A benzotriazole-amide derivative additive and its preparation method

Abstract

The invention provides a benzotriazole-amide derivative additive and a preparation method of the benzotriazole-amide derivative additive. Specifically, the invention discloses an environment-friendly ash-free additive free of sulfur and phosphorus, benzotriazole-alkylamine is used as a raw material, and corresponding benzotriazole-amide derivatives are synthesized by using benzotriazole-alkylamine and acyl chlorides with different structures. Through selection of a substituent R1, an amine chain length n, a substituent R2 and an acyl chloride carbon chain R3 on a benzene ring, the compatibility of the additive and various base oils is regulated and controlled, and the lubricating performance of the additive is effectively regulated and controlled.

Description

(19) State Intellectual Property Office (12) Invention Patent Application (10) Application Publication Number (43) Application Publication Date (21) Application Number 202411695189.0 (22) Application Date 2024.11.25 (71) Applicant Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences Address 345 Lingling Road, Xuhui District, Shanghai 200032 (72) Inventors Yang Hongmei, Yang Fan, Li Zenghui, Tang Yong, Sun Xiuli (74) Patent Agency Shanghai Yiping Intellectual Property Agency Co., Ltd. 31266 Patent Attorney Xu Xun, Gao Yiping (51) Int.Cl. C07D 249 / 18 (2006.01) C10M 133 / 44 (2006.01) C10M 169 / 04 (2006.01) C10N 30 / 00 (2006.01) (54) Invention Title: A Benzotriazole-Amide Derivative Additive and Its Preparation Method (57) Abstract: This invention provides a benzotriazole-amide derivative additive and its preparation method. Specifically, this invention discloses an environmentally friendly, ashless additive that is free of sulfur and phosphorus. Benzotriazole-alkylamine is used as a raw material, and corresponding benzotriazole-amide derivatives are synthesized by combining it with acyl chlorides of different structures. By selecting the substituent R1 on the benzene ring, the amine chain length n, the substituent R2, and the acyl chloride carbon chain R3, the compatibility of the additive with various base oils is controlled, effectively regulating the lubricating performance of the additive. Claims (3 pages), Description (13 pages), Drawings (2 pages), CN 122079909 A 2026.05.26 CN 1 22 07 99 09 A 1. An ashless additive, characterized in that the additive comprises one or more benzotriazole-amide derivative components with the following structure: wherein R1 and R2 are each independently -H, -CmH2m+1 or -CmH2m-1; R3 is -CmH2m+1 or -CmH2m-1; m is an integer from 1 to 20; n is an integer from 1 to 19; and in the additive, the content of the component with the shown structure is ≥50%, preferably ≥70%, more preferably ≥90%, and most preferably ≥95%. 2. The ashless additive according to claim 1, characterized in that the additive comprises one or more benzotriazole-amide derivative components selected from the following formulas (I)-(VI): wherein R1 and R2 are each independently -H, -CmH2m+1 or -CmH2m-1; R3 is -CmH2m+1 or -CmH2m-1; m is an integer from 1 to 20; n is an integer from 1 to 19; and in the additive, the content of the components shown in formulas I, II, III, IV, V and VI is ≥50%, preferably ≥70%, more preferably ≥90%, and most preferably ≥95%.3. The additive as claimed in claim 1, characterized in that the additive is selected from the group consisting of: (Claims 1 / 3 page 2 CN 122079909 A) or combinations thereof. 4. An ashless additive-base oil complex, characterized in that the complex comprises the ashless additive as claimed in claim 1; preferably, in the complex, the amount of the ashless additive added is 0.1-10.0 wt% of the weight of the base oil, more preferably 0.1-5.0 wt%. 5. The complex as claimed in claim 4, characterized in that the base oil is selected from the group consisting of: synthetic hydrocarbon base oils, synthetic ester base oils, polyether base oils, alkylnaphthalene base oils, or combinations thereof. 6. A method for preparing a benzotriazole-amide derivative, characterized by comprising the following steps: Claims 2 / 3, page 3, CN 122079909 A: Under an inert atmosphere and in the presence of an acid-binding agent, the benzotriazole derivative reacts with an acyl chloride R3-C(O)Cl to obtain the benzotriazole-amide derivative; wherein, R1 and R2 are each independently -H, -CmH2m+1, or -CmH2m-1; R3 is -CmH2m+1 or -CmH2m-1; m is an integer from 1 to 20; n is an integer from 1 to 19. 7. The preparation method according to claim 6, wherein the benzotriazole derivative is selected from the group consisting of: 1H-benzotriazole-ethylamine, 2H-benzotriazole-ethylamine, 5-methyl-1H-benzotriazole-ethylamine, 5-methyl-2H-benzotriazole-ethylamine, 6-methyl-1H-benzotriazole-ethylamine, 5-methyl-1H-benzotriazole-butylamine, 5-methyl-2H-benzotriazole-butylamine, 6-methyl-1H-benzotriazole-butylamine, 5-butyl-1H-benzotriazole-ethylamine, 5-butyl-2H-benzotriazole-ethylamine, 6-butyl-1H-benzotriazole-ethylamine, or combinations thereof. 8. The preparation method according to claim 6, wherein the acid-binding agent is selected from the group consisting of triethylamine, pyridine, Na2CO3, NaHCO3, K2CO3, NaOH, KOH, or combinations thereof. 9. The preparation method according to claim 6, wherein the acyl chloride R3-C(O)Cl is selected from the group consisting of butyryl chloride, hexanoyl chloride, octanoyl chloride, isooctanoyl chloride, 2-ethylhexanoyl chloride, nonanoyl chloride, decanoyl chloride, lauroyl chloride, myristoyl chloride, palmitoyl chloride, stearoyl chloride, oleic acid chloride, or combinations thereof. 10. A method for preparing the ashless additive-base oil complex according to claim 4, characterized in that it comprises the following steps: mixing the ashless additive according to claim 1 with a base oil to obtain the complex.Claims 3 / 3 Page 4 CN 122079909 A A Benzotriazole-amide Derivative Additive and Its Preparation Method Technical Field

[0001] This invention belongs to the field of lubricating oil additives, specifically relating to a benzotriazole-amide derivative component additive and its preparation method. Background Art

[0002] In daily life, lubricating materials are often used to reduce friction loss and avoid wear failure. Before the 1830s, additive-free lubricating oil (base oil) could meet the needs of production and life in society at that time. However, with the development of science and technology, people's requirements for the use of mechanical equipment have become more and more stringent, such as higher and higher loads, temperatures, speeds, etc. Base oil can no longer meet the lubrication requirements of harsh working conditions. This demand for high-performance lubricating materials has spurred the development and application research of additives. Generally speaking, depending on the lubricating oil requirements of different applications, the dosage of additives is between 1%wt and 30%wt, which can greatly improve the performance of oil and supplement some characteristics that base oil does not have.

[0003] In terms of performance, synthetic base oils have better heat resistance and oxidation resistance than traditional mineral base oils, and also have a wider operating temperature range, making them the preferred choice for developing high-performance lubricants. However, the compatibility of synthetic base oils, especially synthetic hydrocarbon base oils, with additives is currently one of the challenges.

[0004] Given the increasing precision of machinery and the upgrading of lubricant processes, coupled with the steadily growing demand in the high-end market, the development of ashless additives for synthetic base oils is of great significance for the development of high-performance lubricants. In order to solve the problems of poor compatibility of existing ashless additives with synthetic base oils of different structures, poor effect on reducing the coefficient of friction in low-viscosity base oils, and adverse environmental impact, there is an urgent need in the field to develop an ashless additive with a wide range of applications and good compatibility. Summary of the Invention

[0005] One object of the present invention is to provide a benzotriazole-amide derivative additive with a wide range of applications and good compatibility, and its preparation method.

[0006] In a first aspect of the invention, an ashless additive is provided, the additive comprising one or more benzotriazole-amide derivative components with the following structure:

[0007]

[0008] wherein,

[0009] R1 and R2 are each independently -H, -CmH2m+1 or -CmH2m-1;

[0010] R3 is -CmH2m+1 or -CmH2m-1;

[0011] m is an integer from 1 to 20; n is an integer from 1 to 19;

[0012] and in the additive, the content of the component with the shown structure is ≥50%, preferably ≥70%, more preferably ≥90%, and most preferably ≥95%.

[0013] In another preferred embodiment, n is an integer from 1 to 12; preferably, n is an integer from 1 to 6; more preferably, n is an integer from 1 to 3.Specification 1 / 13 page 5 CN 122079909 A

[0014] In another preferred embodiment, m is an integer from 1 to 15; more preferably, m is an integer from 1 to 10; even more preferably, m is an integer from 1 to 8.

[0015] In another preferred embodiment, the additive comprises one or more benzotriazole-amide derivative components selected from the following formulas (I)-(VI):

[0016]

[0017] wherein,

[0018] R1 and R2 are each independently -H, -CmH2m+1 or -CmH2m-1;

[0019] R3 is -CmH2m+1 or -CmH2m-1;

[0020] m is an integer from 1 to 20; n is an integer from 1 to 19;

[0021] and in the additive, the content of the components shown in formulas I, II, III, IV, V and VI is ≥ 50%, preferably ≥ 70%, more preferably ≥ 90%, and most preferably ≥ 95%.

[0022] In another preferred embodiment, the additive is selected from the group consisting of:

[0023]

[0024] or combinations thereof.

[0025] In a second aspect of the invention, an ashless additive-base oil complex is provided, the complex comprising the ashless additive described in the first aspect of the invention; preferably, the amount of the ashless additive added in the complex is 0.1-10.0 wt% of the weight of the base oil, more preferably 0.1-5.0 wt%.

[0026] In another preferred embodiment, the base oil is selected from the group consisting of: synthetic hydrocarbon base oil, synthetic ester base oil, polyether base oil, alkylnaphthalene base oil, or combinations thereof.

[0027] In another preferred embodiment, the base oil is a mixture of synthetic hydrocarbon base oil and synthetic ester base oil.

[0028] In another preferred embodiment, the mass ratio of the synthetic hydrocarbon base oil to the synthetic ester base oil is (80-99):(1- 20); preferably 90:10.

[0029] In another preferred embodiment, the synthetic hydrocarbon base oil is PAO4.

[0030] In another preferred embodiment, the synthetic ester base oil is polyol ester 3970.

[0031] In a third aspect of the present invention, a method for preparing a benzotriazole-amide derivative is provided, comprising the following steps:

[0032]

[0033] Under an inert atmosphere and in the presence of an acid-binding agent, a benzotriazole derivative is reacted with an acyl chloride R3-C(O)Cl to obtain a benzotriazole-amide derivative;

[0034] wherein,

[0035] R1 and R2 are each independently -H, -CmH2m+1 or -CmH2m-1;

[0036] R3 is -CmH2m+1 or -CmH2m-1;

[0037] m is an integer from 1 to 20; n is an integer from 1 to 19.

[0038] In another preferred embodiment, the method comprises the step of: providing a mixture of a benzotriazole derivative and an acid-binding agent in an inert solvent, adding an acyl chloride solution to react, and obtaining the benzotriazole-amide derivative.

[0039] In another preferred embodiment, the reaction further comprises a post-treatment.

[0040] In another preferred embodiment, the post-processing includes the steps of: quenching with water, extraction, washing, drying, and (column chromatography) purification.

[0041] In another preferred embodiment, the molar ratio of the benzotriazole derivative to the acyl chloride R3-C(O)Cl is 1:(1.2-2); preferably (1.2-1.6); more preferably (1.4-1.5).

[0042] In another preferred embodiment, the molar ratio of the benzotriazole derivative to the acid-binding agent is 1:(2-3); preferably 1:(2-2.5).

[0043] In another preferred embodiment, the inert solvent is selected from the group consisting of C1-C6 alkane solvents, C2-C6 ester solvents, C2-C6 ether solvents, or combinations thereof; preferably, the inert solvent is (anhydrous) DCM.

[0044] In another preferred embodiment, the benzotriazole derivative is selected from the group consisting of: 1H-benzotriazole-ethylamine, 2H-benzotriazole-ethylamine, 5-methyl-1H-benzotriazole-ethylamine, 5-methyl-2H-benzotriazole-ethylamine, 6-methyl-1H-benzotriazole-ethylamine, 5-methyl-1H-benzotriazole-butylamine, 5-methyl-2H-benzotriazole-butylamine, 6-methyl-1H-benzotriazole-butylamine, 5-butyl-1H-benzotriazole-ethylamine, 5-butyl-2H-benzotriazole-ethylamine, 6-butyl-1H-benzotriazole-ethylamine, or combinations thereof.

[0045] In another preferred embodiment, the acid-binding agent is selected from the group consisting of triethylamine, pyridine, Na2CO3, NaHCO3, K2CO3, NaOH, KOH, or combinations thereof.

[0046] In another preferred embodiment, the acyl chloride R3-C(O)Cl is selected from the group consisting of butyryl chloride, hexanoyl chloride, octanoyl chloride, isooctanoyl chloride, 2-ethylhexanoyl chloride, nonanoyl chloride, decanoyl chloride, lauroyl chloride, myristoyl chloride, palmitoyl chloride, stearoyl chloride, oleyl chloride, or combinations thereof.

[0047] In a fourth aspect of the present invention, a method for preparing the ashless additive-base oil complex according to the second aspect of the present invention is provided, comprising the following steps:

[0048] Mixing the ashless additive according to the first aspect of the present invention with a base oil to obtain the complex. Specification 4 / 13 pages 8 CN 122079909 A

[0049] In another preferred embodiment, the mixing temperature of the ashless additive and the base oil is 50-65°C; preferably 55-60°C.

[0050] In another preferred embodiment, the mixing is by stirring.

[0051] In another preferred embodiment, the stirring time is 0.5-2 h; more preferably 0.5-1 h.

[0052] It should be understood that within the scope of this invention, the above-mentioned technical features of this invention and the technical features specifically described below (such as in the examples) can be combined with each other to form new or preferred technical solutions. Due to space limitations, they will not be described in detail here. Brief Description of the Drawings

[0053] Figure 1 is a comparison of the friction curves of the sample oil with the benzotriazole derivative-amide compound prepared in Example 7 of this invention and the blank base oil.

[0054] Figure 2 is a comparison of the friction reduction performance of the sample oil with 0.5 wt.% of the benzotriazole derivative-amide compound prepared in Example 7 of this invention and the blank base oil.

[0055] Figure 3 is a comparison of the anti-wear performance of the sample oil with 0.5 wt.% of the benzotriazole derivative-amide compound prepared in Example 7 of this invention and the blank base oil. Detailed Embodiments

[0056] Through extensive and in-depth research and numerous experiments, the inventors have developed for the first time an ashless, sulfur- and phosphorus-free benzotriazole derivative-amide derivative additive. The benzotriazole-amide derivative is obtained from benzotriazole derivatives and acyl chlorides as raw materials. Its tribological properties can be effectively controlled by adjusting the length of the amide chain R3 and the side chains R1 and R2. The benzotriazole-amide derivative additive is free of metals and elements such as sulfur and phosphorus. Based on this, the inventors completed the present invention.

[0057] Terminology

[0058] As used herein, the term "ashless additive" refers to a class of lubricating oil additives that enhance boundary lubrication, increase the adsorption and wedging capacity of lubricating oil, prevent dry friction, reduce the coefficient of friction, enhance oil film strength, and reduce kinetic energy consumption. Further, the ashless additive refers to a benzotriazole-amide derivative component or a benzotriazole-amide derivative component having the structure shown in Formulas I-VI.

[0059] As used herein, the term "base oil" refers to lubricating oil used in mechanical equipment and industrial equipment, including mineral-based lubricating oils and synthetic lubricating oils.

[0060] As used herein, the term "synthetic hydrocarbon base oil" is polymerized from α-olefins under the action of a catalyst and has excellent comprehensive performance.

[0061] As used herein, the term "synthetic ester base oil" is obtained by dehydration of fatty acids and fatty alcohols through esterification reaction under the action of a catalyst. Depending on the types of fatty acids and fatty alcohols reacted, synthetic esters can be classified as: polyol esters, diesters, and monoesters, etc.

[0062] As used herein, the term "polyether base oil" is the most widely used synthetic base oil, which is obtained from raw materials such as ethylene oxide (EO), propylene oxide (PO), and butane oxide (DB) through ring-opening homopolymerization or copolymerization. It can be classified as water-soluble polyether, water-insoluble polyether, and oil-soluble polyether.

[0063] Ashless Additive

[0064] This invention provides an ashless additive that has good compatibility with various base oils and excellent friction and wear reduction effects. (Instruction manual page 5 / 13, 9 CN 122079909 A) Specifically, the ashless additive includes one or more benzotriazole derivative-amide derivative components with the following structures:

[0065]

[0066] Wherein,

[0067] R1 and R2 are each independently -H, -CmH2m+1, or -CmH2m-1;

[0068] R3 is -CmH2m+1 or -CmH2m-1;

[0069] m is an integer from 1 to 20; n is an integer from 1 to 19;

[0070] And in the additive, the content of the benzotriazole derivative-amide derivative component is ≥50%, preferably ≥70%, more preferably ≥90%, and most preferably ≥95%.

[0071] n is an integer from 1 to 12, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12; preferably, n is an integer from 1 to 6; more preferably, n is an integer from 1 to 3.

[0072] Preferably, m is an integer from 1 to 15; for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12.

[0073] Preferably, the structure of the benzotriazole derivative-amide derivative component is as follows:

[0074]

[0075] Wherein, R1, R2, R3 and n are as described above;

[0076] And in the ashless additive, the content of the components shown in Formula I, Formula II, Formula III, Formula IV, Formula V and Formula VI is ≥50%, preferably ≥70%, more preferably ≥90%, and most preferably ≥95%.

[0077] Preferably, the benzotriazole derivative-amide derivative component is 5-methyl-2H-benzotriazole-2-ethyl-oleic acid amide.

[0078] In a preferred embodiment, when used in a base oil, the amount of the ashless additive added is 0.1-10.0 wt% of the weight of the base oil, preferably 0.1-5.0 wt%; more preferably 0.1-1.0 wt%.

[0079] In a preferred embodiment, the base oil is a synthetic base oil or a mineral base oil.

[0080] In a preferred embodiment, the base oil is selected from the group consisting of: synthetic hydrocarbon base oils, synthetic ester base oils, polyether base oils, alkylnaphthalene base oils, or combinations thereof.

[0081] Preparation method of benzotriazole-amide derivative

[0082] The present invention provides a method for preparing benzotriazole-amide derivative, specifically including the following steps: Specification 6 / 13 pages 10 CN 122079909 A

[0083]

[0084] First, the benzotriazole derivative and the acid-binding agent are mixed in a reactor with a solvent; then, the acyl chloride is dissolved in a solvent and slowly added dropwise to the reactor under an ice-water bath; subsequently, the mixture is stirred until the reaction of the raw material benzotriazole derivative is complete as monitored by TLC, the reaction is quenched with water, and the corresponding benzotriazole-amide derivative compound is obtained after extraction, washing, drying and purification.

[0085] Preferably, the benzotriazole derivative is selected from the group consisting of: 1H-benzotriazole-ethylamine, 2H-benzotriazole-ethylamine, 5-methyl-1H-benzotriazole-ethylamine, 5-methyl-2H-benzotriazole-ethylamine, 6-methyl-1H-benzotriazole-ethylamine, 5-methyl-1H-benzotriazole-butylamine, 5-methyl-2H-benzotriazole-butylamine, 6-methyl-1H-benzotriazole-butylamine, 5-butyl-1H-benzotriazole-ethylamine, 5-butyl-2H-benzotriazole-ethylamine, 6-butyl-1H-benzotriazole-ethylamine, or combinations thereof.

[0086] Preferably, the acid-binding agent is selected from one or more combinations of triethylamine, pyridine, Na2CO3, NaHCO3, K2CO3, NaOH, and KOH.

[0087] Preferably, the acyl chloride (R3-C(O)Cl) is selected from one or more combinations of butyryl chloride, hexanoyl chloride, octanoyl chloride, isooctanoyl chloride, 2-ethylhexanoyl chloride, nonanoyl chloride, decanoyl chloride, lauroyl chloride, myristoyl chloride, palmitoyl chloride, stearoyl chloride, and oleic acid chloride.

[0088] In one embodiment, the inert solvent is selected from the group consisting of C1-C6 alkane solvents, C2-C6 ester solvents, C2-C6 ether solvents, or combinations thereof; preferably, the inert solvent is (anhydrous) DCM.

[0089] In one embodiment, the molar ratio of the benzotriazole derivative to the acyl chloride R3-C(O)Cl is 1:(1.2-2); preferably (1.2-1.6); more preferably (1.4-1.5).

[0090] In one embodiment, the molar ratio of the benzotriazole derivative to the acid-binding agent is 1:(2-3); preferably 1:(2-2.5).

[0091] Compared with the prior art, the main advantages of the present invention include:

[0092] (1) The present application uses inexpensive and readily available benzotriazole and benzotriazole derivatives and alkylamines as raw materials to generate benzotriazole-alkylamines, which are then reacted with aliphatic hydrocarbon acyl chlorides to obtain a class of environmentally friendly ashless additives that are free of metals, sulfur, and phosphorus.

[0093] (2) The preparation method of the benzotriazole-amide derivative additive of the present application has a simple synthetic route, considerable yield, and its tribological properties can be effectively controlled by adjusting the length and structure of the alkyl chain and amide chain.

[0094] (3) When the benzotriazole-amide compound of the present invention is used as an ashless additive, it can form a dense and ordered lubricating film on the friction pair surface through the synergistic effect of polar amide bonds and non-polar alkanes to reduce friction and resist wear, and its friction-reducing effect in synthetic base oils is significant.

[0095] The present invention is further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Experimental methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions or as recommended by the manufacturer. Unless otherwise stated, percentages and parts are by weight.

[0096] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those familiar with the art. In addition, any methods and materials similar to or equivalent to those described herein may be applied to the methods of the present invention. The preferred embodiments and materials described herein are for illustrative purposes only.

[0097] Examples 1-6: Instruction manual 7 / 13 pages 11 CN 122079909 A

[0098] 1) Weigh 100 mmol benzotriazole and 300 mmol NaOH and dissolve them in 150 mL tetrahydrofuran (THF), stirring at room temperature for 30 min. Then add 150 mmol 2-chloroethylamine hydrochloride and 4.17 mmol TBAS, and heat under reflux for 12 h. Monitor the reaction of the benzotriazole starting material by TLC until the reaction is complete, and stop the reaction. Filter the reaction solution and evaporate under reduced pressure to remove the solvent. Dissolve it again with a small amount of DCM, wash twice with saturated sodium chloride solution, extract the organic phase with DCM, remove the water in the organic phase with anhydrous sodium sulfate, evaporate under reduced pressure again to remove the solvent, and separate by column chromatography (developing solvent: DCM:MeOH = 7:1) to obtain benzotriazole-1-ethylamine and benzotriazole-2-ethylamine.

[0099] 2) Weigh 20 mmol of benzotriazole-1-ethylamine or benzotriazole-2-ethylamine into a side-necked round-bottom flask, then add 80 mL of anhydrous DCM and 60 mmol of triethylamine; then slowly add 30 mmol of acyl chloride in an ice-water bath and react at room temperature for 12 h.TLC was used to monitor the complete reaction of the benzotriazole ethylamine, and the reaction was stopped. The solvent was removed by evaporation under reduced pressure. After dissolving in a small amount of DCM, the mixture was washed twice with saturated sodium chloride solution, the organic phase was extracted with DCM, and the water in the organic phase was removed with anhydrous sodium sulfate. The solvent was removed by evaporation under reduced pressure again, and the mixture was separated by column chromatography (developing solvent: PE:EA = 1:1) to obtain benzotriazole-ethylamide compounds (a-f).

[0100]

[0101] (a) Benzotriazole-1-ethyloleamide, white solid. 1H NMR (400MHz, DMSO‑d6) δ8.02(dt,J=8.4,1.0Hz,1H) ,7.90(t,J=5.6Hz,1H) ,7.79(dt,J=8.3,1.0Hz,1H) ,7.53(ddd ,J=8.2, 6.9,1.0Hz,1H) ,7.38(ddd ,J=8.1,6.9,1.0Hz,1H) ,5.39–5.25(m,2H) ,4.75(dd ,J=6.5, 5.2Hz,2H) ,3.57(q ,J=5.8Hz,2H) ,2.03–1.93(m,4H) ,1.90(t,J=7.4Hz,2H) ,1.38–1.13 (m,22H) ,0.89–0.79 (m,3H) .

[0102]

[0103] (b) Benzotriazole-2-ethyloleamide, white solid. 1H NMR (400MHz, DMSO-d6) δ 7.94 (t, J = 5.7Hz, 1H), 7.90 (dd, J = 6.5, 3.1Hz, 2H), 7.42 (dt, J = 6.6, 3.0Hz, 2H), 5.31 (t, J = 4.9Hz, 2H), 4.78 (t, J = 5.9Hz, 2H), 3.69 (q, J = 5.9Hz, 2H), 2.03–1.91 (m, 6H), 1.39 (p, J = 7.3Hz, 2H), 1.33–1.08 (m, 20H), 0.84 (t, J = 6.6Hz, 3H).

[0104]

[0105] (c) Benzotriazole-1-ethyllauramide. White solid.¹H NMR (400MHz, DMSO-d⁶) δ 8.02 (d, J = 8.3Hz, ¹H), 7.92 (d, J = 6.4Hz, ¹H), 7.79 (d, J = 8.3Hz, ¹H), 7.53 (t, J = 7.6Hz, ¹H), 7.39 (t, J = 7.6Hz, ¹H), 4.75 (t, J = 5.8Hz, 2H), 3.56 (q, J = 5.9Hz, 2H), 1.90 (t, J = 7.4Hz, 2H), 1.32 (t, J = 7.3Hz, 2H), 1.20 (d, J = 23.4Hz, 16H), 0.85 (t, J = 6.7Hz, 3H). (Instruction manual, page 8 / 13, 12 CN) 122079909 A

[0106]

[0107] (d) Benzotriazole-2-ethyllauramide. White solid. ¹H NMR (400MHz, DMSO-d₆) δ 7.93 (t, J = 4.6Hz, ¹H), 7.92–7.88 (m, 2H), 7.45–7.39 (m, 2H), 4.78 (dd, J = 6.5, 5.4Hz, 2H), 3.68 (q, J = 5.9Hz, 2H), 1.97 (t, J = 7.4Hz, 2H), 1.39 (p, J = 7.3Hz, 2H), 1.29–1.08 (m, 16H), 0.88–0.81 (m, 3H).

[0108]

[0109] (e) Benzotriazole-1-ethylhexylamide. White solid. 1H NMR (400MHz, DMSO‑d6) δ8.02(dt,J=8.4,1.0Hz,1H) ,7.89(d ,J=5.7Hz,1H) ,7.79(dt,J=8.4,1.0Hz,1H) ,7.53(ddd ,J=8.2, 6.9,1.0Hz,1H) ,7.38(ddd ,J=8.0,6.9,1.0Hz,1H) ,4.79–4.71(m,2H) ,3.56(q,J=5.9Hz, 2H) ,1.90(t,J=7.5Hz,2H) ,1.39–1.27(m,2H) ,1.22–1.13(m,2H) ,1.11–1.03(m,2H) ,0.80 (t,J=7.2Hz,3H) .

[0110]

[0111] (f)Benzotriazole-2-ethylhexylamide. White solid.1H NMR (400MHz, DMSO-d6) δ 7.94 (d, J = 5.8Hz, 1H), 7.91 (dd, J = 6.5, 3.1Hz, 2H), 7.46–7.39 (m, 2H), 4.78 (t, J = 5.9Hz, 2H), 3.68 (q, J = 5.9Hz, 2H), 1.97 (t, J = 7.4Hz, 2H), 1.40 (p, J = 7.4Hz, 2H), 1.25–1.16 (m, 2H), 1.16–1.07 (m, 2H), 0.80 (t, J = 7.1Hz, 3H).

[0112] Examples 7-8:

[0113] 1) Weigh 5g 5-Methyl-1H-benzotriazole and 4.5 g NaOH were dissolved in 80 mL tetrahydrofuran (THF) and stirred at room temperature for 30 min. Then, 6.5 g 2-chloroethylamine hydrochloride and 0.51 g TBAS were added, and the mixture was heated under reflux for 12 h. The reaction mixture was monitored by TLC until the 5-methyl-1H-benzotriazole reacted completely, at which point the reaction was stopped. The reaction solution was filtered, and the solvent was removed by evaporation under reduced pressure. The solution was then dissolved in a small amount of DCM, washed twice with saturated sodium chloride solution, and the organic phase was extracted with DCM. Water in the organic phase was removed with anhydrous sodium sulfate, and the solvent was removed again by evaporation under reduced pressure. The mixture was then separated by column chromatography (developing solvent: DCM:MeOH = 7:1) to obtain 5-methyl-2H-benzotriazole-2-ethylamine.

[0114] 2) Weigh 3g of 5-methyl-2H-benzotriazole-2-ethylamine into a side-necked round-bottom flask, add 50mL of anhydrous DCM and 4.3g of triethylamine; then slowly add 1.5eq. acyl chloride under an ice-water bath and react at room temperature for 12h. Monitor the reaction of 5-methyl-2H-benzotriazole-2-ethylamine by TLC until the reaction is complete, and stop the reaction. Remove the solvent by evaporation under reduced pressure. Dissolve the solvent again with a small amount of DCM, wash twice with saturated sodium chloride solution, extract the organic phase with DCM, and remove the water in the organic phase with anhydrous sodium sulfate. Remove the solvent again by evaporation under reduced pressure, and separate by column chromatography (developing solvent: PE:EA = 1:1) to obtain 5-methyl-2H-benzotriazole-2-ethylamide compound (g-h).

[0115]

[0116] (g) 5-methyl-2H-benzotriazole-2-ethyloleamide, pale yellow solid.1H NMR (400MHz, chloroform‑d) δ7.73(d,J=8.7Hz,1H) ,7.59(s,1H) ,7.23(dd,J=8.8,1.5Hz,1H) ,6.11(t,J=6.0Hz,1H) , 5.37–5.28(m ,2H) ,4 .83–4 .78(m ,2H) ,3 .94(q ,J=5 .7Hz ,2H) ,2 .49(s ,3H) ,2 .14(t ,J=7.6Hz,2H) ,1.99(qt,J=6.7,3.7Hz,4H) ,1.58(p,J=7.1Hz,2H) ,1.25(s,20H) ,0.87(t,J= 6.7Hz,3H).

[0117]

[0118] (h)5-methyl-2H-benzotriazole-2-ethyllauramide, white solid. ¹H NMR (400MHz, tetrachloroethane-d²) δ 7.77 (d, J = 8.7Hz, ¹H), 7.63 (s, ¹H), 7.26 (dd, J = 8.7, 1.5Hz, ¹H), 6.04 (t, J = 5.9Hz, ¹H), 4.81 (dd, J = 6.6, 4.3Hz, 2H), 3.91 (q, J = 5.7Hz, 2H), 2.51 (s, 3H), 2.13 (t, J = 7.6Hz, 2H), 1.55 (q, J = 7.2Hz, 2H), 1.36–1.15 (m, ¹⁶H), 0.88 (t, J = 6.7Hz, 3H).

[0119] Examples 9-10:

[0120] 1) Weigh 20 mmol of 5-butyl-1H-benzotriazole and 60 mmol of NaOH and dissolve them in 80 mL of tetrahydrofuran (THF). Stir at room temperature for 30 min. Then add 30 mmol of 2-chloroethylamine hydrochloride and 0.83 mmol of TBAS, and heat under reflux for 12 h. Monitor the reaction of the reactant 5-butyl-1H-benzotriazole by TLC until the reaction is complete, and stop the reaction. Filter the reaction solution and evaporate under reduced pressure to remove the solvent. Dissolve the solvent in a small amount of DCM, wash twice with saturated sodium chloride solution, extract the organic phase with DCM, remove the water in the organic phase with anhydrous sodium sulfate, evaporate under reduced pressure again to remove the solvent, and separate by column chromatography (developing solvent: DCM:MeOH = 7:1) to obtain 5-butyl-2H-benzotriazole-2-ethylamine.

[0121] 2) Weigh 10 mmol of 5-butyl-2H-benzotriazole-2-ethylamine into a side-necked round-bottom flask, then add 50 mL of anhydrous DCM and 30 mmol of triethylamine; then slowly add 15 mmol of acyl chloride in an ice-water bath and react at room temperature for 12 h.TLC monitoring showed that the reaction of 5-butyl-2H-benzotriazole-2-ethylamine was complete, and the reaction was stopped. The solvent was removed by evaporation under reduced pressure. After dissolving in a small amount of DCM, the mixture was washed twice with saturated sodium chloride solution, the organic phase was extracted with DCM, and the water in the organic phase was removed with anhydrous sodium sulfate. The solvent was removed by evaporation under reduced pressure again, and the mixture was separated by column chromatography (developing solvent: PE:EA = 1:1) to obtain 5-butyl-2H-benzotriazole-2-ethylamide compounds (i-j). Specification 10 / 13 pages 14 CN 122079909 A

[0122]

[0123] (i) 5-butyl-2H-benzotriazole-2-ethyl oleamide, brownish-yellow oil. 1H NMR (400MHz, DMSO‑d6) δ7.92(t,J=5.8Hz,1H) ,7.78(d,J=8.7Hz,1H) ,7.62(s,1H) ,7.27(dd,J=8.8,1.5Hz,1H) , 5.30(t,J=4.8Hz,2H) ,4.74(t,J=5.9Hz,2H) ,3.66(q,J=5.9Hz,2H) ,2.71(t,J=7.7Hz, 2H) ,1.97(q,J=7.1,5.7Hz,6H) ,1.66–1.53(m,2H) ,1.43–1.30(m,4H) ,1.30–1.08(m,20H) , 0.90 (t, J = 7.3 Hz, 3H), 0.86–0.80 (m, 3H).

[0124]

[0125] (j) 5-Butyl-2H-benzotriazole-2-ethyllauramide, light brown solid. 1H NMR (400MHz, DMSO- d6) δ7.93(t,J=5.8Hz,1H) ,7.80(d ,J=8.7Hz,1H) ,7.63(s,1H) ,7.28(dd ,J=8.8,1.6Hz, 1H) ,4.74(t,J=5.9Hz ,2H) ,3.67(q,J=5.9Hz,2H) ,2.71(t,J=7.6Hz,2H) ,1.97(t,J=7.3Hz,2H) ,1.67–1.55(m,2H) ,1.42–1.29(m,4H) ,1.19(dtd ,J=28.1 ,20.8,6.2Hz,17H) , 0.91(t, J=7.4Hz, 3H), 0.87–0.80(m, 3H).

[0126] Example 11:

[0127] 1) Add 60g Cs2CO3 and 20g Boc2NH, 1L DMF to the reaction flask, and stir vigorously for 1h under an argon atmosphere. Then add 99g dibromobutane and react at room temperature for 48h. Filter the reaction solution and evaporate the DMF to dryness.EA and water were added for extraction, followed by washing with saturated NaCl solution, dehydration with anhydrous sodium sulfate, and purification by rotary evaporation and column chromatography to obtain the product di-tert-butyl(4-bromobutyl)iminodicarboxylate. The product was reacted with methyltriazole to generate tert-butyl(4-(5-methyl-2H-benzotriazole-2-yl)butyl)(neopentyloxy) carbonate. Trifluoroacetic acid was added to the product, and the reaction generated 5-methyl-2H-benzotriazole-2-butylamine.

[0128] 2) 6.12 mmol of 5-methyl-2H-benzotriazole-2-butylamine was weighed into a round-bottom flask with a side neck, and 50 mL of anhydrous DCM and 2 mL of triethylamine were added. Then, 9.16 mmol of oleoyl chloride was slowly added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 12 h. The reaction of 5-methyl-2H-benzotriazole-2-butylamine was monitored by TLC until it was completely reacted, and the reaction was stopped. The solvent was removed by evaporation under reduced pressure. After dissolving in a small amount of DCM, the organic phase was washed twice with saturated sodium chloride solution, extracted with DCM, and the water in the organic phase was removed with anhydrous sodium sulfate. The solvent was removed again by vacuum evaporation, and the product was separated by column chromatography (developing solvent: PE:EA = 1:1) to obtain 5-methyl-2H-benzotriazole-2-butyloleamide (k).

[0129]

[0130] (k) 5-methyl-2H-benzotriazole-2-butyloleamide, pale yellow oil. ¹H NMR (400MHz, datasheet, pages 11 / 13, CN 122079909 A Chloroform-d) δ 7.73 (d, J = 8.8 Hz, 1H), 7.59 (s, 1H), 7.22 (d, J = 8.8 Hz, 1H), 5.63 (s, 1H), 5.33 (q, J = 6.0, 4.7 Hz, 2H), 4.72 (t, J = 6.8 Hz, 2H), 3.29 (q, J = 6.5 Hz, 2H), 2.49 (s, 3H), 2.14 (q, J = 6.7, 5.6 Hz, 4H), 2.00 (d, J = 6.5 Hz, 4H), 1.61 (s, 2H) ,1.57–1.50(m,2H) ,1.29 (t,J=10.9Hz,20H) ,0.87(t,J=6.7Hz,3H) .

[0131] Test Example 1: Tribological performance evaluation of benzotriazole-amide derivative additive 5-methyl-2H-benzotriazole-2-ethyl oleamide (compound g)

[0132] Compound g 5-methyl-2H-benzotriazole-2-ethyl oleamide was added to a mixed base oil of low viscosity synthetic hydrocarbon PAO4 and saturated polyol ester 3970 at an addition dose of 0.5 wt.% (mass percentage) (the mass ratio of PAO4 to 3970 is 90:10). The mixture was stirred at 60°C for 30 min to obtain a nearly colorless and transparent sample oil.The friction coefficient and wear scar diameter of the blank base oil (i.e., a mixture of PAO4 and 3970 in a weight ratio of 90:10) and the sample oil were tested using a four-ball friction and wear tester. The test conditions were: load 392N, spindle speed 1200r / min, oil temperature 75℃, and test time 60min. The test results are shown in Figures 1-3.

[0133] It can be seen from the friction curve comparison diagram in Figure 1 that the friction coefficient of the blank base oil fluctuated greatly during the friction process, indicating that its oil film was unstable. The friction curve of the sample oil with 0.5wt.% of 5-methyl-2H-benzotriazole-2-ethyloleamide prepared in Example 7 was more stable, indicating that the benzotriazole derivative-amide compound provided by the present invention can effectively improve the stability of the oil film.

[0134] Comparing the results in Figures 2 and 3, it can be seen that adding 0.5 wt.% of the 5-methyl-2H-benzotriazole-2-ethyloleamide prepared in Example 7 can reduce the average coefficient of friction and the wear scar diameter by 3.2% and 21.6%, respectively. That is, the friction reduction and anti-wear properties of the oil are improved by 3.2% and 21.6%, respectively, indicating that it has good compatibility with low viscosity synthetic base oils and can significantly improve the tribological properties of low viscosity hydrocarbons and synthetic esters.

[0135] In addition, as can be seen from the wear scar morphology in Figure 3, the friction pair surface lubricated by the blank base oil has more furrows caused by abrasive wear. After adding 0.5 wt.% of the 5-methyl-2H-benzotriazole-2-ethyloleamide prepared in Example 7, the furrows are reduced, indicating that the benzotriazole derivative-amide compound provided by the present invention can effectively improve the lubrication durability of low viscosity oils.

[0136] Under the same test conditions, the friction coefficient and wear scar diameter of base oils containing other benzotriazole-amide derivative additives provided by the present invention are shown in the following table:

[0137] Specification 12 / 13 pages 16 CN 122079909 A

[0138]

[0139] All documents mentioned in this invention are incorporated herein by reference as if each document were individually incorporated by reference. Furthermore, it should be understood that after reading the foregoing teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.Description 13 / 13 Pages 17 CN 122079909 A Figure 1 Figure 2 Description Drawings 1 / 2 Pages 18 CN 122079909 A Figure 3 Description Drawings 2 / 2 Pages 19 CN 122079909 A Abstract This invention provides a benzotriazole-amide derivative additive and a preparation method thereof. Specifically, this invention discloses an environmentally friendly, ashless additive that is free of sulfur and phosphorus. Using benzotriazole-alkylamine as a raw material, corresponding benzotriazole-amide derivatives are synthesized by combining the raw material with acyl chlorides of different structures. By selecting the substituent R1 on the benzene ring, the amine chain length n, the substituent R2, and the acyl chloride carbon chain R3, the compatibility of the additive with various base oils can be controlled, and the lubricating performance of the additive can be effectively regulated.

Claims

1. An ashless additive, characterized in that, The additive comprises one or more benzotriazole-amide derivative components with the following structure: in, R1 and R2 are independently -H and -C respectively. m H 2m+1 or -C m H 2m-1 ; R3 is -C m H 2m+1 or -C m H 2m-1 ; m is an integer from 1 to 20; n is an integer from 1 to 19; Furthermore, in the additive, the content of the component with the shown structure is ≥50%, preferably ≥70%, more preferably ≥90%, and most preferably ≥95%.

2. The ashless additive as described in claim 1, characterized in that, The additive comprises one or more benzotriazole-amide derivative components selected from the following formulas (I)-(VI): in, R1 and R2 are independently -H and -C respectively. m H 2m+1 or -C m H 2m-1 ; R3 is -C m H 2m+1 or -C m H 2m-1 ; m is an integer from 1 to 20; n is an integer from 1 to 19; Furthermore, in the additive, the content of the components represented by Formula I, Formula II, Formula III, Formula IV, Formula V and Formula VI is ≥50%, preferably ≥70%, more preferably ≥90%, and most preferably ≥95%.

3. The additive as described in claim 1, characterized in that, The additives mentioned are selected from the following group: Or a combination thereof.

4. An ashless additive-base oil complex, characterized in that, The complex includes the ashless additive as described in claim 1; preferably, the amount of the ashless additive added to the complex is 0.1-10.0 wt% of the weight of the base oil, more preferably 0.1-5.0 wt%.

5. The complex according to claim 4, characterized in that, The base oil is selected from the group consisting of synthetic hydrocarbon base oils, synthetic ester base oils, polyether base oils, alkyl naphthalene base oils, or combinations thereof.

6. A method for preparing a benzotriazole-amide derivative, characterized in that, Includes the following steps: In an inert atmosphere and in the presence of an acid-binding agent, benzotriazole derivatives react with acyl chloride R3-C(O)Cl to give benzotriazole-amide derivatives. in, R1 and R2 are independently -H and -C respectively. m H 2m+1 or -C m H 2m-1 ; R3 is -C m H 2m+1 or -C m H 2m-1 ; m is an integer from 1 to 20; n is an integer from 1 to 19.

7. The preparation method according to claim 6, characterized in that, The benzotriazole derivatives are selected from the group consisting of 1H-benzotriazole-ethylamine, 2H-benzotriazole-ethylamine, 5-methyl-1H-benzotriazole-ethylamine, 5-methyl-2H-benzotriazole-ethylamine, 6-methyl-1H-benzotriazole-ethylamine, 5-methyl-1H-benzotriazole-butylamine, 5-methyl-2H-benzotriazole-butylamine, 6-methyl-1H-benzotriazole-butylamine, 5-butyl-1H-benzotriazole-ethylamine, 5-butyl-2H-benzotriazole-ethylamine, 6-butyl-1H-benzotriazole-ethylamine, or combinations thereof.

8. The preparation method according to claim 6, characterized in that, The acid-binding agent is selected from the group consisting of triethylamine, pyridine, Na2CO3, NaHCO3, K2CO3, NaOH, KOH, or combinations thereof.

9. The preparation method according to claim 6, characterized in that, The acyl chloride R3-C(O)Cl is selected from the following group: butyroyl chloride, hexanoyl chloride, octanoyl chloride, isooctanoyl chloride, 2-ethylhexanoyl chloride, nonanoyl chloride, decanoyl chloride, lauroyl chloride, myristoyl chloride, palmitoyl chloride, stearoyl chloride, oleic acid chloride, or combinations thereof.

10. A method for preparing the ashless additive-base oil complex according to claim 4, characterized in that, Includes the following steps: The ashless additive of claim 1 is mixed with a base oil to obtain the composite.

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