阅读说明：本技术 一种高效咪唑啉型防锈剂的制备方法及其组合应用 (Preparation method and combined application of efficient imidazoline type antirust agent ) 是由 袁小二 徐坤 范金凤 于 2021-07-01 设计创作，主要内容包括：本发明公开了一种高效咪唑啉型防锈剂的制备方法,包括以下步骤：(1)、搭建分水装置,在四口烧瓶中加入称量好的植物油酸,开启搅拌,在氮气保护下开启升温,当温度升至100℃时,开始向反应瓶中滴加多烯多胺,当温度升至140-180℃时,保温反应3-6h；(2)、然后继续升温至180-260℃,并保温反应3-6h,停止反应,并开始降温,即可得到淡黄色咪唑啉衍生物；(3)、当温度降至60℃时,向反应瓶中加入十二烯基丁二酸酐,过程中控制反应温度不超过125℃,温度升至125℃继续反应3-4h,即可获得油溶性良好且防锈性能优越的高效咪唑啉型防锈剂。通过该方法制得的高效咪唑啉型防锈剂在各种粘度基础油中都有优秀的溶解效果。(The invention discloses a preparation method of a high-efficiency imidazoline type antirust agent, which comprises the following steps: (1) building a water distribution device, adding weighed vegetable oleic acid into a four-mouth flask, starting stirring, starting under the protection of nitrogen, heating, starting to dropwise add polyene polyamine into a reaction bottle when the temperature is raised to 100 ℃, and preserving heat for reaction for 3-6 hours when the temperature is raised to 140-180 ℃; (2) then, continuously heating to 180-260 ℃, carrying out heat preservation reaction for 3-6h, stopping the reaction, and beginning cooling to obtain a light yellow imidazoline derivative; (3) when the temperature is reduced to 60 ℃, adding dodecenyl succinic anhydride into a reaction bottle, controlling the reaction temperature not to exceed 125 ℃ in the process, raising the temperature to 125 ℃, and continuing to react for 3-4 hours to obtain the high-efficiency imidazoline type antirust agent with good oil solubility and excellent antirust performance. The high-efficiency imidazoline type antirust agent prepared by the method has excellent dissolving effect in base oil with various viscosities.)

1. The preparation method of the high-efficiency imidazoline type antirust agent is characterized by comprising the following steps:

(1) building a water distribution device, adding weighed vegetable oleic acid into a four-mouth flask, starting stirring, starting under the protection of nitrogen, heating, starting to dropwise add polyene polyamine into a reaction bottle when the temperature is raised to 100 ℃, and preserving heat for reaction for 3-6 hours when the temperature is raised to 140-180 ℃;

(2) then, continuously heating to 180-260 ℃, carrying out heat preservation reaction for 3-6h, stopping the reaction, and beginning cooling to obtain a light yellow imidazoline derivative;

(3) when the temperature is reduced to 60 ℃, adding dodecenyl succinic anhydride into a reaction bottle, controlling the reaction temperature not to exceed 125 ℃ in the process, raising the temperature to 125 ℃, and continuing to react for 3-4 hours to obtain the high-efficiency imidazoline type antirust agent with good oil solubility and excellent antirust performance.

2. The method as claimed in claim 1, wherein the stirring speed in step (1) is 400 r/min.

3. The process according to claim 1, wherein the polyene polyamine in the step (1) is triethylene tetramine.

4. The process according to claim 1, wherein the molar ratio of the polyene polyamine to the vegetable oleic acid in the step (1) is 1.1: 1.

5. the method according to claim 1, wherein the imidazoline derivative of step (1) has the following structural formula:

wherein R1 is heptadecenyl.

6. The method according to claim 1, wherein the mass ratio of the dodecenyl succinic anhydride to the vegetable oleic acid in the step (3) is 1.4 to 1.9: 1.

7. the method of claim 1, wherein the formula of the high-efficiency imidazoline-type rust inhibitor in the step (3) is as follows:

wherein R1 is heptadecenyl and R is dodecenyl.

8. The high-performance imidazoline type rust inhibitor prepared by the preparation method of any one of claims 1 to 7 is combined with triazole derivatives for use.

9. The combined application of claim 8, wherein the molar ratio of the high-efficiency imidazoline-type antirust agent to the triazole-type derivative is (1-3): (0.1-3).

10. The combined use according to claim 9, wherein the triazole derivative is selected from one or more of triazole derivative T406, triazole derivative T551 and triazole derivative T571.

Technical Field

The invention belongs to the technical field of antirust agents, and particularly relates to a preparation method and combined application of a high-efficiency imidazoline type antirust agent.

Background

The metal corrosion causes great loss for national economy, under the background, the application of the antirust agent is generated, and the imidazoline type antirust agent becomes one of the main corrosion inhibitors used at home and abroad due to the characteristics of low toxicity, high performance and good stability, for example, the imidazoline type corrosion inhibitor has high corrosion inhibition performance due to the imidazoline and the derivatives thereof, and the dosage of the imidazoline type corrosion inhibitor is the largest in organic corrosion inhibitors used in a plurality of oil fields at home and abroad. Because the corrosion inhibitor can well form a protective film on the metal surface, the corrosion inhibitor is often used as an antirust agent for lubricating oil.

The imidazoline type antirust agent has the advantage of low acid value, but the traditional imidazoline carboxylate type antirust agents such as T703 and the like or the simple polycyclic imidazoline type antirust agents have the problems of poor oil solubility and the like in application, and the situation that the imidazoline type antirust agent cannot be dissolved clearly often occurs when the imidazoline type antirust agent is used in oil products with high viscosity; on the other hand, the rust inhibitor of the category usually needs a larger dosage to meet the rust prevention requirement of the oil product, namely, the rust prevention performance of the rust inhibitor has a larger difference with the rust inhibitors of other categories. As the lubricating oil additive, the oil solubility and the rust prevention are the most concerned and easily detected indexes by users, and the indexes largely determine the application range of the rust inhibitor.

The patent CN110256353A discloses a method for synthesizing imidazoline rust inhibitor, which considers the oil solubility of imidazoline rust inhibitor in low-viscosity base oil, and by the method, the rust inhibitor which is well applied to low-viscosity oil products can be obtained, but the solubility of the product in high-viscosity oil products is poor, and the application range of the product is limited to a great extent.

When imidazoline type antirust agents on the market are subjected to liquid phase rust detection according to the GB/T11143B method, the fact that a rust-free result cannot be obtained when the adding amount is 0.2% or even 0.5%, the adding amount corresponds to a complexing agent and has a large proportion, so that the rust-free result of seawater rust can not be achieved when the imidazoline type antirust agents are used alone, and good rust prevention effect can be achieved by compounding with other antirust agents in most cases in the prior art, but other properties of the complexing agent are not improved.

Disclosure of Invention

The invention aims to make up the defects of the prior art and provides a preparation method of a high-efficiency imidazoline type antirust agent.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a preparation method of a high-efficiency imidazoline type antirust agent, which comprises the following steps:

(1) building a water distribution device, adding weighed vegetable oleic acid into a four-mouth flask, starting stirring, starting under the protection of nitrogen, heating, starting to dropwise add polyene polyamine into a reaction bottle when the temperature is raised to 100 ℃, and preserving heat for reaction for 3-6 hours when the temperature is raised to 140-180 ℃;

(2) then, continuously heating to 180-260 ℃, carrying out heat preservation reaction for 3-6h, stopping the reaction, and beginning cooling to obtain a light yellow imidazoline derivative;

(3) when the temperature is reduced to 60 ℃, adding dodecenyl succinic anhydride into a reaction bottle, controlling the reaction temperature not to exceed 125 ℃ in the process, raising the temperature to 125 ℃, and continuing to react for 3-4 hours to obtain the high-efficiency imidazoline type antirust agent with good oil solubility and excellent antirust performance.

Preferably, the stirring speed in the step (1) is 300-400 r/min.

Preferably, the polyene polyamine in step (1) is triethylene tetramine.

Preferably, the molar ratio of the polyene polyamine to the vegetable oil acid in step (1) is 1.1: 1.

Preferably, the imidazoline derivative of step (1) has the following structural formula:

wherein R1 is heptadecenyl.

Preferably, the mass ratio of the dodecenyl succinic anhydride to the vegetable oleic acid in the step (3) is vegetable oleic acid (1.4-1.9): 1.

preferably, the formula of the high-efficiency imidazoline type antirust agent in the step (3) is as follows:

wherein R1 is heptadecenyl and R is dodecenyl.

The invention also provides the combined application of the prepared high-efficiency imidazoline type antirust agent and the triazole derivative.

Preferably, the molar ratio of the high-efficiency imidazoline type antirust agent to the triazole derivative is (1-3): (0.1-3).

Preferably, the triazole derivative is selected from one or more of triazole derivative T406, triazole derivative T551 and triazole derivative T571.

The invention has the advantages that:

the high-efficiency imidazoline-type antirust agent prepared by the method is an amide compound, an amide structure is introduced, the polarity is weakened, the oil solubility is enhanced, and the high-efficiency imidazoline-type antirust agent is suitable for oil products with various viscosities, so that the high-efficiency imidazoline-type antirust agent can be better contacted with a metal surface, the antirust performance is improved, in addition, the high-efficiency imidazoline-type antirust agent has high-free-degree-COOH in the structure, has relatively high activity, can better react with the metal surface, and further has a better antirust effect, and the high-efficiency imidazoline-type antirust agent prepared by the method has excellent dissolving effects in base oil with various viscosities; the invention also can enable the imidazoline type antirust agent to have good antirust effect at low dosage by compounding with the triazole derivative, and can remarkably improve the oxidation resistance of the imidazoline type antirust agent.

Drawings

FIG. 1 shows the chemical reaction formula of the high-efficiency imidazoline type antirust agent, wherein R1 is heptadecenyl, and R is dodecenyl.

Detailed Description

The following examples are merely illustrative of the present invention in detail, but it should be understood that the scope of the present invention is not limited to these examples.

Example 1

A preparation method of a high-efficiency imidazoline type antirust agent comprises the following steps:

(1) the water separation device is built, 42.37g of weighed vegetable oleic acid is added into a four-mouth flask, stirring is started, the stirring speed is 300r/min, the temperature is raised under the protection of nitrogen, triethylene tetramine is dripped into a reaction bottle when the temperature is raised to 100 ℃, and the molar ratio of the triethylene tetramine to the vegetable oleic acid is 1.1: 1, when the temperature is raised to 140 ℃, keeping the temperature for reaction for 6 hours;

(2) then, continuously heating to 180 ℃, keeping the temperature for reaction for 6 hours, stopping the reaction, and beginning to cool to obtain a faint yellow imidazoline derivative;

(3) and when the temperature is reduced to 60 ℃, 60g of dodecenyl succinic anhydride is added into a reaction bottle, the reaction temperature is controlled not to exceed 125 ℃ in the process, the temperature is increased to 125 ℃, and the reaction is continued for 3 hours, so that the high-efficiency imidazoline type antirust agent with good oil solubility and excellent antirust performance can be obtained.

Example 2

A preparation method of a high-efficiency imidazoline type antirust agent comprises the following steps:

(1) the water separation device is built, 42.37g of weighed vegetable oleic acid is added into a four-mouth flask, stirring is started, the stirring speed is 350r/min, the temperature is raised under the protection of nitrogen, triethylene tetramine is dripped into a reaction bottle when the temperature is raised to 100 ℃, and the molar ratio of the triethylene tetramine to the vegetable oleic acid is 1.1: 1, when the temperature is increased to 160 ℃, keeping the temperature for reaction for 4.5 hours;

(2) then, continuously heating to 220 ℃, carrying out heat preservation reaction for 4.5 hours, stopping the reaction, and beginning to cool to obtain a faint yellow imidazoline derivative;

(3) and when the temperature is reduced to 60 ℃, 70g of dodecenyl succinic anhydride is added into a reaction bottle, the reaction temperature is controlled not to exceed 125 ℃ in the process, the temperature is increased to 125 ℃, and the reaction is continued for 3.5 hours, so that the high-efficiency imidazoline type antirust agent with good oil solubility and excellent antirust performance can be obtained.

Example 3

A preparation method of a high-efficiency imidazoline type antirust agent comprises the following steps:

(1) the water separation device is built, 42.37g of weighed vegetable oleic acid is added into a four-mouth flask, stirring is started, the stirring speed is 400r/min, the temperature is raised under the protection of nitrogen, triethylene tetramine is dripped into a reaction bottle when the temperature is raised to 100 ℃, and the molar ratio of the triethylene tetramine to the vegetable oleic acid is 1.1: 1, when the temperature is increased to 180 ℃, keeping the temperature and reacting for 3 hours;

(2) then, continuously heating to 260 ℃, keeping the temperature for reaction for 3 hours, stopping the reaction, and beginning to cool to obtain a faint yellow imidazoline derivative;

(3) and when the temperature is reduced to 60 ℃, adding 80g of dodecenyl succinic anhydride into a reaction bottle, controlling the reaction temperature not to exceed 125 ℃ in the process, raising the temperature to 125 ℃, and continuing to react for 4 hours to obtain the high-efficiency imidazoline type antirust agent with good oil solubility and excellent antirust performance.

Example 4

The high-efficiency imidazoline type antirust agent prepared in the example 1 and a triazole derivative T406 are mixed according to a molar ratio of 1: 0.1, compounding.

Example 5

Mixing the high-efficiency imidazoline type antirust agent prepared in the embodiment 2 with triazole derivatives T406, T551 and T571 in a molar ratio of 3: 1: 1: 1, compounding.

Example 6

The high-efficiency imidazoline type antirust agent in the embodiment 3 is mixed with triazole derivative T551 and triazole derivative T571 according to the molar ratio of 2: 1: 1, compounding.

Comparative example 1:

imidazoline-type rust inhibitors synthesized according to the method disclosed in patent CN 110256353A.

The results of comparing the rust inhibitive performance, oxygen resistance and oil solubility (in 80 w/90) of the imidazoline type rust inhibitive agent prepared in comparative example 1 with those of the high efficiency imidazoline type rust inhibitive agents of examples 1 to 3 are shown in Table 1:

TABLE 1

The performance results of the rust inhibitors prepared by compounding the high-efficiency imidazoline type rust inhibitor and the triazole derivative in the examples 4 to 6 on rust resistance, oxygen resistance and oil solubility (in 80 w/90) are shown in the following table 2:

TABLE 2

Product batch number	Rust resistance b	Oil solubility	Rotating oxygen bomb/min
				T406	Heavy rust	/	＜300
T551	Heavy rust	/	＜300
				T571	Heavy rust	/	＜300
Example 4	Non-rust	1% still clear	700
				Example 5	Non-rust	1% still clear	1150
Example 6	Non-rust	1% still clear	1130

Rust resistance a: blending 0.5% of oil sample, and carrying out rust resistance detection according to GB/T11143B;

rust resistance b: blending 0.1% of oil sample, and carrying out rust resistance detection according to GB/T11143B;

from the above results, it can be seen that: when the imidazoline type antirust agent synthesized according to the patent CN110256353A is used, the oil solubility of the product in 80w/90 is poor, and the antirust property and the rotating oxygen bomb test are not ideal; when the high-efficiency imidazoline type antirust agent prepared by the method is tested for the performances, the obtained results are obviously improved, and the results can prove that: the improved method is an efficient synthesis method, and oil solubility, rust resistance and oxygen resistance of the product can be effectively improved after the method is improved; meanwhile, the invention also can remarkably improve the oxidation resistance of the imidazoline type antirust agent by compounding with the triazole derivative.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.