contact angles is small and even no change, otherwise, the contact angles are obviously increased, and the results are shown in table 5.

TABLE 5 hydrolytic stability test results

As can be seen from Table 4, the spray cleaners obtained in examples 1-2 remained clear under different alkali concentrations, indicating that the spray cleaners obtained in examples 1-2 remained stable for a long period of time under medium and high alkali conditions. As is clear from Table 5, the spray cleaning agents obtained in examples 1 to 2 can maintain the hydrolytic stability for a long period of time.

The foregoing is only a preferred embodiment of the present application and it should be noted that those skilled in the art can make several improvements and modifications without departing from the principle of the present application, and these improvements and modifications should also be considered as the protection scope of the present application.

Claims (9)

1. A spray cleaning agent is characterized by comprising

Potassium n-heptanoate, PEG400MO phosphate, an alkaline auxiliary agent, an organic solvent, a chelating agent and water;

the potassium n-heptanoate has a structure shown in the formula I;

calculated according to the mass percentage, the method comprises the following steps:

2. the spray cleaning agent as claimed in claim 1, wherein the preparation method of potassium n-heptonate comprises the following steps:

reacting n-heptanoic acid with potassium hydroxide aqueous solution to obtain potassium n-heptanoate.

3. The spray cleaner of claim 2, wherein the molar ratio of n-heptanoic acid to potassium hydroxide is from 1: (1.1-1.3).

4. The spray cleaning agent according to claim 2, wherein the mass fraction of the aqueous solution of potassium hydroxide is 20% to 30%.

5. The spray cleaning agent according to claim 2, wherein the reaction temperature is 50 ℃ to 60 ℃; the reaction time is 2-3 h.

6. The spray cleaner of claim 1, wherein the alkaline builder is selected from one or more of caustic alkali, sodium carbonate, anhydrous sodium metasilicate, sodium bicarbonate, and triethanolamine.

7. The spray cleaning agent according to claim 1, wherein the chelating agent is one or more selected from the group consisting of ethylenediaminetetraacetic acid tetrasodium salt, sodium tartrate, sodium alginate, sodium gluconate, sodium tripolyphosphate, and potassium pyrophosphate.

8. The spray cleaner of claim 1, wherein the organic solvent is selected from one or more of isopropyl alcohol, ethylene glycol monobutyl ether, dipropylene glycol butyl ether, diethylene glycol butyl ether, and dipropylene glycol methyl ether.

9. The preparation method of the spray cleaning agent as claimed in any one of claims 1 to 8, characterized by comprising the following steps:

mixing potassium n-heptanoate, PEG400MO phosphate, an alkaline auxiliary agent, an organic solvent, a chelating agent and water to prepare the spray cleaning agent.