CN112626531B

CN112626531B - Surfactant and application thereof

Info

Publication number: CN112626531B
Application number: CN202011361702.4A
Authority: CN
Inventors: 王宪章; 何锦梅
Original assignee: Dexu New Materials Guangzhou Co ltd
Current assignee: Dexu New Materials Guangzhou Co ltd
Priority date: 2020-11-27
Filing date: 2020-11-27
Publication date: 2022-06-03
Anticipated expiration: 2040-11-27
Also published as: CN112626531A

Abstract

The application belongs to the technical field of surfactants, and particularly relates to a surfactant and application thereof. The application provides the application of potassium n-heptanoate in a surfactant; the potassium n-heptanoate has a structure shown in the formula I; in a second aspect, the present application provides a surfactant comprising potassium n-heptanoate, said potassium n-heptanoate having the structure of formula i below. The third aspect of the application provides a preparation method of potassium n-heptonate, which comprises the following steps: reacting n-heptanoic acid with a potassium hydroxide aqueous solution to prepare potassium n-heptanoate; the application of the surfactant in metal cleaning is provided in a fourth aspect, and the surfactant effectively overcomes the technical defects of poor cleaning performance, caustic alkali resistance and easiness in foaming of the existing surfactant.

Description

Surfactant and application thereof

Technical Field

The application belongs to the technical field of surfactants, and particularly relates to a surfactant and application thereof.

Background

Surfactant (surfactant) is a substance added in a small amount to change the interface state of a solution system obviously. Has fixed hydrophilic and lipophilic groups and can be directionally arranged on the surface of the solution. The surfactant is an important component of the detergent and plays an important role in removing various dirt in the washing process, and in recent years, with the continuous development of the detergent industry, various novel surfactants are continuously disclosed, so that more choices and opportunities are provided for the formula of the detergent.

The commonly used surfactants at present mainly comprise anionic surfactants such as alkyl sulfate and alkyl sulfonate, nonionic surfactants such as fatty alcohol-polyoxyethylene ether and amphoteric surfactants such as betaine. The surfactants have the problem of abundant foam, and the abundant foam not only influences decontamination, but also is difficult to rinse and easy to remain. The low foam can be realized by the block polyethers, various end-capped alcohol ethers and the surfactant composition containing the defoaming agent on the market, but the process with strict requirements on foam, such as spraying, cannot well meet the requirements, and the problems of silicon spots and the like caused by the addition of the defoaming agent.

Disclosure of Invention

In view of the above, the present application provides a surfactant and an application thereof, which effectively solve the technical defects of poor cleaning performance, caustic alkali intolerance and easy foaming of the existing surfactants.

The application discloses the application of potassium n-heptanoate in a surfactant in a first aspect; the potassium n-heptanoate has a structure shown in the formula I;

in a second aspect, the present application provides a surfactant comprising potassium n-heptanoate, said potassium n-heptanoate having the structure of formula i below;

the surfactant of the present application may further include auxiliary substances acceptable for the surfactant, i.e., substances mixed with potassium n-heptanoate to form a composite surfactant, such as an auxiliary agent, a solvent, and the like.

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, the reaction temperature is 50-60 ℃; the reaction time is 2-3 h.

In a second aspect, the use of said surfactant in hard water is disclosed. In particular, the surfactants provided herein function as surface active agents in hard water, such as non-foaming, oil removal, and corrosion inhibition in hard water.

Preferably, the hard water has a hardness of 500 to 50000 ppm.

In a third aspect of the application, the use of said surfactant in a lye is disclosed. Specifically, the surfactant provided by the application plays a role in surface activity in alkali liquor.

Preferably, the alkali solution is 2-20% caustic alkali solution.

In a fourth aspect, the present application provides the use of said surfactant for cleaning metals.

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 application aims to develop the surfactant which does not contain a defoaming agent, is foamless, has good cleaning power and strong alkali resistance (can resist 20% caustic alkali) and has good corrosion inhibition effect on metals. The present application has discovered that potassium n-heptanoate has superior 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.

Compared with the prior art, the surfactant disclosed by the application has the following advantages compared with the commonly used surfactants and potassium oleate on the market:

1. the surfactant has the advantages of no foam, alkali resistance, hard water resistance and good oil removal effect. The detergent can be widely applied to alkalinity, especially to a strong alkaline system used as a cleaning detergent, and has good system compatibility and excellent effect.

2. The surfactant does not contain harmful components such as benzene rings and the like, and is healthy and environment-friendly.

3. The preparation method of the surfactant is simple, easy to operate, relatively low in production cost and more beneficial to industrialization.

Detailed Description

The application provides potassium n-heptanoate, a preparation method and application thereof, which are used for solving the technical defects of poor cleaning force, no caustic alkali resistance and easy foaming of the existing surfactant.

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 commercially or self-made, the potassium oleate of the comparative example 1 is commercially available potassium oleate, and the nonylphenol polyoxyethylene ether of the comparative example 1 is commercially available nonylphenol polyoxyethylene ether.

Example 1

The application provides a surfactant, and the specific preparation method comprises the following steps:

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.

Example 2

The embodiment of the application provides foaming tests of different surfactants, and the foaming tests comprise the following specific steps:

the foaming power of example 1, comparative example 1 (potassium oleate), comparative example 2 (nonylphenol polyoxyethylene ether) was tested according to the method of testing foaming power in GB/T7462-94 "determination of foaming power of surfactant modified Ross-Miles method".

1. Preparing a working solution: respectively preparing 0.25% of working solution from example 1, comparative example 1 (potassium oleate) and comparative example 2 (nonylphenol polyoxyethylene ether), wherein the solute in the working solution is water in example 1, comparative example 1 (potassium oleate) and comparative example 2 (nonylphenol polyoxyethylene ether);

2. the temperature of the working solution of the embodiment 1, the working solution of the comparative example 1 and the working solution of the comparative example 2 is controlled to be 50 +/-0.5 ℃ in a constant-temperature water bath with a circulating water pump;

3. cleaning an instrument: washing with water, and rinsing with a small amount of solution to be detected;

4. filling part of the solution to be detected in the step 2 into a separating funnel to a 150mm scale;

5. filling part of the solution to be detected in the step 2 into a measuring cylinder to 50ml of scale;

6. weighing 500ml of solution to be tested which is 0.25 percent of the working solution of example 1, comparative example 1 (potassium oleate) and comparative example 2 (nonylphenol polyoxyethylene ether) and is kept at 50 +/-0.5 ℃ and pouring the solution to be tested into a separating funnel, and slowly performing the operation to avoid generating foams;

7. enabling the liquid in the separating funnel to continuously flow down until the liquid level is reduced to the scale of 150 mm;

8. the results are expressed in milliliters of foam formed (foam volume) at 30s, 3min, 5min, 8min, 10min, 12min and 15min after the flow had stopped.

9. The test results are shown in table 1.

TABLE 1 foam height at different times

As can be seen from Table 1, the working fluid of comparative example 1 had an initial foam amount of 55ml, a foam amount of 15ml at 15min, and a moderate foam amount, but the foam was hardly disappeared. Comparative example 2 was very rich in foam, which was not suitable for spray and the like requiring a bubble-free cleaning process. The working solution in the embodiment 1 has the initial foam amount of 0, belongs to a non-foaming surfactant, can avoid the negative influence caused by foam in the application process, and has good practical application prospect.

Example 3

The embodiment of the application provides a removal efficiency test of artificial oil stains of different surfactants, which comprises the following specific steps:

the removal efficiency of artificial oil stains in example 1, comparative example 1 (potassium oleate), and comparative example 2 (nonylphenol polyoxyethylene ether) were tested by referring to the test method for oil removal rate in JB/T4323.2-1999 "test method for water-based metal cleaner".

1. Preparing a working solution: respectively preparing 0.25% of working solution from example 1, comparative example 1 (potassium oleate) and comparative example 2 (nonylphenol polyoxyethylene ether), wherein the solute in the working solution is the working solution of example 1, comparative example 1 (potassium oleate) and comparative example 2 (nonylphenol polyoxyethylene ether), and the solvent in the working solution is water;

hanging 3 polished and cleaned test pieces with hooks, weighing on a balance to 0.1mg, wherein the weight is P₁Represents;

2. and (3) immersing the weighed test piece into artificial oil stain which is heated to 55 +/-2 ℃ in advance for more than 5min, taking out the test piece after the temperature of the test piece is the same as that of the oil, and draining until no obvious oil drops drop at the bottom of the test piece. Weighing together with the original hook, this weight being P₂And (4) showing. P₂-P₁The oil dip coating amount of the test piece was used.

3. Soaking the test pieces (fixed by original hook) in the liquid to be tested, ultrasonic cleaning at 25 deg.C for 2min, oven drying at 55 + -2 deg.C for 30min, cooling to room temperature, weighing, and weighing with weight of P₃And (4) showing. P₂-P₃The weight of the oil stain is washed off; the solutions to be tested are 0.25% of working solutions of example 1, comparative example 1 (potassium oleate) and comparative example 2 (nonylphenol polyoxyethylene ether).

4. And (4) evaluating the result: the cleaning power is expressed in terms of the oil-washing rate h and calculated according to the formula (1): the hi values of 3 samples are respectively calculated, the arithmetic mean value h of the hi values is calculated, the hi value with the error of not more than +/-2 percent is an effective value compared with the mean value h, and the mean value of the effective value is the final test result. If the effective value is less than 2, the test should be repeated.

5. The test results are shown in table 2.

TABLE 2 oil removal Rate

As is clear from table 2, the oil removal rates of example 1, comparative example 1 (potassium oleate), and comparative example 2 (nonylphenol polyoxyethylene ether) were 84.64%, 66.86%, and 77.33%, respectively. The oil removal rate was the lowest for comparative example 1 and the highest for example 1. It can be seen that example 1 has a good oil removing effect and can be used as an oil removing and degreasing agent in cleaning.

Example 4

The embodiment of the application provides hard water resistance tests of different surfactants, which specifically comprise the following steps:

hard water refers to water containing more soluble calcium magnesium compounds, and the higher the water hardness, the more likely it is to cause surface scum. Artificial water with different hardness is prepared, and the hard water resistance of the artificial water is respectively tested in example 1, comparative example 1 (potassium oleate) and comparative example 2 (nonylphenol polyoxyethylene ether).

1. With CaCl₂Preparing artificial water with different hardness with distilled water, wherein the hardness of the artificial water is respectively 500ppm, 1000ppm, 5000ppm, 10000ppm, 20000ppm and 50000 ppm.

2. Artificial water of different hardness was used to prepare 1% strength solutions of the surfactant of example 1, comparative example 1 (potassium oleate), and comparative example 2 (nonylphenol polyoxyethylene ether).

3. The stability of the solutions of example 1, comparative example 1 (potassium oleate) and comparative example 2 (nonylphenol polyoxyethylene ether) having a concentration of 1% was observed under water conditions of different hardness, and if no floc or precipitate was present, the sample was judged to be acceptable and hard water-resistant.

4. The test results are shown in table 3.

TABLE 3 hard water resistance

As can be seen from Table 3, comparative example 1 has no resistance to hard water at all, and a 1% concentration aqueous solution is white-precipitated under 500ppm hard water, comparative example 2 has a certain hard water resistance and can resist 10000ppm hard water, but 20000ppm hard water causes precipitates, example 1 has an excellent hard water resistance, and a 1% concentration aqueous solution is clear and transparent under 50000ppm ultra-high hard water without flocs or precipitates. Example 1 has a good adaptation to water hardness compared to comparative examples 1 and 2, which provides good conditions for its use in different water hardness areas.

Example 5

The embodiment of the application provides a corrosion inhibition performance test of different surfactants on red copper and brass H62, which comprises the following specific steps:

in the embodiment of the application, the corrosion inhibition performance of the surfactant in the example 1, the comparative example 1 (potassium oleate) and the comparative example 2 (nonylphenol polyoxyethylene ether) on red copper and brass H62 is tested by referring to a corrosion test method in GB6144-2010 synthetic cutting fluid.

1. Preparing a working solution: the surfactant of example 1, comparative example 1 and comparative example 2 were respectively prepared into 0.5% working solutions, wherein the solute in the working solution was the surfactant of example 1, the comparative example 1 and comparative example 2, the solvent was water, and the blank comparative example was tap water.

2. Setting the thermostat to 55 ℃, and preheating;

3. taking out the metal test piece, and washing the rust-proof oil with absolute ethyl alcohol;

4. after the metal test piece is dried, polishing the surface by 400-mesh sand paper to ensure that the surface has no pits, scratches or rusts;

5. cleaning the ground metal test piece with absorbent cotton in absolute ethyl alcohol, and wiping the metal test piece with filter paper;

6. putting the wiped metal test pieces into 50ml beakers respectively, and requiring the working solution in the step 1 to immerse the metal test pieces;

7. covering the culture dish, putting the beaker into a thermostat which is kept at the constant temperature of 55 +/-2 ℃, and recording the time for starting corrosion;

8. continuously standing for 8h, taking out the metal test piece, and comparing the metal test piece with the metal test piece before the test;

9. and (4) judging the standard: the red copper or brass H62 is qualified when reaching A or B grade.

TABLE 4 Corrosion criteria for Red copper and Brass H62

No rust and luster like new	Class A
		Slight discoloration	Class B
Moderate color change	Class C
		Severe discoloration	Class D

10. The test results are shown in table 5.

TABLE 5 Corrosion test results for copper and brass H62

As can be seen from table 5, comparative example 1 and comparative example 2, both at a concentration of 0.5%, had no corrosion inhibition on red copper and brass H62, which, as a result of the corrosion inhibition on red copper and brass H62, such as tap water, resulted in severe discoloration of red copper and brass H62. The surfactant of example 1 at a concentration of 0.5% was effective in preventing corrosion of red copper and brass H62, and had a good protective effect on red copper and brass H62.

Example 6

The embodiment of the application provides the maximum alkali resistance tests of different surfactants, and the specific steps are as follows:

aqueous solutions of different sodium hydroxide concentrations were prepared and tested for maximum alkali resistance in example 1, comparative example 1 (potassium oleate), and comparative example 2 (nonylphenol polyoxyethylene ether), respectively.

1. Preparing aqueous solutions with different alkalinity by using sodium hydroxide and distilled water.

2. Aqueous solutions of different basicities were used to prepare solutions of 1% concentration example 1, comparative example 1 (potassium oleate), and comparative example 2 (nonylphenol polyoxyethylene ether), and a 2% aqueous sodium hydroxide solution, a 3% aqueous sodium hydroxide solution, a 4% aqueous sodium hydroxide solution, a 10% aqueous sodium hydroxide solution, a 15% aqueous sodium hydroxide solution, and a 20% aqueous sodium hydroxide solution were prepared, respectively.

3. The stability of 1% concentration of the solution obtained in example 1, comparative example 1 (potassium oleate) and comparative example 2 (nonylphenol polyoxyethylene ether) in different alkalinity water conditions is observed, and the amount of alkali used when delamination or oil bleaching occurs is the maximum alkali resistance.

4. The test results are shown in Table 6.

TABLE 6 alkali resistance

From the alkali resistance test of table 6, it can be seen that comparative example 1 (potassium oleate) is not resistant to caustic soda flakes, comparative example 2 (nonylphenol polyoxyethylene ether) is resistant to up to 4% caustic soda flakes, and example 1 is resistant to 20% caustic soda flakes, which is far superior to comparative example 1 (potassium oleate) and comparative example 2 (nonylphenol polyoxyethylene ether), in alkali resistance, which is very advantageous for the application of the surfactant of the present application in alkaline and strongly alkaline cleaners.

By comparing example 1, comparative example 1 (potassium oleate), comparative example 2 (nonylphenol polyoxyethylene ether), it was found that: comparative example 1 (potassium oleate) is a carboxylate as in example 1, but comparative example 1 (potassium oleate) is not hard water resistant and has poor oil removal. Comparative example 2 (nonylphenol polyoxyethylene ether) had a certain oil-removing effect, but was rich in foam and corroded with red copper and brass H62. The embodiment 1 combines all the advantages of the comparative example 1 (potassium oleate) and the comparative example 2 (nonylphenol polyoxyethylene ether), has more excellent performance, is free of bubbles, is alkali-resistant and hard-water-resistant, and has good corrosion inhibition on red copper and brass H62, and the surfactant in the embodiment of the application has a good oil removing effect on the artificial oil stain.

Comparative example 3

The application provides a first contrast potassium n-heptate, which is prepared by the following specific steps:

the comparative potassium n-heptanoate of the present application was prepared in a similar manner to that of example 1 except that n-heptanoate was used in an excessive amount and the molar ratio of n-heptanoate to potassium hydroxide was 1:0.5 to obtain product 1, and the water solubility of product 1 was examined from example 1, and it was found that the water solubility of product 1 synthesized in the comparative example of the present application was poor.

Comparative example 4

The application provides a second control potassium n-heptanoate, which comprises the following specific preparation methods:

the preparation method of the comparative potassium n-heptanoate is similar to that of the example 1, and is different from the method in that the mass fraction of the potassium hydroxide solution is too high, the molar ratio of the n-heptanoic acid to the potassium hydroxide is 1:1.2, the mass fraction of the potassium hydroxide solution is 60%, the product 2 is prepared, the property of the product 2 is detected, and the product 2 synthesized by the comparative example is pasty, pasty or powdery, wherein the potassium n-heptanoate of the product 2 is high in viscosity, easy to agglomerate and inconvenient to store.

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

1. The potassium n-heptate is used as an oil removing and degreasing agent in metal cleaning; the potassium n-heptanoate has a structure shown in the formula I;

formula I;

the preparation method of the potassium n-heptate comprises the following steps:

reacting n-heptanoic acid with a potassium hydroxide aqueous solution to prepare potassium n-heptanoate;

the molar ratio of the n-heptanoic acid to the potassium hydroxide aqueous solution is 1: (1.1-1.3); the mass fraction of the potassium hydroxide aqueous solution is 20-30%.

2. The use of claim 1, wherein the reaction temperature is 50 ℃ to 60 ℃; the reaction time is 2-3 h.

3. Use according to claim 1, wherein the potassium n-heptanoate is used in hard water.

4. The use of claim 3, wherein the hard water has a hardness of 500 to 50000 ppm.

5. Use according to claim 1, wherein the potassium n-heptanoate is used in a lye.

6. The use according to claim 5, wherein the lye is 2% to 20% caustic solution.