CN112479907A

CN112479907A - Triisopropanolamine n-heptanoate soap, preparation method and application thereof, and metal cleaning agent

Info

Publication number: CN112479907A
Application number: CN202011354850.3A
Authority: CN
Inventors: 何彦波; 何锦梅
Original assignee: Dexu New Materials Fogang Co ltd
Current assignee: Dexu New Materials Fogang Co ltd
Priority date: 2020-11-27
Filing date: 2020-11-27
Publication date: 2021-03-12
Anticipated expiration: 2040-11-27
Also published as: CN112479907B

Abstract

The application belongs to the technical field of surfactants, and particularly relates to triisopropanolamine n-heptanoate soap, a preparation method and application thereof, and a metal cleaning agent. The application provides triisopropanolamine n-heptanoate soap in a first aspect, and the structural formula of the triisopropanolamine n-heptanoate soap is shown as a formula I. In a second aspect, the present application provides a method for preparing triisopropanolamine n-heptanoate soap, comprising the steps of: heating n-heptanoic acid and triisopropanolamine to react to prepare the triisopropanolamine soap of n-heptanoic acid. In a third aspect, the present application provides a metal cleaner comprising triisopropanolamine n-heptanoate soap. The triisopropanolamine n-heptanoate soap, the preparation method and the application thereof, and the metal cleaning agent can effectively overcome the defects that the existing surfactant can not have the performances of rust prevention, lubrication, cleaning, no/low foam, alkali resistance and hard water resistance.

Description

Triisopropanolamine n-heptanoate soap, preparation method and application thereof, and metal cleaning agent

Technical Field

The application belongs to the technical field of surfactants, and particularly relates to triisopropanolamine n-heptanoate soap, a preparation method and application thereof, and a metal cleaning agent.

Background

The metal cleaning is one of indispensable processes in modern industrial production, and aims at cleaning and washing before and after metal processing and during the use of metal equipment. The existence of the dirt not only affects the appearance quality, the service performance and the service life of the product, but also affects the whole process when the dirt is serious.

The metal cleaning agents commonly used at present are generally classified into solvent type, semi-solvent type and water-based type. The solvent type cleaning mainly depends on organic solvent to dissolve dirt to achieve the purpose of cleaning, has good cleaning effect, is volatile, has low flash point and strong toxicity, generates a large amount of VOC emission, and is not environment-friendly. The semi-solvent type also has the problem of environmental protection. The water-based metal cleaning agent mainly comprises a surfactant, and a small amount of a builder, a corrosion inhibitor, a defoaming agent, a cosolvent, an anti-redeposition agent and the like are added.

The development and cleaning effect is good, the efficiency is high, the cost is low, the range is wide, and the cleaner which is more environment-friendly becomes the inevitable trend of the metal cleaning development, so that the selection of the surfactant plays a critical role. The prior surfactant can not have multiple performances of rust prevention, lubrication, cleaning, no/low foam, alkali resistance, hard water resistance and the like. Therefore, it is an urgent technical problem to be solved by those skilled in the art to develop a substance having various properties such as rust prevention, lubrication, cleaning, no/low foaming, alkali resistance, and hard water resistance.

Disclosure of Invention

In view of the above, the application provides triisopropanolamine n-heptanoate soap, a preparation method and application thereof, and a metal cleaning agent, and effectively overcomes the defects that the existing surfactant cannot have the performances of rust prevention, lubrication, cleaning, no/low foam, alkali resistance and hard water resistance.

The application provides a triisopropanolamine n-heptanoate soap, which has a structural formula shown as a formula I:

in a second aspect, the present application provides a method for preparing triisopropanolamine n-heptanoate soap, comprising the steps of:

heating n-heptanoic acid and triisopropanolamine to react to prepare the triisopropanolamine soap of n-heptanoic acid.

In the preparation method of the triisopropanolamine n-heptanoate soap, n-heptanoic acid with a low carbon chain is selected to react with isomeric triisopropanolamine, so that the triisopropanolamine n-heptanoate soap has no/low foaming property.

Preferably, the temperature of the heating reaction is 110-130 ℃; the heating reaction time is 2-4 h.

Preferably, the n-heptanoic acid is n-heptanoic acid with a temperature of 75 ℃ to 85 ℃.

Preferably, the method comprises the following steps of:

18 to 25 percent of n-heptanoic acid;

75 to 82 percent of triisopropanolamine.

More preferably, the method comprises the following steps of:

21% of n-heptanoic acid;

79% of triisopropanolamine.

In particular, in the preparation method of the n-heptanoic acid triisopropanolamine soap, the reaction ratio of n-heptanoic acid and triisopropanolamine influences the performance of the composition. The higher the proportion of n-heptanoic acid, the better the lubricity and the poorer the water solubility. Accordingly, the more triisopropanolamine, the better the water solubility. The key point is the reaction ratio of the heptanoic acid and the triisopropanolamine to obtain the multifunctional surfactant with good water solubility, good lubricating property and good rust prevention.

The third aspect of the application provides the application of the triisopropanolamine n-heptanoate soap or the triisopropanolamine n-heptanoate soap prepared by the preparation method in a metal cleaning agent.

The fourth aspect of the application provides a metal cleaning agent, which comprises the triisopropanolamine n-heptanoate soap or the triisopropanolamine n-heptanoate soap prepared by the preparation method.

Preferably, the metal cleaner comprises: triisopropanolamine n-heptanoate soap, an alkaline assistant, an organic solvent, a chelating agent and water.

Preferably, the method comprises the following steps of:

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

the organic solvent is selected from one or more of isopropanol, ethylene glycol monobutyl ether, dipropylene glycol butyl ether, diethylene glycol butyl ether and dipropylene glycol methyl ether;

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

More preferably, the metal cleaning agent comprises the following components in percentage by mass

Preferably, the pH value of the metal cleaning agent is 9.0-10.0.

It is noted that the addition of an alkaline assistant, particularly a strong alkali such as caustic soda, is effective for improving the cleaning property of the metal cleaner. In general, alkaline cleaning systems, the higher the alkalinity, the more advantageous the cleaning. However, too high alkalinity also tends to cause problems such as hand injury, corrosion of metals, and the like. The metal cleaning agent has the pH value of 9.0-10.0, and can realize the cleaning effect of a strong alkaline cleaning agent.

The application aims to develop a multifunctional surfactant which has multiple performances of rust prevention, lubrication, cleaning, no/low foam, alkali resistance, hard water resistance and the like, is comprehensive and superior in performance, enables metal cleaning to be convenient, cheap and efficient, and effectively solves the problems of incompatibility, layering, precipitation and the like of components in the existing metal cleaning agent. The application provides triisopropanolamine n-heptanoate soap, a preparation method and application thereof, and a metal cleaning agent, wherein the triisopropanolamine n-heptanoate soap has the following advantages compared with a surfactant and an oleic acid potassium salt which are commonly used on the market:

1. the preparation method of the n-heptanoic acid triisopropanolamine soap is simple, easy to operate, relatively low in production cost and more beneficial to industrialization.

2. The n-heptanoic acid triisopropanol amine soap does not contain harmful components such as benzene rings and the like, and is healthy and environment-friendly.

3. The triisopropanolamine n-heptanoate soap has the advantages of no bubbles, alkali resistance, oil removal and good compatibility in practical application. Can be widely applied to systems with different alkalinity as cleaning surfactants.

4. The n-heptanoic acid triisopropanolamine soap has good antirust property, can reduce the dosage of an antirust agent in practical application, and saves production cost.

In summary, the triisopropanolamine n-heptanoate soap simultaneously has the performances of no/low foamability, lubrication, rust prevention, alkali resistance, cleaning, alkali resistance and no need of adding a defoaming agent.

Drawings

In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.

FIG. 1 is a graph of the infrared spectrum of triisopropanolamine n-heptanoate soap provided herein in deuterium water;

FIG. 2 is a graph showing the results of NMR spectroscopy in deuterium for triisopropanolamine n-heptanoate provided herein;

FIG. 3 is a comparative reference chart of the judgment criteria for 2h cast iron scrap in example 6 provided in the present application.

Fig. 4 is a tapping torque graph of various lubricants provided in embodiments of the present application.

Detailed Description

The application provides triisopropanolamine n-heptanoate soap, a preparation method and application thereof, and a metal cleaning agent, which are used for solving the defects that in the prior art, a surfactant cannot always have the performances of rust prevention, lubrication, cleaning, no/low foam, alkali resistance and hard water resistance.

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.

The preparation method of the triisopropanolamine n-heptanoate comprises the following steps:

(1) putting 18-25% by mass of n-heptanoic acid into a reaction kettle, and heating to 80 ℃ for later use;

(2) triisopropanolamine with the mass percent of 75-82% is slowly put into a reaction kettle to react for 2-4 h at the temperature of 110-130 ℃,

(3) stopping heating, naturally cooling to room temperature, and discharging to obtain the triisopropanolamine n-heptanoate soap.

Wherein, the reagents or raw materials used in the following examples are all sold in the market or made by the user; wherein, the comparative example 1 is the prior commonly used metal cleaning agent, namely triethanolamine oleic acid soap; comparative example 2 is a conventional nonionic surfactant, fatty acid methyl ester polyoxyethylene ether.

Example 1

The embodiment of the application provides a first preparation method of triisopropanolamine n-heptanoate, which comprises the following steps:

(1) putting 21% n-heptanoic acid into a reaction kettle, and heating to 80 ℃ for later use;

(2) 79 percent of triisopropanolamine is slowly put into a reaction kettle to react for 3 hours at the temperature of 125 ℃,

(3) the heating was stopped, the mixture was allowed to cool to room temperature, and the product was discharged and labeled as example 1.

The results of the infrared spectrogram and the nuclear magnetic resonance hydrogen spectrum detection of the triisopropanolamine n-heptanoate prepared in the examples are shown in fig. 1-2, and fig. 1-2 illustrate that the triisopropanolamine n-heptanoate soap successfully prepared in the examples is shown in the examples.

Example 2

The embodiment of the application provides a second preparation method of triisopropanolamine n-heptanoate, which comprises the following steps:

(1) putting 18% of n-heptanoic acid into a reaction kettle, and heating to 80 ℃ for later use;

(2) slowly adding 82% triisopropanolamine into a reaction kettle, reacting for 3 hours at 125 ℃,

(3) the heating was stopped, allowed to cool to room temperature and the batch discharged, as labeled in example 2.

Example 3

The embodiment of the application provides a preparation method of a third triisopropanolamine n-heptanoate soap:

(1) putting 25% of n-heptanoic acid into a reaction kettle, and heating to 80 ℃ for later use;

(2) slowly adding 75% triisopropanolamine into a reaction kettle, reacting for 3 hours at 125 ℃,

(3) the heating was stopped, allowed to cool to room temperature and the batch discharged, as identified in example 3.

Example 4

The examples of the present application provide tests for measuring the foaming power of the triisopropanolamine n-heptanoate soap of example 1, comprising the following specific steps:

the foaming power of example 1, comparative example 1 (triethanolamine oleate soap), comparative example 2 (fatty acid methyl ester polyoxyethylene ether) was tested according to the method of GB/T7462-94 measurement of foaming power of surfactant modified Ross-Miles method for foaming power.

1. Preparing a working solution: respectively configuring example 1, comparative example 1 and comparative example 2 into 0.25% of working solutions, wherein the solute in the working solutions is example 1, comparative example 1 and comparative example 2, and the solvent is tap water;

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

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

4. filling part of liquid to be detected into a separating funnel to a 150mm scale;

5. filling part of liquid to be detected into a measuring cylinder to 50ml of scale;

6. weighing 500ml of liquid to be detected which is kept at 50 +/-0.5 ℃ and poured into a separating funnel, and slowly performing the operation to avoid generating foams, wherein the liquid to be detected is 0.25% of the working solution of the example 1, the comparative example 1 and the comparative example 2 respectively;

7. the liquid in the separating funnel continuously flows down until the liquid level drops to the 150mm scale;

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 for example 1, comparative example 1 and comparative example 2

10. And (4) test conclusion:

comparative example 1 the initial amount of foam was 320ml and the amount of foam at 15min was 90ml, which was very rich in foam. Comparative example 2 had a small amount of foam and was a low foam product. The initial foam amount of the foam is 0 in example 1, the foam belongs to a non-foaming surfactant, negative effects caused by foam in the application process can be avoided, and the foam has a good practical application prospect.

Example 5

The embodiment of the application provides a test for measuring the removal efficiency of the triisopropanolamine n-heptanoate soap of embodiment 1 on artificial oil stains, and the specific steps are as follows:

the removal efficiency of the artificial oil stains in example 1, comparative example 1 and comparative example 2 was tested with reference to the test method for oil removal rate in JB/T4323.2-1999 test method for Water-based Metal cleaners.

1. 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, the 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 15-30min, cooling to room temperature, weighing, and weighing₃And (4) showing. P₂-P₃The weight of the oil stain is washed off.

4. And (4) evaluating the result:

the cleaning power is expressed in terms of the oil-washing rate hi and is calculated according to the formula (1): the hi values of 3 samples are respectively obtained, the arithmetic mean value h 'of the hi values is obtained, the hi values of the samples are compared with the arithmetic mean value h', the hi values with the error of not more than +/-2% are effective values, and the mean value of the effective values 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 rates of example 1, comparative example 1 and comparative example 2

6. And (4) experimental conclusion:

the oil removal rates of example 1, comparative example 1, and comparative example 2 were 78.56%, 54.97%, and 69.71%, respectively. Therefore, the oil removal rate of comparative example 1 was the lowest, and the oil removal rate of example 1 was the highest. It can be seen that example 1 has a better oil removal effect and can be applied to cleaning as an oil removal degreasing agent.

Example 6

The examples of the present application provide a test for determining the iron filings of the triisopropanolamine n-heptanoate soap of example 1, comprising the following specific steps:

1. preparing a working solution: respectively configuring example 1, comparative example 1 and comparative example 2 into 1% of corresponding working solutions, wherein the solute in the working solutions is example 1, comparative example 1 and comparative example 2, and the solvent is tap water; the blank comparative example was tap water.

2. The test steps are as follows: putting filter paper into a culture dish, weighing 2g +/-0.1 g of GG25 cast iron chips, spreading the GG25 cast iron chips on the filter paper, transferring 2ml of liquid to be detected by a dropper to wet all the cast iron chips, covering the culture dish, naturally placing for 2 hours at 18-28 ℃, washing off the cast iron chips on the filter paper by tap water, soaking the filter paper in acetone liquid for 5 seconds, and naturally drying at room temperature (18-28 ℃), wherein the evaluation standard of the cast iron chips is shown in Table 3. The test result is evaluated according to the number of rusty spots on the filter paper according to a grade of 0-4;

TABLE 3 existing criterion for evaluation of 2h cast iron filings

3. The test results are shown in Table 4.

TABLE 4 2h cast iron scrap test results of example 1, comparative example 1 and comparative example 2

4. And (4) test conclusion:

the results of the 2h tap water cast iron filing test show that example 1 has excellent rust inhibitive properties. The rust inhibitive performance of comparative example 1 and comparative example 2 was also inferior to that of example 1 of the present application.

Example 7

The examples of the present application provide the maximum alkali resistance test for the triisopropanolamine n-heptanoate soap of example 1, comprising the following specific steps:

aqueous solutions of different sodium hydroxide concentrations were prepared and tested for maximum alkali resistance for example 1, comparative example 1, and comparative example 2, respectively.

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

2. Aqueous solutions of different alkalinity were used to prepare solutions of 1% concentration example 1, comparative example 2.

3. The stability of the 1% concentration example 1, the comparative example 1 and the comparative example 2 under different alkalinity water conditions is observed, and the alkali dosage when layering or floating oil occurs is the maximum alkali resistance.

4. The test results are shown in table 6.

TABLE 6 alkali resistance of example 1, comparative example 1 and comparative example 2

5. And (4) test conclusion:

according to the alkali resistance test, the comparative example 1 cannot resist caustic soda flakes, and the comparative example 2 can resist 4% of caustic soda flakes at most, so that the conventional surfactant cannot resist strong alkali and can be layered in a strong alkali system; in contrast, no delamination occurs in the case of 2-20% caustic soda flake system in example 1, and it can be seen that the triisopropanolamine n-heptanoate soap of the present application can resist 20% caustic soda flake and has an alkali resistance far superior to that of comparative examples 1 and 2, and it can be seen that the triisopropanolamine n-heptanoate soap of the present application can be widely applied to alkaline and strongly alkaline cleaning agents.

By comparing example 1, comparative example 1 and comparative example 2, it was found that: comparative example 1 is soap like example 1, but comparative example 1 has abundant foam and is difficult to eliminate, the oil removal rate is also poor, and the rust resistance is general. Comparative example 2 has a certain oil removing effect, but the rust prevention is poor. The embodiment 1 has all the advantages of the comparative example 1 and the comparative example 2, has more excellent performance, has no bubbles, good alkali resistance and good rust resistance, has good oil removing effect on artificial oil stains by using a single agent, and is a multifunctional surfactant.

Example 8

The embodiment of the application provides the tapping tests of the embodiment 1, the comparative example 1 and the comparative example 2, and the specific steps comprise:

a metal material provided with a prepared hole was directly subjected to a tapping test using a simulation tester, and the lubricating property of the machining was evaluated using an average torque value. Theoretically, the lower the tapping torque value, the better the lubricity.

1% working solutions of example 1, comparative example 1 and comparative example 2 were prepared using the solutes of example 1, comparative example 1 and comparative example 2, respectively, and tap water as a solvent.

The 1% working fluids of example 1, comparative example 1 and comparative example 2 were subjected to tapping tests, respectively. The test parameters were as follows: rotating speed: 1200 rpm; tapping depth: 12 mm; torsion: 400 Ncm; the tap type: m4 press tap; the material quality of the test block is as follows: 7075 and (3) aluminum. The average torque values are shown in table 7 and the tapping torque profile is shown in fig. 4.

TABLE 7 mean Torque values

Example 9

The embodiment of the application provides a metal cleaning agent, and the specific preparation method comprises the following steps:

according to the total mass of the preset metal cleaning agent, 12% by mass of triisopropanolamine n-heptanoate soap, 2% by mass of sodium hydroxide, 5% by mass of sodium metasilicate pentahydrate, 3% by mass of sodium carbonate, 1% by mass of tetrasodium ethylenediaminetetraacetate and 77% by mass of deionized water are sequentially added. Stir well with a stirrer until well mixed and labeled product 1.

Comparative example 3

The embodiment of the application provides a reference product, and the specific preparation method comprises the following steps:

according to the total mass of the preset control product, 12% by mass of triethanolamine oleate soap, 2% by mass of sodium hydroxide, 5% by mass of sodium metasilicate pentahydrate, 3% by mass of sodium carbonate, 1% by mass of ethylenediaminetetraacetic acid tetrasodium salt and 77% by mass of deionized water are sequentially added. . Stir well with a stirrer until well mixed, and mark as product 2.

Example 10

The present application provides a test for determining the removal efficiency of the product 1 of example 9 and the product 2 of comparative example 3 for artificial oil stains, comprising the following specific steps:

the test methods of the examples of the present application were as described in example 5, and the test results are shown in Table 8.

TABLE 8 oil removal rates for product 1 and product 2

As can be seen from table 8, the oil removal rates of product 1 of example 9 and product 2 of comparative example 3 were 96.48% and 77.06%, respectively. Therefore, the triisopropanolamine n-heptanoate soap can be applied to metal cleaning agents as an oil removal degreasing agent.

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 triisopropanolamine n-heptanoate soap is characterized by having a structural formula shown as a formula I:

2. the method for producing triisopropanolamine n-heptanoate soap according to claim 1, comprising the steps of:

3. The preparation method according to claim 2, wherein the temperature of the heating reaction is 110 ℃ to 130 ℃; the heating reaction time is 2-4 h.

4. The production method according to claim 2, wherein the n-heptanoic acid is n-heptanoic acid having a temperature of 75 ℃ to 85 ℃.

5. The preparation method according to claim 2, comprising the following steps of:

18 to 25 percent of n-heptanoic acid;

75 to 82 percent of triisopropanolamine.

6. Use of triisopropanolamine n-heptanoate soap according to claim 1 or the preparation process according to any one of claims 2 to 5 in metal cleaners.

7. A metal cleaner comprising the triisopropanolamine n-heptanoate soap according to claim 1 or the triisopropanolamine n-heptanoate soap produced by the production method according to any one of claims 2 to 5.

8. The metal cleaner of claim 7, comprising: triisopropanolamine n-heptanoate soap, an alkaline assistant, an organic solvent, a chelating agent and water.

9. The metal cleaner as claimed in claim 8, which comprises the following components by mass percent:

10. the metal cleaner according to claim 8, wherein the alkaline assistant is one or more selected from caustic alkali, sodium carbonate, anhydrous sodium metasilicate, sodium bicarbonate, and triethanolamine;