阅读说明：本技术 一种脂肪酸衍生物、其制备方法和应用 (Fatty acid derivative, preparation method and application thereof ) 是由 李寅 任鹏 平原 马敏 于 2021-04-02 设计创作，主要内容包括：本发明涉及一种脂肪酸衍生物,脂肪酸衍生物的结构通式如式(1)所示：其中,R-1为(CH-2)-7、(CH-2)-(10)、(CH-2)-(11)中的任一种,R-2为CH-3、CH-3CH-2、CH(CH-3)-2、CH-3(CH-2)-3中的任一种,R-3为CH-3(CH-2)-7、CH-3(CH-2)-4、CH-3(CH-2)-5中的任一种,R-4为饱和烃基或不饱和烃基。本发明中的脂肪酸衍生物,具有羧酸根阴离子、亚氨基、羟基和酯基等多个功能性基团,能有效抵挡高盐体系中的离子引起的结构分解,从而提高结构的稳定性；并且能在高盐体系下形成带正电的离子结合态,牢牢吸附在金属表面,且能够形成润滑膜,始终保持较佳的润滑性能。(The invention relates to a fatty acid derivative, the structural general formula of which is shown as formula (1): wherein R is 1 Is (CH) 2 ） 7 、（CH 2 ） 10 、（CH 2 ） 11 Any one of (1), R 2 Is CH 3 、CH 3 CH 2 、CH（CH 3 ） 2 、CH 3 （CH 2 ） 3 Any one of (1), R 3 Is CH 3 （CH 2 ） 7 、CH 3 （CH 2 ） 4 、CH 3 （CH 2 ） 5 Any one of (1), R 4 Is a saturated hydrocarbon group or an unsaturated hydrocarbon group. The fatty acid derivative has a plurality of functional groups such as carboxylate anions, imino, hydroxyl, ester groups and the like, and can effectively resist structural decomposition caused by ions in a high-salt system, so that the structural stability is improved; and can form a positively charged ion binding state in a high-salt system, firmly adsorb on the metal surface, form a lubricating film and always keep better lubricating performance.)

1. A fatty acid derivative characterized by: the structural general formula of the fatty acid derivative is shown as a formula (1):

wherein, R is₁Is (CH)₂）₇、（CH₂）₁₀、（CH₂）₁₁Any one of (1), the R₂Is CH₃、CH₃CH₂、CH（CH₃）₂、CH₃（CH₂）₃Any one of (1), the R₃Is CH₃（CH₂）₇、CH₃（CH₂）₄、CH₃（CH₂）₅Any one of (1), the R₄Is a saturated hydrocarbon group or an unsaturated hydrocarbon group.

2. The fatty acid derivative according to claim 1, wherein: the R is₄Is a linear alkyl group having 6 to 22 carbon atoms or a linear alkenyl group having 6 to 22 carbon atoms.

3. The fatty acid derivative according to claim 1 or 2, characterized in that: the fatty acid derivative is one or more of the substances shown in the following structural formula:

。

4. a method for producing the fatty acid derivative according to any one of claims 1 to 3, characterized in that: carrying out epoxidation reaction on a substance with a structural general formula shown as a formula (2) to obtain an epoxy ester substance, then reacting the epoxy ester substance with hydroxyethyl ethylenediamine to obtain a hydroxyethyl ethylenediamine derivative, and then reacting the hydroxyethyl ethylenediamine derivative with a substance with a formula (3) to obtain the fatty acid derivative; wherein the general structural formula of the substance shown in the formula (2) isR in the formula (2)₁、R₂、R₃And R in the formula (1)₁、R₂、R₃The same; the general structural formula of the substance shown in the formula (3) isR in the formula (3)₄And R in the formula (1)₄The same is true.

5. The method for producing a fatty acid derivative according to claim 4, wherein: the epoxidation reaction comprises the following steps: reacting the substance shown in the formula (2) with hydrogen peroxide in the presence of formic acid and sulfuric acid, wherein the charging mass ratio of the substance shown in the formula (2), the formic acid and the sulfuric acid is 100: (5-10): (0.2-0.8); the adding mass of the hydrogen peroxide is 10-15 times of that of the formic acid, and the mass concentration of the hydrogen peroxide is 30-50%; and controlling the temperature of the epoxidation reaction to be 40-70 ℃.

6. The method for producing a fatty acid derivative according to claim 4, wherein: the epoxy ester substance and the hydroxyethyl ethylenediamine react in the presence of zinc oxide, the pressure in the reaction process is controlled to be 0.1-0.6 MPa, the temperature is controlled to be 110-130 ℃, and the feeding mass ratio of the epoxy ester substance to the hydroxyethyl ethylenediamine to the zinc oxide is 100: (70-80): (0.5 to 1.0).

7. The method for producing a fatty acid derivative according to claim 4, wherein: controlling the feeding mass ratio of the hydroxyethyl ethylenediamine derivative to the substance shown in the formula (3) to be 1: (1-2), and controlling the reaction temperature to be 60-120 ℃.

8. The method for producing a fatty acid derivative according to claim 4 or 5, characterized in that: the substance shown in the formula (2) comprises one or more of methyl oleate, soybean oil methyl ester, rapeseed oil methyl ester, ethyl oleate, soybean oil ethyl ester, rapeseed oil ethyl ester, isopropyl oleate, soybean oil isopropyl ester, rapeseed oil isopropyl ester, butyl oleate, soybean oil butyl ester and rapeseed oil butyl ester.

9. The method for producing a fatty acid derivative according to claim 4 or 7, characterized in that: the substance shown in the formula (3) comprises one or more of oleic acid, soybean oil fatty acid, palm oil fatty acid and coconut oil fatty acid.

10. Use of a fatty acid derivative according to any of claims 1 to 3 and/or a fatty acid derivative prepared according to the preparation process of any of claims 4 to 9 as a lubricity additive in a drilling fluid.

Technical Field

The invention relates to a fatty acid derivative, a preparation method and application thereof.

Background

The lubricating additive for drilling fluid in industry is generally compounded by white oil, vegetable oil esters and the like, but has the defects that the white oil has no lubricity and the vegetable oil esters are easily decomposed. In addition, under the conditions of a seawater system and high temperature, the lubricity of vegetable oil and vegetable oil esters is greatly reduced, so that the drilling fluid cannot meet the use requirement.

At present, in a seawater and high-salt system, most of domestic lubricating additives cannot meet the use requirements, imported products still occupy the main market, and the market prospect of the suitable lubricating additives is wide.

Disclosure of Invention

The invention aims to solve the technical problem of providing a fatty acid derivative which has good lubricating property and is not easy to decompose in a high-salt system.

The second technical problem to be solved by the present invention is to provide a method for preparing the above fatty acid derivative.

The third technical problem to be solved by the invention is to provide an application of the fatty acid derivative as a lubricating additive in drilling fluid.

In order to achieve the purpose, the invention adopts the technical scheme that:

in a first aspect of the present invention, a fatty acid derivative is provided, wherein the structural general formula of the fatty acid derivative is represented by formula (1):

wherein, R is₁Is (CH)₂）₇、（CH₂）₁₀、（CH₂）₁₁Any one of (1), the R₂Is CH₃、CH₃CH₂、CH（CH₃）₂、CH₃（CH₂）₃Any one of (1), the R₃Is CH₃（CH₂）₇、CH₃（CH₂）₄、CH₃（CH₂）₅Any one of (1), the R₄Is a saturated hydrocarbon group or an unsaturated hydrocarbon group.

Preferably, said R is₄Is a linear alkyl group having 6 to 22 carbon atoms or a linear alkenyl group having 6 to 22 carbon atoms.

Preferably, the fatty acid derivative is one or more of the following substances represented by the following structural general formula:

。

further preferably, the fatty acid derivative is one or more of the following substances represented by the following structural formula:

。

the second aspect of the invention provides a preparation method of a fatty acid derivative, which comprises the steps of carrying out epoxidation reaction on a substance with a structural general formula shown as a formula (2) to obtain an epoxy ester substance, then reacting the epoxy ester substance with hydroxyethyl ethylenediamine to obtain a hydroxyethyl ethylenediamine derivative, and then reacting the hydroxyethyl ethylenediamine derivative with a substance with a formula (3) to obtain the fatty acid derivative; wherein the general structural formula of the substance shown in the formula (2) isR in the formula (2)₁、R₂、R₃And R in the formula (1)₁、R₂、R₃The same; the general structural formula of the substance shown in the formula (3) isR in the formula (3)₄And R in the formula (1)₄The same is true.

According to some specific and preferred embodiments, the epoxidation reaction comprises the steps of: reacting the substance shown in the formula (2) with hydrogen peroxide in the presence of formic acid and sulfuric acid. Wherein the reaction formula of the epoxidation reaction is as follows:

。

further preferably, the feeding mass ratio of the substance shown in the formula (2), the formic acid and the sulfuric acid is 100: (5-10): (0.2 to 0.8), further 100: (8-10): (0.5-0.8).

More preferably, the addition amount of the hydrogen peroxide is 10-15 times of the mass of the formic acid.

More preferably, the mass concentration of the hydrogen peroxide is 30-50%, further 35-45%, and further 40-45%.

According to some further specific and preferred embodiments, in the epoxidation reaction, the hydrogen peroxide is added in a dropwise manner, the dropwise addition time is controlled to be 1-2 hours, and the reaction is continued for 1-3 hours after the dropwise addition is completed.

Preferably, the temperature of the epoxidation reaction is controlled to be 40-70 ℃, further 50-70 ℃, further 60-70 ℃, further 65-70 ℃.

According to some specific and preferred embodiments, the epoxy ester species is reacted with the hydroxyethylethylenediamine in the presence of zinc oxide. Wherein, zinc oxide is used as a catalyst, and the reaction formula of the reaction of the epoxy ester substance and the hydroxyethyl ethylene diamine is as follows:

。

further preferably, the pressure in the reaction process is controlled to be 0.1-0.6 MPa.

Further preferably, the temperature in the reaction process is controlled to be 110-130 ℃, further 120-130 ℃.

Further preferably, the feeding mass ratio of the epoxy ester substances, the hydroxyethyl ethylenediamine and the zinc oxide is 100: (70-80): (0.5 to 1.0), further 100: (70-75): (0.5-0.8).

According to some specific and preferred embodiments, the epoxy value of the epoxy ester is 1 to 5%, preferably 2 to 3%.

Preferably, the preparation method of the hydroxyethyl ethylenediamine derivative further comprises a step of obtaining the hydroxyethyl ethylenediamine derivative by negative pressure distillation after the reaction is finished.

Further preferably, the distillation pressure is controlled to be 0.4-0.5MPa and the temperature is controlled to be 210-230 ℃.

According to some specific and preferred embodiments, the feeding mass ratio of the hydroxyethyl ethylenediamine derivative to the substance represented by the formula (3) is controlled to be 1: (1-2), preferably 1: (1.2-2), more preferably 1: (1.2-1.5). Wherein the reaction formula of the reaction of the hydroxyethyl ethylene diamine derivative and the substance shown in the formula (3) is as follows:

。

preferably, the temperature of the reaction between the hydroxyethyl ethylenediamine derivative and the substance represented by the formula (3) is controlled to be 60 to 120 ℃, further 70 to 100 ℃, and further 80 to 90 ℃.

According to some specific and preferred embodiments, the substance represented by formula (2) comprises one or more of methyl oleate, soybean oil methyl ester, rapeseed oil methyl ester, ethyl oleate, soybean oil ethyl ester, rapeseed oil ethyl ester, isopropyl oleate, soybean oil isopropyl ester, rapeseed oil isopropyl ester, butyl oleate, soybean oil butyl ester, and rapeseed oil butyl ester.

The raw materials of the methyl oleate, the soybean oil methyl ester, the rapeseed oil methyl ester and the like are derived from natural vegetable oil, and the hydroxyethyl ethylenediamine derivative synthesized by using the methyl oleate, the soybean oil methyl ester, the rapeseed oil methyl ester and the like as reactants and hydroxyethyl ethylenediamine has good fat solubility, is easy to degrade, has low toxicity, and is green and environment-friendly.

Preferably, the substance represented by the formula (3) comprises one or more of oleic acid, soybean oil fatty acid, palm oil fatty acid and coconut oil fatty acid. The fatty acid in the invention is preferably natural fatty acid, is easy to degrade and is environment-friendly.

In a third aspect of the invention, there is provided the use of a fatty acid derivative as a lubricity additive in a drilling fluid.

Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the fatty acid derivative has a plurality of functional groups such as carboxylate anions, imino, hydroxyl, ester groups and the like, and can effectively resist structural decomposition caused by ions in a high-salt system, so that the structural stability is improved; and can form a positively charged ion binding state in a high-salt system, so that the drilling fluid can be firmly adsorbed on the metal surface, and a lubricating film can be formed, so that the drilling fluid can always keep better lubricating performance.

Drawings

FIG. 1 is a hydrogen spectrum of a fatty acid derivative in example 1;

FIG. 2 is a nuclear magnetic carbon spectrum of the fatty acid derivative in example 1.

Detailed Description

The present invention will be further described with reference to the following examples. However, the present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not mentioned are conventional conditions in the industry. The technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other. In the present invention, "plural" means 2 or more unless otherwise specified.

Example 1

1. Mixing methyl oleate, formic acid and sulfuric acid according to a mass ratio of 100: 8: 0.5, adding into a reaction kettle, stirring uniformly, heating to 70 ℃, adding hydrogen peroxide with the mass content of 40% which is 10 times that of formic acid at a constant speed, dropwise adding within 1-2 h, continuing to react for 3h, and distilling to obtain epoxy methyl oleate with the epoxy value of 2%.

2. Epoxy methyl oleate, hydroxyethyl ethylenediamine and zinc oxide are mixed according to the mass ratio of 100: 75: 0.6, putting the mixture into a pressure reaction kettle, heating the mixture to 120 ℃, reacting the mixture at a constant temperature for 1 hour, pouring the mixture into a distillation flask after the pressure is zero, and distilling the mixture at the negative pressure of 0.4-0.5MPa and the temperature of 210 ℃ and 230 ℃ to obtain the fraction, namely the hydroxyethyl ethylenediamine derivative.

3. The preparation method comprises the following steps of (1): 1.5 putting into a reaction kettle, heating to 80 ℃, and reacting for 2 hours at constant temperature to obtain the fatty acid derivative 1.

The chemical structure formula of the main product in the product of the example isThe correlation spectra are shown in figure 1 and figure 2, and are brownish red viscous liquid at room temperature (25 ℃) and the viscosity (40 ℃) is 46.8mm²(s) density 0.898g/cm³With a slight organic amine odour.

Example 2

1. Mixing methyl oleate, formic acid and sulfuric acid according to a mass ratio of 100: 10: 0.8, adding into a reaction kettle, uniformly stirring, heating to 65 ℃, adding hydrogen peroxide with the mass content of 40% and 15 times of that of formic acid at a constant speed, dropwise adding within 1-2 h, continuing to react for 3h, and distilling to obtain epoxy methyl oleate with the epoxy value of 2.3%.

2. Epoxy methyl oleate, hydroxyethyl ethylenediamine and zinc oxide are mixed according to the mass ratio of 100: 70: 0.5, putting the mixture into a pressure reaction kettle, heating the mixture to 120 ℃, reacting the mixture at a constant temperature for 1.5h, pouring the mixture into a distillation flask after the pressure is zero, and distilling the mixture at the negative pressure of 0.4-0.5MPa and the temperature of 210 ℃ and 230 ℃ to obtain the fraction, namely the hydroxyethyl ethylenediamine derivative.

3. The preparation method comprises the following steps of (1): 1.2 putting into a reaction kettle, heating to 80 ℃, and reacting for 1.5 hours at constant temperature to obtain the fatty acid derivative 2.

The chemical structure formula of the main product in the product of the example isA brownish red viscous liquid at room temperature (25 ℃), a viscosity (40 ℃) of 53.1mm²(s) density 0.902g/cm³With a slight organic amine odour.

The products prepared in the above examples and hydroxyethyl ethylenediamine were added to white oil to prepare fatty acid derivatives or systems with hydroxyethyl ethylenediamine at a mass concentration of 10% to 80%, and the test results are shown in table 1, and it can be seen from table 1 that the fatty acid derivatives prepared in each example are miscible with white oil, but hydroxyethyl ethylenediamine is immiscible with white oil.

The products prepared in the examples are respectively added into white oil or methyl oleate, the reduction rate of the lubricating coefficient is detected in seawater slurry, the related results are shown in Table 2, and the detection standard of the reduction rate of the lubricating coefficient is Q/SY 17008-2016.

The present invention has been described in detail in order to enable those skilled in the art to understand the invention and to practice it, and it is not intended to limit the scope of the invention, and all equivalent changes and modifications made according to the spirit of the present invention should be covered by the present invention.