阅读说明：本技术 苯并三氮唑功能化的季铵盐离子液体及其制备方法和应用 (Benzotriazole functionalized quaternary ammonium salt ionic liquid and preparation method and application thereof ) 是由 周峰 于强亮 张朝阳 蔡美荣 裴小维 刘志鲁 于波 刘维民 于 2019-12-04 设计创作，主要内容包括：本发明提供了苯并三氮唑功能化的季铵盐离子液体及其制备方法和应用,属于润滑技术领域。本发明提供的苯并三氮唑功能化的季铵盐离子液体,其阳离子为带有不同烷基链长的苯并三氮唑功能化季铵盐,阴离子为三氮唑。本发明在季铵盐结构中引入苯并三氮唑官能团和无卤素绿色的阴离子三氮唑,所得离子液体具有优异的水溶性、摩擦学性能和抗腐蚀性能,且绿色环保,可以作为水基润滑剂添加剂使用。(The invention provides benzotriazole functionalized quaternary ammonium salt ionic liquid, and a preparation method and application thereof, and belongs to the technical field of lubrication. According to the benzotriazole functionalized quaternary ammonium salt ionic liquid provided by the invention, cations are benzotriazole functionalized quaternary ammonium salts with different alkyl chain lengths, and anions are triazole. According to the invention, benzotriazole functional groups and halogen-free green anionic triazole are introduced into the quaternary ammonium salt structure, and the obtained ionic liquid has excellent water solubility, tribological property and corrosion resistance, is green and environment-friendly, and can be used as a water-based lubricant additive.)

1. The benzotriazole functionalized quaternary ammonium salt ionic liquid is characterized by having a structure shown in a formula I:

in the formula I, R is C₁～C₁₈Alkyl group of (1).

2. The benzotriazole-functionalized quaternary ammonium salt ionic liquid of claim 1, wherein R is methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, octyl, isooctyl, decyl, isodecyl, dodecyl, tetradecyl, hexadecyl, or octadecyl.

3. The preparation method of benzotriazole functionalized quaternary ammonium salt ionic liquid of claim 1 or 2, which is characterized by comprising the following steps:

mixing chloromethyl benzotriazole, N-dimethyl alkylamine and an organic solvent, and then carrying out quaternization reaction to obtain benzotriazole functionalized N, N-dimethyl alkylammonium bromide;

mixing the benzotriazole functionalized N, N-dimethyl alkyl ammonium bromide, triazole sodium, water and an organic solvent, and then carrying out an ion exchange reaction to obtain a benzotriazole functionalized quaternary ammonium salt ionic liquid;

wherein the N, N-dimethyl alkylamine has a structure shown in formula II:

in the formula II, R is C₁～C₁₈Alkyl group of (1).

4. The preparation method according to claim 3, wherein the molar ratio of the chloromethyl benzotriazole to the N, N-dimethyl alkylamine is 1: (1-1.2).

5. The preparation method according to claim 3, wherein the temperature of the quaternization reaction is 75-85 ℃ and the time is 8-48 h.

6. The method according to any one of claims 3 to 5, further comprising, after completion of the quaternization reaction: and (3) decompressing the obtained system, distilling off the solvent, and washing the remainder by using petroleum ether to obtain the benzotriazole functionalized N, N-dimethyl alkyl ammonium bromide.

7. The preparation method according to claim 3, characterized in that the molar ratio of benzotriazole functionalized N, N-dimethyl alkyl ammonium bromide to triazole sodium is 1: (1-1.2).

8. The preparation method according to claim 3, wherein the temperature of the ion exchange reaction is room temperature, and the time is 10-15 h.

9. The method of claim 3, 7 or 8, wherein the ion exchange reaction is completed and further comprises: separating the obtained system, drying the obtained organic phase, and then decompressing and evaporating the solvent to obtain the benzotriazole functionalized quaternary ammonium salt ionic liquid.

10. The use of benzotriazole-functionalized quaternary ammonium salt ionic liquid of claim 1 or 2 as a water-based lubricant additive.

Technical Field

The invention relates to the technical field of lubrication, in particular to benzotriazole functionalized quaternary ammonium salt ionic liquid and a preparation method and application thereof.

Background

The rapid development of the industry accelerates the excessive consumption of energy, wherein the consumption of energy due to abnormal wear of machinery resulting from lubrication failure accounts for as much as 24% of all primary energy consumption. Therefore, the development of efficient lubrication means, especially the use of high performance lubricants, is the most effective means to reduce friction, reduce or avoid wear.

At present, the mineral oil-based lubricant is widely applied to the industrial field with excellent antifriction and antiwear performances, so that the energy consumption of mechanical equipment caused by friction is greatly reduced, and the service life of the mechanical equipment is prolonged. However, in some special fields such as working conditions of coal mines, metal processing and the like, the mineral oil-based lubricant has limited its application due to the disadvantages of low flash point, flammability, small heat conductivity and the like, and with the continuous enhancement of the awareness of environmental protection of human beings, people realize that the problem of environmental pollution caused by the mineral oil-based lubricant is more and more serious, and gradually affect our daily life and physical and mental health, so people begin to actively search for alternatives in the lubrication field. The water-based lubricant is regarded as a novel green lubricant and is continuously developed and widely applied to the fields of flame-resistant hydraulic fluid and metal working fluid due to the advantages of excellent cooling, flame retardancy, low pollution, high thermal conductivity, high specific heat capacity and the like.

However, compared with oil-based lubricants, the existing water-based lubricants have the problem of poor lubricity and rust resistance, which greatly limits the development of water-based lubricants, so research and development of an efficient water-based lubricant additive are key points for improving the comprehensive properties of the water-based lubricants and further widening the application range of the water-based lubricants.

Ionic liquids, as the most important class of lubricants and additives, have been the focus of common research in the global academia and industry since the first report in 2001 by the applicant (Ye C, Liu W, Chen Y, et al, from-temporal Chemical requirements: a novel versatility [ J ]. Chemical Communications,2001(21): 2244) and 2245). Ionic liquids are widely studied as lubricating oils, additives and lubricating films due to their unique physicochemical properties and good lubricating properties (m.h.yao, m.j.fan, y.m, Liang, f.zhou, y.q.xia, Wear268(2010) 67-71); x.q.liu, m.r.cai, z.zhao, y.m.liang, f.zhou, w.m.liu, tribol.lett.40(2010)215-224.), it also has potential to be developed as a highly effective water-based lubricant additive.

Some ionic liquids reported at present as water lubricating additives still have the problems of poor water solubility, poor stability, poor lubricating performance, corrosion to substrates and the like, and the application of the ionic liquids in the field of water-based lubricating additives is greatly limited. Therefore, the development of high-performance water-soluble ionic liquid lubricating additives is a problem which is urgently needed to be solved at present.

Disclosure of Invention

The invention aims to provide benzotriazole-functionalized quaternary ammonium salt ionic liquid, and a preparation method and application thereof.

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

the invention provides benzotriazole functionalized quaternary ammonium salt ionic liquid, which has a structure shown in a formula I:

in the formula I, R is C₁～C₁₈Alkyl group of (1).

Preferably, R is methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, octyl, isooctyl, decyl, isodecyl, dodecyl, tetradecyl, hexadecyl or octadecyl.

The invention provides a preparation method of benzotriazole functionalized quaternary ammonium salt ionic liquid, which comprises the following steps:

mixing chloromethyl benzotriazole, N-dimethyl alkylamine and an organic solvent, and then carrying out quaternization reaction to obtain benzotriazole functionalized N, N-dimethyl alkylammonium bromide;

mixing the benzotriazole functionalized N, N-dimethyl alkyl ammonium bromide, triazole sodium, water and an organic solvent, and then carrying out an ion exchange reaction to obtain a benzotriazole functionalized quaternary ammonium salt ionic liquid;

wherein the N, N-dimethyl alkylamine has a structure shown in formula II:

in the formula II, R is C₁～C₁₈Alkyl group of (1).

Preferably, the molar ratio of the chloromethyl benzotriazole to the N, N-dimethyl alkylamine is 1: (1-1.2).

Preferably, the temperature of the quaternization reaction is 75-85 ℃, and the time is 8-48 h.

Preferably, the quaternization reaction further comprises, after completion: and (3) decompressing the obtained system, distilling off the solvent, and washing the remainder by using petroleum ether to obtain the benzotriazole functionalized N, N-dimethyl alkyl ammonium bromide.

Preferably, the molar ratio of the benzotriazole functionalized N, N-dimethyl alkyl ammonium bromide to triazole sodium is 1: (1-1.2).

Preferably, the temperature of the ion exchange reaction is room temperature, and the time is 10-15 h.

Preferably, the ion exchange reaction further comprises: separating the obtained system, drying the obtained organic phase, and then decompressing and evaporating the solvent to obtain the benzotriazole functionalized quaternary ammonium salt ionic liquid.

The invention provides application of benzotriazole functionalized quaternary ammonium salt ionic liquid as a water-based lubricant additive.

The invention provides benzotriazole functionalized quaternary ammonium salt ionic liquid, wherein cations are benzotriazole functionalized quaternary ammonium salts with different alkyl chain lengths, and anions are triazole. According to the invention, benzotriazole functional groups and halogen-free green anionic triazole are introduced into a quaternary ammonium salt structure, and the obtained ionic liquid can be used as a green, environment-friendly and non-corrosive water-based lubricant additive. Specifically, the ionic liquid provided by the invention has good solubility, can be fully dissolved in organic solvents with different polarities such as chloroform, methanol and the like, and also has good water solubility; and the benzotriazole group is introduced, so that the ionic liquid has excellent tribological property and corrosion resistance, the water added with the ionic liquid is used as a lubricant of a steel/steel friction pair, has excellent antifriction and wear resistance and high bearing capacity, can effectively reduce the corrosion of water to metal, and can be used as a water-based lubricant additive to be applied to the water-based lubricating processing fluid or cutting fluid industry.

Detailed Description

The invention provides benzotriazole functionalized quaternary ammonium salt ionic liquid, which has a structure shown in a formula I:

in the formula I, R is C₁～C₁₈Alkyl group of (1).

In the present invention, the R is preferably methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, octyl, isooctyl, decyl, isodecyl, dodecyl, tetradecyl, hexadecyl or octadecyl, more preferably dodecyl or hexadecyl.

The invention provides a preparation method of benzotriazole functionalized quaternary ammonium salt ionic liquid, which comprises the following steps:

mixing chloromethyl benzotriazole, N-dimethyl alkylamine and an organic solvent, and then carrying out quaternization reaction to obtain benzotriazole functionalized N, N-dimethyl alkylammonium bromide;

mixing the benzotriazole functionalized N, N-dimethyl alkyl ammonium bromide, triazole sodium, water and an organic solvent, and then carrying out an ion exchange reaction to obtain a benzotriazole functionalized quaternary ammonium salt ionic liquid;

wherein the N, N-dimethyl alkylamine has a structure shown in formula II:

in the formula II, R is C₁～C₁₈Alkyl group of (1).

According to the invention, chloromethyl benzotriazole, N-dimethyl alkylamine and an organic solvent are mixed and then subjected to quaternization reaction to obtain benzotriazole functionalized N, N-dimethyl alkylammonium bromide. In the invention, the N, N-dimethyl alkylamine has a structure shown in a formula II, wherein R in the formula II is C₁～C₁₈Preferably methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, octyl, isooctyl, decyl, isodecyl, dodecyl, tetradecyl, hexadecyl or octadecyl, more preferably dodecyl or hexadecyl; in an embodiment of the invention, the N, N-dimethyl alkylamine is in particular N, N-dimethyldodecylamine or N, N-dimethylhexadecylamine. In the present invention, the molar ratio of the chloromethyl benzotriazole to N, N-dimethyl alkylamine is preferably 1: (1-1.2). The type of the organic solvent is not particularly limited, and the organic solvent can be any conventional organic solvent, such as acetonitrile, methanol or isopropanol, and preferably acetonitrile; the amount of the organic solvent is not particularly limited, and specifically, the ratio of the amount of the chloromethyl benzotriazole to the amount of the organic solvent is preferably 0.3 mol: (140-160) mL. According to the invention, preferably, chloromethyl benzotriazole and N, N-dimethyl alkylamine are mixed, then an organic solvent is added for mixing, and the quaternization reaction is carried out after the materials are uniformly mixed.

In the invention, the temperature of the quaternization reaction is preferably 75-85 ℃, and more preferably 80 ℃; the time is preferably 8 to 48 hours, more preferably 20 to 30 hours, and further preferably 24 hours.

In the present invention, it is preferable that the quaternization reaction further comprises: and (3) decompressing the obtained system, distilling off the solvent, and washing the remainder by using petroleum ether to obtain the benzotriazole functionalized N, N-dimethyl alkyl ammonium bromide. The invention has no special limitation on the specific operation of distilling the solvent out under reduced pressure and washing with petroleum ether, and the method well known by the technicians in the field can be adopted; the petroleum ether is preferably anhydrous petroleum ether.

After the benzotriazole functionalized N, N-dimethyl alkyl ammonium bromide is obtained, the benzotriazole functionalized N, N-dimethyl alkyl ammonium bromide, triazole sodium, water and an organic solvent are mixed for ion exchange reaction to obtain the benzotriazole functionalized quaternary ammonium salt ionic liquid. In the invention, the molar ratio of the benzotriazole functionalized N, N-dimethyl alkyl ammonium bromide to triazole sodium is preferably 1: (1-1.2). The type of the organic solvent is not particularly limited, and the organic solvent can be any conventional organic solvent, such as dichloromethane, acetonitrile or methanol, and dichloromethane is preferred; in the present invention, the amount of water and the organic solvent is not particularly limited, and specifically, the ratio of the amount of the sodium triazole to the amount of water and the organic solvent is preferably 0.3 mol: (25-35) mL: (25-35) mL. According to the invention, sodium triazole is preferably dissolved in water to obtain a sodium triazole aqueous solution, then the sodium triazole aqueous solution is mixed with benzotriazole functionalized N, N-dimethyl alkyl ammonium bromide and an organic solvent, and the ion exchange reaction is carried out after the materials are uniformly mixed.

In the present invention, the temperature of the ion exchange reaction is preferably room temperature, i.e., no additional heating or cooling is required; the time is preferably 10-15 h, and more preferably 12 h; the ion exchange reaction is preferably carried out under stirring conditions, and the stirring rate is not particularly limited in the present invention, and may be a conventional stirring rate.

In the present invention, it is preferable that the ion exchange reaction further comprises: separating the obtained system, drying the obtained organic phase, and then decompressing and evaporating the solvent to obtain the benzotriazole functionalized quaternary ammonium salt ionic liquid. In the invention, the drying is preferably carried out by using a solid drying agent, the solid drying agent is preferably anhydrous sodium sulfate, and the drying time is preferably 10-15 h, and more preferably 12 h. In the present invention, the drying preferably further comprises filtering to remove the solid desiccant. The present invention is not particularly limited to the specific operation of distilling off the solvent under reduced pressure, and a method known to those skilled in the art may be employed.

In the invention, the reaction process for preparing the benzotriazole functionalized quaternary ammonium salt ionic liquid is as follows:

the invention provides application of benzotriazole functionalized quaternary ammonium salt ionic liquid as a water-based lubricant additive. The application of the invention is not specially limited, and the addition amount of the benzotriazole functionalized quaternary ammonium salt ionic liquid is determined according to actual needs.

The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. 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 invention.