A benzotriazole-amide derivative additive and its preparation method

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, using benzotriazole-alkylamine as a raw material, and synthesizing corresponding benzotriazole-amide derivatives 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 can be controlled, effectively regulating the lubricating performance of the additive.

Description

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 Technology

[0002] In daily life, lubricating materials are commonly used to reduce friction loss and prevent wear failure. Before the 1830s, additive-free lubricating oils (base oils) could meet the needs of production and daily life. However, with the development of technology, people have increasingly stringent requirements for the use of mechanical equipment, such as higher loads, temperatures, and speeds. Base oils can no longer meet the lubrication needs 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 ranges from 1%wt to 30%wt. They can significantly improve the performance of oils and supplement some characteristics that base oils do not possess.

[0003] In terms of performance, synthetic base oils offer better heat resistance and oxidation resistance compared to traditional mineral base oils, while also providing a wider operating temperature range, making them a preferred choice for developing high-performance lubricants. However, the compatibility of synthetic base oils, especially synthetic hydrocarbon base oils, with additives remains a challenge.

[0004] Given the increasing precision requirements of machinery and the upgrading of lubricating oil 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. To address the problems of poor compatibility of existing ashless additives with synthetic base oils of different structures, ineffective reduction of the coefficient of friction in low-viscosity base oils, and adverse environmental impacts, there is an urgent need in this field to develop a widely applicable and highly compatible ashless additive. Summary of the Invention

[0005] One object of the present invention is to provide a benzotriazole-amide derivative additive with wide applicability and good compatibility, and a method for preparing the same.

[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] in,

[0009] R1 and R2 are independently -H and -C respectively. m H 2m+1 or -C m H 2m-1 ;

[0010] R3 is -C m H 2m+1 or -C m H 2m-1 ;

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

[0012] Furthermore, 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; more preferably, n is an integer from 1 to 6; even more preferably, n is an integer from 1 to 3.

[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 formulas (I)-(VI):

[0016]

[0017] in,

[0018] R1 and R2 are independently -H and -C respectively. m H 2m+1 or -C m H 2m-1 ;

[0019] R3 is -C m H 2m+1 or -C m H 2m-1 ;

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

[0021] 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%.

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

[0023]

[0024] Or a combination 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 oils, synthetic ester base oils, polyether base oils, alkylnaphthalene base oils, 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); more preferably, it is 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] 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.

[0034] in,

[0035] R1 and R2 are independently -H and -C respectively. m H 2m+1 or -C m H 2m-1 ;

[0036] R3 is -C m H 2m+1 or -C m H 2m-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 includes the steps of: providing a mixture of a benzotriazole derivative and an acid-binding agent in an inert solvent, reacting it with an acyl chloride solution to obtain the benzotriazole-amide derivative.

[0039] In another preferred embodiment, the reaction further includes post-processing.

[0040] In another preferred embodiment, the post-processing includes the steps of: water quenching, 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); more preferably (1.2-1.6); and even 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); more preferably, it is 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 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.

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

[0048] The ashless additive described in the first aspect of the present invention is mixed with a base oil to obtain the composite.

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

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

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

[0052] It should be understood that, within the scope of this invention, the above-described technical features of this invention and the technical features specifically described below (such as in the embodiments) 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. Attached Figure Description

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

[0054] Figure 2 The friction-reducing properties of the sample oil with 0.5 wt.% of the benzotriazole derivative-amide compound prepared in Example 7 of this invention added were compared with those of the blank base oil.

[0055] Figure 3 The anti-wear properties of the sample oil containing 0.5 wt.% of the benzotriazole derivative-amide compound prepared in Example 7 of this invention were compared with those of the blank base oil. Detailed Implementation

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

[0057] the term

[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, strengthen 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 oils used in mechanical equipment and industrial machinery, including mineral-based and synthetic lubricating oils.

[0060] As used in this article, the term "synthetic hydrocarbon base oil" refers to oils produced by the polymerization of α-olefins under the action of a catalyst, which have excellent overall performance.

[0061] As used in this article, the term "synthetic ester base oil" is produced by dehydration of fatty acids and fatty alcohols through an esterification reaction in the presence of a catalyst. Depending on the types of fatty acids and fatty alcohols involved in the reaction, synthetic esters can be classified as polyol esters, diesters, and monoesters, etc.

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

[0063] Ashless additives

[0064] This invention provides an ashless additive that exhibits good compatibility with various base oils and excellent friction and wear reduction effects. Specifically, the ashless additive comprises one or more benzotriazole derivative-amide derivative components with the following structures:

[0065]

[0066] in,

[0067] R1 and R2 are independently -H and -C respectively. m H 2m+1 or -C m H 2m-1 ;

[0068] R3 is -C m H 2m+1 or -C m H 2m-1 ;

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

[0070] Furthermore, 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; even better, 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] Furthermore, in the ashless 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%.

[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 ashless additive is added at an amount of 0.1-10.0 wt% of the base oil weight, more preferably 0.1-5.0 wt%, and even 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 derivatives

[0082] This invention provides a method for preparing a benzotriazole derivative-amide derivative, specifically comprising the following steps:

[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 benzotriazole derivative is complete as monitored by TLC. The reaction is then quenched with water. After extraction, washing, drying and purification, the corresponding benzotriazole-amide derivative compound is obtained.

[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) This 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 this application has a simple synthetic route, a 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 orderly lubricating film through the synergistic effect of polar amide bonds and non-polar alkanes on the surface of the friction pair to reduce friction and resist wear, and has a significant friction-reducing effect in synthetic base oils.

[0095] The present invention will be 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, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. Percentages and parts are by weight unless otherwise stated.

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

[0097] Examples 1-6:

[0098] 1) Weigh 100 mmol of benzotriazole and 300 mmol of NaOH and dissolve them in 150 mL of tetrahydrofuran (THF). Stir at room temperature for 30 min. Then add 150 mmol of 2-chloroethylamine hydrochloride and 4.17 mmol of TBAS, and heat under reflux for 12 h. Monitor the reaction of the benzotriazole starting material by TLC until complete, and then 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 water from 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, add 80 mL of anhydrous DCM and 60 mmol of triethylamine; then slowly add 30 mmol of acyl chloride dropwise under an ice-water bath, and react at room temperature for 12 h. Monitor the reaction of the benzotriazole-ethylamine by TLC until complete, and then stop the reaction. Remove the solvent by evaporation under reduced pressure. Dissolve the compound in a small amount of DCM, wash twice with saturated sodium chloride solution, extract the organic phase with DCM, remove water from 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 the benzotriazole-ethylamide compound (af).

[0100]

[0101] (a) Benzotriazole-1-ethyloleamide, white solid. 1 H 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 (400 MHz, DMSO-d6) δ 7.94 (t, J = 5.7 Hz, 1H), 7.90 (dd, J = 6.5, 3.1 Hz, 2H), 7.42 (dt, J = 6.6, 3.0 Hz, 2H), 5.31 (t, J = 4.9 Hz, 2H), 4.78 (t, J = 5.9 Hz, 2H), 3.69 (q, J = 5.9 Hz, 2H), 2.03–1.91 (m, 6H), 1.39 (p, J = 7.3 Hz, 2H), 1.33–1.08 (m, 20H), 0.84 (t, J = 6.6 Hz, 3H).

[0104]

[0105] (c) Benzotriazole-1-ethyllauramide. White solid. 1 H NMR (400MHz, DMSO-d6) δ8.02(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).

[0106]

[0107] (d) Benzotriazole-2-ethyllauramide. White solid. 1 H NMR(400MHz, DMSO-d6)δ7.93(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,2 H),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. 1 H NMR(400MHz,DMSO-d6)δ8.02(dt,J=8.4,1.0Hz,1H),7.89(d,J=5.7Hz,1H),7.7 9(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. 1 H NMR(400MHz, DMSO-d6)δ7.94(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 of 5-methyl-1H-benzotriazole and 4.5g of NaOH and dissolve them in 80mL of tetrahydrofuran (THF). Stir at room temperature for 30min. Then add 6.5g of 2-chloroethylamine hydrochloride and 0.51g of TBAS, and heat under reflux for 12h. Monitor the reaction of the reactant 5-methyl-1H-benzotriazole by TLC until complete, and stop the reaction. Filter the reaction solution and evaporate under reduced pressure to remove the solvent. Dissolve the solvent again with a small amount of DCM, wash twice with saturated sodium chloride solution, extract the organic phase with DCM, remove water from 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-methyl-2H-benzotriazole-2-ethylamine.

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

[0115]

[0116] (g) 5-Methyl-2H-benzotriazole-2-ethyloleamide, pale yellow solid. 1 H 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. 1¹H NMR (400 MHz, tetrachloroethane-d²) δ 7.77 (d, J = 8.7 Hz, 1H), 7.63 (s, 1H), 7.26 (dd, J = 8.7, 1.5 Hz, 1H), 6.04 (t, J = 5.9 Hz, 1H), 4.81 (dd, J = 6.6, 4.3 Hz, 2H), 3.91 (q, J = 5.7 Hz, 2H), 2.51 (s, 3H), 2.13 (t, J = 7.6 Hz, 2H), 1.55 (q, J = 7.2 Hz, 2H), 1.36–1.15 (m, 16H), 0.88 (t, J = 6.7 Hz, 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 starting material 5-butyl-1H-benzotriazole by TLC until the reaction is complete, and then 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 water from 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 round-bottom flask with a side neck, add 50 mL of anhydrous DCM and 30 mmol of triethylamine; then slowly add 15 mmol of acyl chloride dropwise under an ice-water bath, and react at room temperature for 12 h. Monitor the reaction of 5-butyl-2H-benzotriazole-2-ethylamine by TLC until complete, and stop the reaction. Remove the solvent by evaporation under reduced pressure. Dissolve the compound again with a small amount of DCM, wash twice with saturated sodium chloride solution, extract the organic phase with DCM, remove water from 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 the 5-butyl-2H-benzotriazole-2-ethylamide compound (ij).

[0122]

[0123] (i) 5-Butyl-2H-benzotriazole-2-ethyloleamide, 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=7.3Hz,3H),0.86–0.80(m,3H).

[0124]

[0125] (j) 5-Butyl-2H-benzotriazole-2-ethyllauramide, light brown solid. 1 H 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),2.7 1(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 a reaction flask, and stir vigorously for 1 hour under an argon atmosphere. Then add 99g dibromobutane and react at room temperature for 48 hours. Filter the reaction solution and evaporate the DMF to dryness. Add EA and water for extraction, wash with saturated NaCl solution, remove water with anhydrous sodium sulfate, evaporate to dryness, and purify by column chromatography to obtain the product di-tert-butyl(4-bromobutyl)iminodicarboxylate. React the product with methylbenzyltriazole to generate tert-butyl(4-(5-methyl-2H-benzotriazole-2-yl)butyl)(neopentyloxy) carbonate. Add trifluoroacetic acid to generate 5-methyl-2H-benzotriazole-2-butylamine.

[0128] 2) Weigh 6.12 mmol of 5-methyl-2H-benzotriazole-2-butylamine into a round-bottom flask with a side neck, add 50 mL of anhydrous DCM and 2 mL of triethylamine; then slowly add 9.16 mmol of oleoyl chloride dropwise under an ice-water bath, and react at room temperature for 12 h. Monitor the reaction by TLC until the 5-methyl-2H-benzotriazole-2-butylamine has completely reacted, then stop the reaction. Remove the solvent by evaporation under reduced pressure. Dissolve the oleoylamine in a small amount of DCM, wash twice with saturated sodium chloride solution, extract the organic phase with DCM, remove water from 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-butyloleamide (k).

[0129]

[0130] (k)5-Methyl-2H-benzotriazole-2-butyloleamide, pale yellow oil. 1 H NMR (400MHz, Chloroform-d) δ7.73 (d, J = 8.8 Hz, 1H), 7.59 (s, 1H), 7.22 (d, J = 8. 8Hz,1H),5.63(s,1H),5.33(q,J=6.0,4.7Hz,2H),4.72(t,J=6.8Hz,2H),3.29(q ,J=6.5Hz,2H),2.49(s,3H),2.14(q,J=6.7,5.6Hz,4H),2.00(d,J=6.5Hz,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 property evaluation of benzotriazole-amide derivative additive 5-methyl-2H-benzotriazole-2-ethyloleamide (compound g)

[0132] Compound g, 5-methyl-2H-benzotriazole-2-ethyloleamide, was added at a dosage of 0.5 wt.% (mass percentage) to a mixed base oil of low-viscosity synthetic hydrocarbon PAO4 and saturated polyol ester 3970 (PAO4 to 3970 mass ratio of 90:10). The mixture was stirred at 60°C for 30 min to obtain a nearly colorless and transparent sample oil. The coefficient of friction and wear scar diameter of the blank base oil (i.e., the mixed base oil of PAO4 and 3970 at 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 392 N, spindle speed 1200 r / min, oil temperature 75°C, and test time 60 min. The test results are shown in [Figure number missing]. Figure 1-3 .

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

[0134] contrast Figure 2 and Figure 3 The results show that adding 0.5 wt.% of 5-methyl-2H-benzotriazole-2-ethyloleamide prepared in Example 7 can reduce the average friction coefficient and 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. This indicates 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, by Figure 3 The wear scar morphology shows that the friction pair surface lubricated by the blank base oil has many ploughing grooves caused by abrasive wear. After adding 0.5 wt.% of 5-methyl-2H-benzotriazole-2-ethyloleamide prepared in Example 7, the ploughing grooves are reduced, indicating that the benzotriazole derivative-amide compound provided by the present invention can effectively improve the lubrication durability of low viscosity oil.

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

[0137]

[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 this invention, and these equivalent forms also fall within the scope defined by the appended claims.

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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