Hydraulic oil composition and preparation method thereof

Abstract

The invention provides a hydraulic oil composition and a preparation method thereof. The hydraulic oil composition of the present invention comprises: (A) an imidazoline derivative; (B) an anti-wear agent; (C) an antioxidant; (D) a metal deactivator; (E) a demulsifier; (F) an anti-foaming agent; (G) base oil; wherein the structure of the imidazoline derivative is shown as a formula (I), in the formula (I), n is an integer between 1 and 10, and each R group is independently selected from C2-C5 alkylene; the R0 group is selected from C15-C20 alkyl, cycloalkyl or alkenyl; and each R'group is independently selected from C1-C20 alkyl groups. The hydraulic oil composition disclosed by the invention has excellent anti-rust and anti-corrosion properties, oxidation resistance, wear resistance and long-term stability, and is long in service life.

Description

Technical Field

[0001] The present invention relates to the field of lubricating oils, and in particular to a hydraulic oil composition having excellent anti-rust and anti-corrosion properties, antioxidant properties, anti-wear properties and long-term stability, and a preparation method thereof. Background Art

[0002] Hydraulic oil is the transmission medium used in hydraulic systems and also provides lubrication, rust prevention, corrosion protection, and cooling. Its usage accounts for over 40% of all industrial lubricant products. With the rapid advancement of modern hydraulic technology, hydraulic equipment is becoming increasingly smaller and more sophisticated, resulting in increasingly demanding operating conditions for hydraulic systems, with ever-increasing operating pressures and temperatures. During hydraulic oil operation, high temperatures accelerate the oil's oxidation, small molecular weight acids generated by additive degradation, and corrosive media such as moisture enter the oil. These reactions can cause chemical or electrochemical reactions on metal surfaces in the hydraulic system, generating a mixture of oxides and hydroxides, leading to rust and compromising the stability and reliability of the hydraulic equipment. However, hydraulic oil cannot alter the inherent corrosion resistance of the metal materials it contacts. Therefore, the addition of functional rust inhibitors is necessary to prevent rust during operation, extend the service life of hydraulic machinery, and prolong the hydraulic oil change interval.

[0003] Currently, rust inhibitors widely used in the field of hydraulic oils include sulfonates, alkenyl succinic acid, alkenyl succinic anhydride, and alkenyl succinates, but they still have the disadvantages of high ash content and high acid value. In comparison, imidazoline rust inhibitors have become a very promising rust inhibitor due to their low toxicity, high stability, and low acid value, but their oil solubility and antioxidant properties need to be further improved. CN 102653696 discloses a method for attaching imidazoline groups to ethylene-propylene copolymers using chemical modification to produce a multifunctional additive with good dispersion, rust prevention, and improved viscosity-temperature properties. However, the product has a high viscosity and is not suitable for the field of hydraulic oils. Developing rust inhibitors and hydraulic oils with excellent anti-rust, anti-corrosion, and antioxidant properties remains a goal of those skilled in the art. Summary of the Invention

[0004] The invention provides a hydraulic oil composition and a preparation method thereof.

[0005] The hydraulic oil composition of the present invention comprises: (A) an imidazoline derivative; (B) an antiwear agent; (C) an antioxidant; (D) a metal deactivator; (E) a demulsifier; (F) an antifoaming agent; and (G) a base oil. The structure of the imidazoline derivative is shown in formula (I):

[0006]

[0007] In formula (I), n is an integer between 1 and 10, each R group is independently selected from a C2 to C5 alkylene group; R0 group is selected from C 15 ~C 20 alkyl, cycloalkyl or alkenyl; each R' group is independently selected from C1 to C 20 of alkyl.

[0008] According to the present invention, the R0 group can be C 15 ~C 20 The alkyl group can also be C 15 ~C 20 The cycloalkyl group can also be C 15 ~C 20 The alkenyl group. 15 ~C 20 The alkenyl group may be a group containing one or more carbon-carbon double bonds within the group and an alkyl group at the end of the group, a group with a carbon-carbon double bond at the end of the group, or a group containing one or more carbon-carbon double bonds within the group and a carbon-carbon double bond at the end of the group.

[0009] According to the present invention, preferably, in formula (I), n is an integer between 1 and 5 (for example, 1, 2, 3, 4 or 5), each R group is independently selected from ethylene or propylene; R0 group is selected from C 16 ~C 18 Each R' group is independently selected from a C2 to C8 alkyl group.

[0010] According to the present invention, the imidazoline derivative may be one or more of the following compounds:

[0011]

[0012] According to the present invention, the preparation method of the imidazoline derivative comprises the following steps:

[0013] (1) reacting CS2 with a compound represented by formula (X);

[0014]

[0015] The R' groups are independently selected from C1 to C 20 Alkyl;

[0016] (2) reacting the reaction product of step (1) with a compound represented by formula (Y), and collecting the product;

[0017]

[0018] wherein n is an integer between 1 and 10, each R group is independently selected from a C2 to C5 alkylene group; R0 group is selected from a C15 ~C 20 an alkyl, cycloalkyl or alkenyl group.

[0019] According to the present invention, preferably, n is an integer between 1 and 5 (for example, 1, 2, 3, 4 or 5), each R group is independently selected from ethylene or propylene; R0 group is selected from C 16 ~C 18 Each R' group is independently selected from a C2 to C8 alkyl group.

[0020] According to the present invention, in step (1), the reaction formula between CS2 and the compound represented by formula (X) is as follows.

[0021]

[0022] According to the present invention, in step (2), the reaction formula between the reaction product of step (1) and the compound represented by formula (Y) is as follows.

[0023]

[0024] According to the present invention, in step (1), the molar ratio between CS2 and the compound represented by formula (X) can be 0.8 to 1.3:1, preferably 0.9 to 1.2:1; in step (2), the molar ratio between the compound represented by formula (Y) and CS2 in step (1) can be 1:0.5 to 1.5, preferably 1:0.8 to 1.2.

[0025] According to the present invention, in step (1), the temperature for the reaction between CS2 and the compound represented by formula (X) can be 10 to 50° C., preferably 15 to 25° C.; the reaction time is usually 0.5 to 5 h, preferably 0.5 to 2.5 h; in step (2), the temperature for the reaction between the reaction product of step (1) and the compound represented by formula (Y) can be 60 to 100° C., preferably 70 to 90° C.; the reaction time is usually 0.5 to 3 h, preferably 1 to 2 h.

[0026] According to the present invention, the compound represented by formula (Y) can be prepared by subjecting the compound represented by formula (α) and the compound represented by formula (β) to an amidation dehydration reaction followed by a cyclodehydration reaction;

[0027]

[0028] wherein n is an integer between 1 and 10, each R group is independently selected from a C2 to C5 alkylene group; R0 group is selected from a C 15 ~C 20 an alkyl, cycloalkyl or alkenyl group.

[0029] According to the present invention, preferably, n is an integer between 1 and 5 (for example, 1, 2, 3, 4 or 5), each R group is independently selected from ethylene or propylene; R0 group is selected from C 16 ~C 18 alkyl or alkenyl.

[0030] According to the present invention, the molar ratio between the compound represented by formula (α) and the compound represented by formula (β) can be 1 to 2:1, preferably 1 to 1.5:1; during the reaction of the compound represented by formula (α) and the compound represented by formula (β), the temperature for the amidation dehydration reaction can be 140 to 180°C, preferably 140 to 160°C, and the reaction time is usually 1 to 3 hours, preferably 1 to 2 hours; the temperature for the cyclodehydration reaction can be 180 to 250°C, preferably 220 to 240°C, and the reaction time is usually 2 to 6 hours, preferably 3 to 5 hours.

[0031] According to the present invention, a water-carrying agent may or may not be added during the reaction between the compound represented by formula (α) and the compound represented by formula (β). The water-carrying agent may be an aromatic hydrocarbon solvent, such as xylene.

[0032] According to the present invention, the compound represented by formula (X) can be selected from one or more of di-n-butylamine, di-n-pentylamine and di-n-hexylamine, the compound represented by formula (α) can be selected from one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine, and the compound represented by formula (β) can be selected from one or more of hexadecanoic acid, octadecanoic acid, oleic acid and linoleic acid.

[0033] According to the present invention, in step (2), the product of the reaction product of step (1) and the compound shown in formula (Y) reacts comprises the imidazoline derivative main product and a small amount of by-products. Since these by-products themselves can be used as additives, these by-products can be separated out in step (2), or these by-products can be retained in the product and directly used as additives. Those skilled in the art can obtain pure imidazoline derivatives by purification or separation methods, such as those that can be enumerated by vacuum distillation, molecular distillation, column chromatography or preparative chromatography.

[0034] According to the present invention, the antiwear agent of component (B) can be selected from one or more of polysulfide compounds, phosphates, sulfur phosphates and phosphorus-nitrogen type extreme pressure antiwear agents, for example, aminothioesters, sulfurized isoolefins, alkyl polysulfides, trialkyl phosphates, trialkyl phosphites, dialkyl phosphites, trialkyl thiophosphates, dithiophosphates, thiophosphate complexes, dithiophosphate derivatives, phosphate amine salts and acidic phosphate amine salts. Common trade names include T323, TPS32, TPS20, TPS44, T321, T306, T304, T451, T353, T63, T309, T307, T305, T308, T349, T120, T8828, etc.

[0035] According to the present invention, the antioxidant of component (C) can be selected from one or more of phenol ester type, thiophenol type, hindered phenol type and hindered amine type antioxidants, for example, (3,5-di-tert-butyl-4-hydroxyphenyl)-isooctyl propionate, 2,2'-thiobis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)ethyl propionate], 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,6-bis(octylthiomethyl)-o-cresol, 2,6-di-tert-butyl-α-dimethylamino-p-cresol, 2,6-di-tert-butyl-p-cresol, 4,4-methylenebis(2,6-di-tert-butylphenol), alkylated diphenylamine and phenyl-α-naphthylamine. Common trade names include T512, IRGANOX L-135, T535, L115, L118, T501, IRGANOX L-01, IRGANOX L-57, T534, LZ5150A, VANLUBE NA, VANLUBE 961, VANLUBE 81, RC7001, N438L, etc. The antioxidant of component (C) is preferably a composite antioxidant comprising a phenolic ester antioxidant and a thiophenolic antioxidant, wherein the phenolic ester antioxidant accounts for 50% to 90% of the total weight of the composite antioxidant, and the thiophenolic antioxidant accounts for 10% to 50% of the total weight of the composite antioxidant.

[0036] According to the present invention, the metal deactivator of the component (D) can be selected from one or more of thiadiazole derivatives, benzotriazole derivatives and propionohydrazide, for example, one or more of 2,5-bis(tert-nonyldithio)-1,3,4-thiadiazole, N,N'-dibutylaminomethylenebenzotriazole and 1,2-bis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propiono]hydrazide can be selected. Common trade names include T571, T551, T561, IR39, IR42, ANOX-1024 and the like.

[0037] According to the present invention, the demulsifier of component (E) can be selected from one or more of propylene oxide diamine polycondensate, polymer polyether, ethylene glycol ester and ethylene glycol ether. Common trade names include T1001, T1002, DL32, M10394 and the like.

[0038] According to the present invention, the antifoaming agent of component (F) can be selected from one or more of methyl silicone oil, acrylic acid and ether copolymer and polyacrylate. Common trade names include T901, T911, T912, T921, T922 and the like.

[0039] According to the present invention, the base oil of component (G) can be selected from one or more of mineral base oil, synthetic ester oil and poly-α-olefin synthetic oil. The mineral base oil can be selected from HIV II / II+ base oil and HIVIII / III+ base oil; the synthetic ester oil can be selected from dioctyl sebacate, saturated trimethylolpropane ester and pentaerythritol ester; the poly-α-olefin synthetic oil can be selected from one or more of PAO-4, PAO-6, PAO-10, PAO-40 and PAO-100.

[0040] According to the present invention, the component (A) accounts for 0.01% to 5% (preferably 0.02% to 3%) of the total mass of the hydraulic oil composition; the component (B) accounts for 0.1% to 10% (preferably 0.2% to 5%) of the total mass of the hydraulic oil composition; the component (C) accounts for 0.1% to 10% (preferably 0.2% to 5%) of the total mass of the hydraulic oil composition; the component (D) accounts for 0.001% to 5% (preferably 0.01% to 3%) of the total mass of the hydraulic oil composition; the component (E) accounts for 0.0001% to 0.1% (preferably 0.0005% to 0.05%) of the total mass of the hydraulic oil composition; the component (F) accounts for 0.01% to 0.1% (preferably 0.02% to 0.05%) of the total mass of the hydraulic oil composition; and the component (G) constitutes the main component of the hydraulic oil composition.

[0041] The method for preparing the hydraulic oil composition of the present invention comprises the step of mixing the above components at a mixing temperature preferably between 40° C. and 90° C. and a mixing time preferably between 1 hour and 6 hours.

[0042] The hydraulic oil composition of the present invention has excellent anti-rust and anti-corrosion performance, anti-oxidation performance, anti-wear performance and long-term stability performance and a long service life. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 This is the LC-MS chart of the alkyl-substituted imidazoline product of step (1) in Example 1.

[0044] Figure 2 LC-MS chart of the product of step (3) in Example 1 (i.e., imidazoline derivative). DETAILED DESCRIPTION

[0045] The present invention is further described below by way of examples, which are not intended to limit the present invention. The main raw materials used are as follows:

[0046] Raw material name Specification Source of raw materials Dibutylamine 99％ Zhejiang Jiande Jianye Organic Chemical Co., Ltd. Carbon disulfide analytically pure Sinopharm Chemical Reagent Co., Ltd. Oleic acid, linoleic acid analytically pure Beijing Inokai Technology Co., Ltd. diethylenetriamine 98％ Tianjin Beilian Fine Chemical Co., Ltd.

[0047] Example 1

[0048] (1) 113 g of diethylenetriamine was added to a reaction kettle, and 282 g of oleic acid was added dropwise to the reaction kettle at 90° C. The temperature was raised to 160° C. for amidation dehydration. After 18 ml of water was removed, the temperature was raised to 240° C. for cyclization dehydration. After another 18 mL of water was removed, the reaction was stopped to obtain a hydrocarbon-substituted imidazoline.

[0049]

[0050] The prepared alkyl substituted imidazoline was subjected to high performance liquid chromatography-mass spectrometry analysis using a Waters liquid chromatography-mass spectrometer. Figure 1 . Figure 1 The upper middle graph is the UV absorption peak graph, and the lower graph is the mass spectrum signal graph. Figure 1 It can be seen that the mass-to-charge ratio of the molecular ion peak corresponding to the two peaks at 0.33-0.55 min is 350.7 m / z, and these two peaks correspond to the peaks of the hydrocarbon-substituted imidazoline; the mass-to-charge ratio of the molecular ion peak corresponding to the peak at 0.6-0.75 min is 368.7 m / z, which corresponds to the peak of the oleamide by-product that failed to cyclize; the peaks at 4.6 and 4.8 min correspond to the peaks of the by-products of the continued amidation of imidazoline and oleic acid, and the continued amidation of oleamide and oleic acid, respectively.

[0051] (2) 129 g of di-n-butylamine and 76 g of carbon disulfide were reacted in 100 mL of water at a reaction temperature of 20° C. for 2 hours to generate a dithiocarbamic acid intermediate.

[0052]

[0053] (3) The hydrocarbon-substituted imidazoline obtained in step (1) is added to the dithiocarbamic acid intermediate obtained in step (2), and the mixture is reacted at 80° C. for 2 hours, and hydrogen sulfide is removed to obtain the imidazoline derivative of the present invention, which is denoted as A1.

[0054]

[0055] The prepared imidazoline derivatives were subjected to HPLC-MS analysis using Waters liquid chromatography-mass spectrometry. Figure 2 . Figure 2 The upper middle graph is the UV absorption peak graph, and the lower graph is the mass spectrum signal graph. Figure 2 It can be seen that the ion peak of 0.8min corresponds to the product of step (1); the ion peak of 1-1.3min corresponds to the imidazoline derivative; the ion peaks between 1.6-1.8min and 7-9min are the residual by-products in step (1).

[0056] Example 2

[0057] (1) 113 g of diethylenetriamine was added to a reaction kettle, and 280 g of linoleic acid was added dropwise to the reaction kettle at 90° C. The temperature was raised to 160° C. for amidation dehydration. After 18 ml of water was removed, the temperature was raised to 240° C. for cyclization dehydration. After another 18 mL of water was removed, the reaction was stopped to obtain a hydrocarbon-substituted imidazoline.

[0058] (2) 129 g of di-n-butylamine and 76 g of carbon disulfide were reacted in 100 mL of water at a reaction temperature of 20° C. for 2 hours to generate a dithiocarbamic acid intermediate.

[0059] (3) The hydrocarbon-substituted imidazoline obtained in step (1) is added to the dithiocarbamic acid intermediate obtained in step (2), and the mixture is reacted at 80° C. for 2 hours, followed by dehydrogenation to obtain the imidazoline derivative of the present invention, designated as A2. The structure of the imidazoline derivative is shown below.

[0060]

[0061] Commercial products of alkenyl succinic acid type rust preventive T746 and sulfonate type rust preventive T705 were used as comparative rust preventives for the imidazoline derivatives of the present invention.

[0062] Examples I-1 to I-3 of Hydraulic Oil Compositions and Comparative Examples DI-1 to DI-2

[0063] Hydraulic oil compositions of Examples I-1 to I-3 and Comparative Examples DI-1 to DI-2 were prepared by mixing the compositions in Table 1 at 50°C for 1 hour. The performance of these hydraulic oil compositions was evaluated using methods including GB / T 265, GB / T 1995, GB / T 3535, SH / T 0189, SH / T 0301, SH / T 0209, GB / T 5096, GB / T 7305, GB / T 11143, GB / T 12579, and SH / T 0306. The evaluation results are shown in Table 2. The main raw materials used in these hydraulic oil compositions include aminothioester antiwear agent T323, phenolic ester antioxidant T512, thiophenol antioxidant T535, metal deactivator T571, demulsifier T1001, antifoaming agent T921, HIV II+6, dioctyl sebacate, PAO-6, and PAO-10, all of which are sourced from Beijing Huarui Xincheng Technology Co., Ltd. and are all industrial products.

[0064] Table 1

[0065]

[0066]

[0067] Table 2

[0068]

[0069]

Claims

1. A hydraulic oil composition comprising: (A) imidazoline derivative; (B) antiwear agent; (C) an antioxidant; (D) a metal deactivator; (E) a demulsifier; (F) an antifoaming agent; and (G) a base oil; wherein the structure of the imidazoline derivative is as shown in formula (I): In formula (I), n is an integer between 1 and 10, each R group is independently selected from a C2 to C5 alkylene group; R0 group is selected from C 15 ~C 20 alkyl, cycloalkyl or alkenyl; each R' group is independently selected from C1 to C 20 of alkyl.

2. The hydraulic oil composition according to claim 1, characterized in that In formula (I), n is an integer between 1 and 5, each R group is independently selected from ethylene or propylene; R0 group is selected from C 16 ~C 18 Each R' group is independently selected from a C2 to C8 alkyl group.

3. The hydraulic oil composition according to claim 1, characterized in that The imidazoline derivatives are one or more of the following compounds:

4. The hydraulic oil composition according to claim 1, characterized in that The preparation method of the imidazoline derivative comprises the following steps: (1) reacting CS2 with a compound represented by formula (X); The R' groups are independently selected from C1 to C 20 Alkyl; (2) reacting the reaction product of step (1) with a compound represented by formula (Y), and collecting the product; wherein n is an integer between 1 and 10, each R group is independently selected from a C2 to C5 alkylene group; R0 group is selected from a C 15 ~C 20 an alkyl, cycloalkyl or alkenyl group.

5. The hydraulic oil composition according to claim 4, characterized in that: n is an integer between 1 and 5, each R group is independently selected from ethylene or propylene; R0 group is selected from C 16 ~C 18 Each R' group is independently selected from a C2 to C8 alkyl group.

6. The hydraulic oil composition according to claim 4, characterized in that: In step (1), the molar ratio of CS2 to the compound represented by formula (X) is 0.8 to 1.3:1; in step (2), the molar ratio of the compound represented by formula (Y) to CS2 in step (1) is 1:0.5 to 1.

5.

7. The hydraulic oil composition according to claim 4, characterized in that In step (1), the temperature for the reaction between CS2 and the compound represented by formula (X) is 10 to 50° C., and the reaction time is 0.5 to 5 h. In step (2), the temperature for the reaction between the reaction product of step (1) and the compound represented by formula (Y) is 60 to 100° C., and the reaction time is 0.5 to 3 h.

8. The hydraulic oil composition according to any one of claims 1 to 7, characterized in that: The antiwear agent of the component (B) is selected from one or more of polysulfide compounds, phosphates, sulfur phosphates and phosphorus-nitrogen type extreme pressure antiwear agents; the antioxidant of the component (C) is selected from one or more of phenol ester type, thiophenol type, hindered phenol type and hindered amine type antioxidants; the metal deactivator of the component (D) is selected from one or more of thiadiazole derivatives, benzotriazole derivatives and propionyl hydrazide; the demulsifier of the component (E) is selected from one or more of propylene oxide diamine condensate, high molecular weight polyether, ethylene glycol ester and ethylene glycol ether; the antifoaming agent of the component (F) is selected from one or more of methyl silicone oil, acrylic acid and ether copolymer and polyacrylate; the base oil of the component (G) is selected from one or more of mineral base oil, synthetic ester oil and poly-α-olefin synthetic oil.

9. The hydraulic oil composition according to any one of claims 1 to 7, characterized in that: The component (A) accounts for 0.01% to 5% of the total mass of the hydraulic oil composition; the component (B) accounts for 0.1% to 10% of the total mass of the hydraulic oil composition; the component (C) accounts for 0.1% to 10% of the total mass of the hydraulic oil composition; the component (D) accounts for 0.001% to 5% of the total mass of the hydraulic oil composition; the component (E) accounts for 0.0001% to 0.1% of the total mass of the hydraulic oil composition; the component (F) accounts for 0.01% to 0.1% of the total mass of the hydraulic oil composition; and the component (G) constitutes the main component of the hydraulic oil composition.

10. The method for preparing the hydraulic oil composition according to any one of claims 1 to 9, comprising the step of mixing the components thereof.

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