Hydraulic oil composition and preparation method thereof

Abstract

The invention provides a hydraulic oil composition and a preparation method thereof. The hydraulic oil composition comprises the following components: (A) phosphate ester salt accounting for 0.1-10% of the total mass of the composition; (B) a viscosity index improver accounting for 0.5-30% of the total mass of the composition; (C) a pour point depressant accounting for 0.1-3% of the total mass of the composition; (D) an antioxidant accounting for 0.1%-10% of the total mass of the composition; (E) an antirust agent accounting for 0.001%-5% of the total mass of the composition; (F) a metal deactivator accounting for 0.01%-5% of the total mass of the composition; (G) a defoaming agent accounting for 0.001%-0.1% of the total mass of the composition; and (H) a lubricant base oil constituting the main component of the composition. The hydraulic oil composition disclosed by the invention has excellent anti-wear bearing performance, thermal stability and copper corrosion resistance.

Description

Technical Field

[0001] The invention relates to the field of lubricating oil, in particular to an ashless hydraulic oil composition. Background Art

[0002] Hydraulic oil is the most widely used oil in industrial lubricants. It is used as an energy transfer medium in hydraulic transmission systems to transfer power, reduce friction, isolate wear surfaces, prevent corrosion and rust, and is widely used in machinery manufacturing, agricultural machinery, aerospace and other fields. However, with the continuous development of hydraulic technology, the operating environment of hydraulic equipment has become more and more changeable, making the working conditions of hydraulic systems more and more harsh. High temperature and high pressure working environment will cause the lubrication performance of oil products to deteriorate, increase friction in hydraulic valves, and cause problems such as sticking valves. In addition, high temperature environment will accelerate the oxidation and degradation of hydraulic oil, thereby generating acidic substances and sludge, which puts higher requirements on the anti-wear load-bearing and thermal oxidation stability of hydraulic oil.

[0003] Anti-wear hydraulic oil can be divided into two types: ash-containing (metal-containing) and ash-free. Ash-containing hydraulic oil often uses ZDDP, because it contains metals, sulfur, phosphorus and other elements, which can easily accelerate the oxidation of oil and cause sludge and sediment. In addition, increasingly stringent environmental regulations have also restricted the industrial application of ash-containing hydraulic oil.

[0004] In recent years, ashless anti-wear hydraulic oil has been extensively researched and developed. The hydraulic oil proposed in CN 102399612B meets the specifications of the superior anti-wear hydraulic oil in the national standard GB11118.1-94, but the hydraulic oil contains a calcium salt detergent dispersant, and the anti-wear performance is seriously weakened under high load conditions. CN 115895753A proposes an ashless hydraulic oil composition, which contains an organic friction modifier of tetrapentanol esters, which can reduce the friction coefficient of the hydraulic oil, but the anti-wear load-bearing performance of the hydraulic oil composition does not show technical advantages.

[0005] At present, developing high-performance ashless extreme pressure anti-wear agents is still an effective way to improve the performance of ashless hydraulic oil. Summary of the invention

[0006] In order to solve the above technical problems, the present invention provides a hydraulic oil composition and a preparation method thereof.

[0007] The hydraulic oil composition of the present invention comprises the following components:

[0008] (A) phosphate salt, accounting for 0.1% to 10% of the total weight of the composition, preferably 0.2% to 5%;

[0009] (B) a viscosity index improver, accounting for 0.5% to 30% by weight of the total composition, preferably 1% to 25%;

[0010] (C) a pour point depressant, accounting for 0.1% to 3% of the total weight of the composition, preferably 0.1% to 2%;

[0011] (D) antioxidant, accounting for 0.1% to 10% of the total weight of the composition, preferably 0.2% to 5%;

[0012] (E) rust inhibitor, accounting for 0.001% to 5% of the total mass of the composition, preferably 0.01% to 3%;

[0013] (F) metal deactivator, accounting for 0.01% to 5% of the total mass of the composition, preferably 0.02% to 3%;

[0014] (G) a defoaming agent, accounting for 0.001% to 0.1% of the total mass of the composition, preferably 0.001% to 0.05%;

[0015] (H) lubricating base oil, constituting the main component of the composition;

[0016] The phosphate salt comprises a structural unit represented by formula (1) and at least one of the structural units represented by formula (2), formula (3) and formula (4),

[0017] wherein R1 and R2 are each independently selected from hydrogen, a hydrocarbon group, a substituted hydrocarbon group or a heteroalkyl group;

[0018] wherein X1 is selected from nitrogen or methine, R and R' are each independently selected from hydrogen or a C1-C4 hydrocarbon group; R3, R4 and R5 are each independently selected from a C1-C5 hydrocarbon group, and r1 and r2 are each independently 0 or 1;

[0019] wherein R6, R7 and R8 are each independently selected from a C1-C5 hydrocarbon group, and r3 and r4 are each independently 0 or 1;

[0020] Wherein, R" is selected from hydrogen or C1-C4 hydrocarbon group, R9, R 10 and R 11 r5 and r6 are each independently selected from a C1-C5 hydrocarbon group, and are each independently 0 or 1.

[0021] According to the present invention, the preparation method of the phosphate salt comprises:

[0022] The acidic phosphate having the structure shown in formula (5) is contacted with a nitrogen-containing organic substance having a bicyclic structure to react with a phosphate salt;

[0023] wherein R1 and R2 are each independently selected from hydrogen, a hydrocarbon group, a substituted hydrocarbon group or a heteroalkyl group;

[0024] The nitrogen-containing organic compound has at least one of the structures shown in formula (6), formula (7) and formula (8),

[0025] wherein X1 is selected from nitrogen or methine, R and R' are each independently selected from hydrogen or a C1-C4 hydrocarbon group; R3, R4 and R5 are each independently selected from a C1-C5 hydrocarbon group, and r1 and r2 are each independently 0 or 1;

[0026] wherein R6, R7 and R8 are each independently selected from a C1-C5 hydrocarbon group, and r3 and r4 are each independently 0 or 1;

[0027] Wherein, R" is selected from hydrogen or C1-C4 hydrocarbon group, R9, R 10 and R 11 r5 and r6 are each independently selected from a C1-C5 hydrocarbon group, and are each independently 0 or 1.

[0028] According to the present invention, the phosphate ester salt does not contain metal elements, is not easy to produce ash, shows significant anti-wear properties at a relatively small dosage, and can effectively improve the anti-wear performance and load-bearing capacity of lubricating oil. In addition, when the phosphate ester salt is used as a lubricating oil anti-wear additive, it has low metal corrosion while showing excellent anti-wear properties.

[0029] According to the present invention, the viscosity index improver can be polymethacrylate and / or polyisobutylene, and common trade names include Viscoplex 8-219, TK-Chem6350, Viscoplex 8-310, Viscoplex 12-075, PIB1400, etc., preferably with a kinematic viscosity of 500 to 1500 mm at 100°C. 2 / s polymethacrylate and / or polyisobutylene having a number average molecular weight of 1000 to 3400.

[0030] According to the present invention, the pour point depressant may be a polymethacrylate pour point depressant and / or a poly-α-olefin pour point depressant, preferably a polymethacrylate pour point depressant, and common trade names include T866, T803 and the like.

[0031] According to the present invention, the antioxidant can be selected from one or more of alkylated diphenylamine, N-phenyl-α-naphthylamine, shielded phenol and phenol ester, for example, dibutyl diphenylamine, dioctyl diphenylamine, butyl / octyl diphenylamine, didodecyl diphenylamine, dipentyl diphenylamine, N-phenyl-α-naphthylamine, 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl-4-hydroxyphenyl propionate. Common trade names include IRGANOX L-57, T534, T531, T501, T512, IRGANOX L-135, etc. The antioxidant is preferably a mixture of alkylated diphenylamine and phenol ester, and the mass ratio between the two is preferably 1:0.5-2.

[0032] According to the present invention, the rust inhibitor can be selected from one or more of alkenyl imidazoline alkenyl succinate, alkenyl succinate, petroleum sulfonate, cyclopentaneate and benzotriazole. For example, one or more of heptadecenyl imidazoline alkenyl succinate, heptadecenyl succinate, sodium petroleum sulfonate, barium petroleum sulfonate and zinc cyclopentaneate can be selected. Common trade names include T703, T746, T702, T701, T704 and the like.

[0033] According to the present invention, the metal deactivator is selected from one or more of alkylaminomethylenebenzotriazole, benzotriazole dialkylamine formaldehyde condensate, thiadiazole polysulfide and thiadiazole alkylthiol hydrogen peroxide condensate; common trade names include T551, T552, T553, T571, T561, etc.

[0034] According to the present invention, the defoaming agent is selected from one or more of dimethyl silicone oil, polyacrylate, and composite antifoaming agent. Common trade names include T901, T911, T912, T921, T922, etc., preferably T921.

[0035] According to the present invention, the lubricating oil base oil can be selected from one or more of API I, II, III, IV and V base oils, for example, one or more of Class I base oil, Class II hydrogenated base oil, Class III hydrogenated base oil, poly-α-olefin, ester base oil, more preferably one or more of Class II hydrogenated base oil, Class III hydrogenated base oil and diester base oil.

[0036] The method for preparing the hydraulic oil composition of the present invention comprises the step of mixing various additives therein with the base oil.

[0037] The hydraulic oil composition of the invention has excellent anti-wear load-bearing property, thermal stability and copper corrosion resistance. DETAILED DESCRIPTION

[0038] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0039] The present invention is further described in detail below in conjunction with the examples, but the present invention is not limited thereto. Unless otherwise specified, all ratios and parts are calculated by mass.

[0040] The first aspect of the present invention provides a phosphate salt, wherein the phosphate salt comprises a structural unit represented by formula (1) and at least one of the structural units represented by formula (2), formula (3) and formula (4),

[0041] wherein R1 and R2 are each independently selected from hydrogen, a hydrocarbon group, a substituted hydrocarbon group or a heteroalkyl group;

[0042] wherein X1 is selected from nitrogen or methine, R and R' are each independently selected from hydrogen or a C1-C4 hydrocarbon group; R3, R4 and R5 are each independently selected from a C1-C5 hydrocarbon group, and r1 and r2 are each independently 0 or 1;

[0043] wherein R6, R7 and R8 are each independently selected from a C1-C5 hydrocarbon group, and r3 and r4 are each independently 0 or 1;

[0044] Wherein, R" is selected from hydrogen or C1-C4 hydrocarbon group, R9, R 10 and R 11 r5 and r6 are each independently selected from a C1-C5 hydrocarbon group, and are each independently 0 or 1.

[0045] In the prior art, phosphate amine salts are usually used as lubricating oil anti-wear additives and require a relatively high dosage. The inventors of the present invention have found through continuous research that phosphate organic alkali salts with a nitrogen-containing bicyclic structure can show significant anti-wear properties at a relatively low dosage level, and can effectively improve the anti-wear performance and load-bearing capacity of lubricating oil. The phosphate ester salt does not contain metal elements, is not easy to produce ash, and has low metal corrosion while showing excellent anti-wear properties, which is a significant improvement over the phosphate amine salt compounds of the prior art.

[0046] In the present invention, R1 and R2 are each independently selected from hydrogen, a hydrocarbon group, a substituted hydrocarbon group or a heteroalkyl group. Preferably, R1 and R2 are not hydrogen at the same time.

[0047] Wherein, "hydrocarbyl" has the conventional meaning known in the art, including but not limited to straight or branched alkyl, straight or branched alkenyl, straight or branched alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl or a combination thereof. Preferably, the hydrocarbyl is a C1-C20 hydrocarbyl, including but not limited to a C1-C20 straight or branched alkyl, a C2-C20 straight or branched alkenyl, a C2-C20 straight or branched alkynyl, a C3-C20 cycloalkyl, a C3-C20 cycloalkenyl, a C3-C20 cycloalkynyl, a C6-C20 aryl or a combination thereof.

[0048] In the present invention, the "substituted hydrocarbon group" refers to a group obtained by directly replacing one or more hydrogen atoms in a hydrocarbon molecule with a substituent, and the substituent includes but is not limited to at least one of a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, a mercapto group, an alkoxy group and an alkylthio group.

[0049] In the present invention, the "heteroalkyl" refers to a group obtained by directly replacing one or more carbon atoms in the alkyl molecular structure (excluding the ends of the main chain or any side chain in the alkyl molecular structure) with heteroatoms. It is understood that from the perspective of structural stability, when there are multiple heteroatoms, these heteroatoms are not directly bonded. In the present invention, although the number of carbon atoms in the alkyl group is reduced accordingly because the carbon atoms are replaced by heteroatoms, for the sake of simplicity, the number of carbon atoms in the alkyl group before the replacement is still used to refer to the number of carbon atoms in the heteroalkyl group.

[0050] For example, a C4 straight chain alkyl group such as (The group indicated by the arrow is at the end of the main chain) is directly replaced by a replacement group -O- to obtain -CH2-O-CH2-CH3 or -CH2-CH2-O——CH3, which is called C4 straight-chain heteroalkyl. Alternatively, C4 branched alkyl such as (where the group indicated by the arrow is not inside the molecular structure, but at the end of the main chain and the side chain) is directly replaced by a replacement group -N< It is called C4 branched heteroalkyl. According to the present invention, the heteroalkyl includes but is not limited to C3-C20 straight chain or branched heteroalkyl, preferably C3-C10 straight chain or branched heteroalkyl.

[0051] Preferably, the heteroatom in the heteroalkyl group is at least one of O, N and S, preferably O and / or S, and more preferably S.

[0052] According to the present invention, preferably, R1 and R2 are each independently selected from a C4-C18 hydrocarbon group, a C4-C18 hydroxy-substituted hydrocarbon group or a C3-C20 heteroalkyl group, including but not limited to n-butyl, isobutyl, tert-butyl, n-hexyl, 2-ethylhexyl, n-octyl, 1-methylheptyl, 3,5,5-trimethylhexyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, 9-octadecenyl, 9,12-octadecadienyl, 12-hydroxy-9-octadecenyl, cyclohexyl, phenyl, methylphenyl or dimethylphenyl.

[0053] According to the present invention, in formula (2), r1 and r2 are each independently 0 or 1. It is understood that when r1 is 0, it means that the R4 group does not exist, and the N atoms and C atoms on both sides of R4 in formula (2) are directly connected. Similarly, when r2 is 0, it means that the R5 group does not exist, and the N and X1 on both sides of R5 in formula (2) are directly connected. The meanings of r3, r4, r5 and r6 in formula (3) and formula (4) are the same as those of r1 and r2, and are not repeated here.

[0054] In the present invention, as long as the phosphate salt has a phosphate group and a nitrogen-containing bicyclic structure, the anti-wear performance of the lubricant can be improved. By controlling the size (carbon number) of the bicyclic ring, the anti-wear performance and metal corrosion resistance can be further optimized. For example, by adjusting the main chain carbon number of the R3, R4 and R5 groups in formula (2), the size of the bicyclic structure in formula (2) can be controlled. Similarly, in the structures shown in formula (3) and formula (4), by adjusting R6, R7 and R8 and R9, R 10 and R 11 The number of main chain carbon atoms of the group can control the size of the bicyclic structure in formula (2) and formula (3).

[0055] According to the present invention, preferably, in formula (2) to formula (4), R3, R6, and R9 are each independently -(CH2) a -, wherein a is selected from 2-5.

[0056] According to the present invention, preferably, R4, R7, R 10 Each independently is -(CH2) b -, where b is 1-2.

[0057] According to the present invention, preferably, R5, R8, R 11 Each independently is -(CH2) c -, where c is 1-3.

[0058] The ring number and stereostructure of the above-mentioned preferred nitrogen-containing organic compound can control the basicity and dispersibility of such compound in the base oil, and the nitrogen-containing organic compound with sufficiently stable chemical properties can also be selected according to the use environment.

[0059] According to the present invention, the phosphate salt can exist, be manufactured or used in the form of a single (pure) compound, or in the form of a mixture of two or more thereof (in any proportion), which does not affect the realization of the effects of the present invention.

[0060] According to the present invention, there is no particular limitation on the preparation method of the phosphate ester salt, and the phosphate ester salt can be prepared by any method known in the art.

[0061] The second aspect of the present invention provides a method for preparing the phosphate ester salt, the method comprising:

[0062] The acidic phosphate having the structure shown in formula (5) is contacted with a nitrogen-containing organic substance having a bicyclic structure to react with a phosphate salt;

[0063] wherein R1 and R2 are each independently selected from hydrogen, a hydrocarbon group, a substituted hydrocarbon group or a heteroalkyl group;

[0064] The nitrogen-containing organic compound has at least one of the structures shown in formula (6), formula (7) and formula (8),

[0065] wherein X1 is selected from nitrogen or methine, R and R' are each independently selected from hydrogen or a C1-C4 hydrocarbon group; R3, R4 and R5 are each independently selected from a C1-C5 hydrocarbon group, and r1 and r2 are each independently 0 or 1;

[0066] wherein R6, R7 and R8 are each independently selected from a C1-C5 hydrocarbon group, and r3 and r4 are each independently 0 or 1;

[0067] Wherein, R" is selected from hydrogen or C1-C4 hydrocarbon group, R9, R 10 and R 11 r5 and r6 are each independently selected from a C1-C5 hydrocarbon group, and are each independently 0 or 1.

[0068] In the present invention, the acidic phosphate ester can be directly a commercially available product, or can be manufactured by a conventional method known in the art, and the present invention has no particular limitation thereto. In addition, the acidic phosphate ester can be used alone or in combination of two or more, as long as the structure shown in formula (5) is satisfied.

[0069] According to the present invention, preferably, in formula (5), R1 and R2 are not hydrogen at the same time.

[0070] Preferably, R1 and R2 are each independently selected from a C4-C18 hydrocarbon group, a C4-C18 hydroxy-substituted hydrocarbon group or a C3-C20 heteroalkyl group.

[0071] Preferably, the heteroatom in the heteroalkyl group is at least one of O, N and S, preferably O and / or S, and more preferably S.

[0072] Preferably, R1 and R2 are each independently selected from n-butyl, isobutyl, tert-butyl, n-hexyl, 2-ethylhexyl, n-octyl, 1-methylheptyl, 3,5,5-trimethylhexyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, 9-octadecenyl, 9,12-octadecadienyl, 12-hydroxy-9-octadecenyl, cyclohexyl, phenyl, methylphenyl or dimethylphenyl.

[0073] According to the present invention, the acidic phosphate ester includes but is not limited to mono-n-butyl phosphate (CAS: 1623-15-0), di-n-butyl phosphate (CAS: 107-66-4), mono-isobutyl phosphate (CAS: 2466-73-1), di-isobutyl phosphate (CAS: 6303-30-6), mono-tert-butyl phosphate (CAS: 2382-75-4), di-tert-butyl phosphate (CAS: 33494-81-4), mono-n-hexyl phosphate (CAS: 3900-04-7), di-n-hexyl phosphate (CAS: 3900- 13-8), monophenyl phosphate (CAS: 701-64-4), diphenyl phosphate (CAS: 838-85-7), benzyl phosphate (CAS: 1623-07-0), dibenzyl phosphate (CAS: 1623-08-1), mono(methylphenyl) phosphate, di(methylphenyl) phosphate, mono-n-octyl phosphate (CAS: 3991-73-9), di-n-octyl phosphate (CAS: 3115-39-7), mono(2-ethylhexyl) phosphate (CAS: 1070-03-7), di(2- Phosphate (CAS: 298-07-7), mono(1-methylheptyl) phosphate (CAS: 10353-73-8), di(1-methylheptyl) phosphate (CAS: 77076-28-9), mono(3,5,5-trimethylhexyl) phosphate (CAS: 85006-34-4), di(3,5,5-trimethylhexyl) phosphate (CAS: 7153-98-2), mono-n-decyl phosphate (CAS: 3921-30-0), di-n-decyl phosphate (CAS: 7795-87-1) , monolauryl phosphate, dilauryl phosphate, monomyristyl phosphate, dimyristyl phosphate, mono(hexadecyl) phosphate, di(hexadecyl) phosphate, monostearyl phosphate, distearyl phosphate, mono(9-octadecenyl) phosphate, di(9-octadecenyl) phosphate, mono(9,12-octadecadienyl) phosphate, di(9,12-octadecadienyl) phosphate, mono(12-hydroxy-9-octadecenyl) phosphate and di(12-hydroxy-9-octadecenyl) phosphate or at least one of the isomers of the above compounds.

[0074] The present invention has no particular limitation on the source of the nitrogen-containing organic compound having a bicyclic structure, and commercially available products can be used directly, or they can be prepared by conventional methods known in the art. The nitrogen-containing organic compound can be used alone or in combination of two or more, as long as it satisfies at least one of the structures shown in formula (6), formula (7) and formula (8).

[0075] According to the present invention, preferably, in formula (6) to formula (8), R3, R6, and R9 are each independently -(CH2)a, wherein a is selected from 2-5.

[0076] Preferably, R4, R7, R 10 Each independently is -(CH2) b -, where b is 1-2.

[0077] Preferably, R5, R8, R 11 Each independently is -(CH2) c , where c is 1-3.

[0078] According to the present invention, the nitrogen-containing organic matter includes but is not limited to 1,4-diazabicyclo[2.2.2]octane (CAS: 280-57-9), 1-azabicyclo[2.2.2]octane (quinuclidine, CAS: 100-76-5), 1,5-diazabicyclo[4.3.0]-5-nonene (CAS: 3001-72-7), 1,8-diazabicyclo[5.4.0]undec-7-ene (abbreviated as DBU, CAS: 6674-22-2), and any mixture of the above compounds.

[0079] In the present invention, preferably, the molar ratio of the acidic phosphate to the nitrogen-containing organic matter is 1:0.1-10, preferably 1:0.4-5, and more preferably 1:0.5-2.

[0080] The present invention has a wide range of selection for the reaction temperature of the phosphate salt. Preferably, the reaction temperature is 0-200°C, preferably 20-150°C, and more preferably 60-120°C. The present invention has no special requirements for the reaction time. In order to ensure sufficient reaction, preferably, the reaction time is 0.1-24h, preferably 0.5-12h, and more preferably 1-5h.

[0081] The present invention has no particular limitation on the reaction pressure and atmosphere for the reaction of the phosphate ester salt, and the reaction can be carried out under normal pressure and air conditions.

[0082] According to the present invention, the phosphate salt reaction can be carried out in the presence of a solvent or in the absence of a solvent, and the reaction can be achieved. Preferably, the phosphate salt reaction is carried out in the presence of a solvent, for example, the acidic phosphate and the nitrogen-containing organic matter are added to a reactor containing a solvent for contact, or the acidic phosphate and the nitrogen-containing organic matter are dissolved in a solvent respectively, and then both are added to a reactor for the phosphate salt reaction. The present invention has no special requirements for the reactor, as long as the reaction conditions can be controlled within the above range, conventional reaction devices in the art can be applied to the present invention.

[0083] The present invention has no particular requirements for the specific operating conditions for adding the above-mentioned reactants to the reactor, and can be carried out in a conventional operating manner in the art. Preferably, the reactants are slowly added in batches or dropwise to the reactor, and the temperature is controlled within the above-mentioned reaction temperature range.

[0084] The present invention has no particular limitation on the order of adding the reaction raw materials, and they can be added in any order.

[0085] Preferably, the solvent is selected from at least one of C6-C10 alkanes, C6-C20 aromatic hydrocarbons, C5-C10 fatty ethers, C2-C20 halogenated hydrocarbons and C3-C10 amides. The C6-C10 alkanes include but are not limited to at least one of n-hexane, cyclohexane and petroleum ether; the C6-C20 aromatic hydrocarbons include but are not limited to at least one of benzene, toluene, xylene and isopropylbenzene; the C2-C20 halogenated hydrocarbons include but are not limited to at least one of dichloromethane, carbon tetrachloride, chlorobenzene and 1,2-dichlorobenzene; the C5-C10 fatty ethers include but are not limited to at least one of methyl tert-butyl ether, 1,2-dimethoxyethane, ethylene glycol diethyl ether and 1,4-dioxane; the C3-C10 amides include but are not limited to at least one of dimethylformamide, dimethylacetamide and N-methylpyrrolidone.

[0086] According to the present invention, preferably, the mass ratio of the total mass of the acidic phosphate and the nitrogen-containing organic matter to the solvent is 1:0.5-10, preferably 1:0.5-5, and more preferably 1:0.8-3.

[0087] According to the present invention, the solvent may be used alone or in combination of two or more. Preferably, the preparation method further comprises recovering the solvent after the reaction and recycling it in the same reaction. For example, the solvent may be recovered by vacuum distillation.

[0088] According to the present invention, in the preparation method of the phosphate salt, the obtained reaction product can be a single phosphate salt or a mixture containing multiple phosphate salts. These reaction products are all expected by the present invention, and the phosphate salts all have the structural unit shown in formula (1), and at least one of the structural units shown in formula (2), formula (3) and formula (4), and the difference in their specific existence forms does not affect the realization of the effect of the present invention. Therefore, in the context of this specification, these reaction products are collectively referred to as the phosphate salts of the present invention without distinction.

[0089] Therefore, in the present invention, the product obtained by the reaction of the phosphate ester salt may be purified or not. In order to further improve the performance of the phosphate ester salt, preferably, the preparation method further comprises: purifying the product obtained by the reaction of the phosphate ester salt. The phosphate ester salt of a specific structure is separated from the product obtained by the reaction of the phosphate ester salt by the purification.

[0090] The purification may be carried out by any conventional purification or separation method in the art, and the present invention has no particular limitation thereto. For example, the reaction product may be purified by column chromatography or preparative chromatography.

[0091] The present invention will be described in detail below through examples.

[0092] In the following examples and comparative examples, unless otherwise specified, the raw materials used were commercially available.

[0093] Example 1

[0094] In a 250mL three-necked flask equipped with a magnetic stirrer, a thermometer, a condenser and a dropping funnel, add 5.59 grams (49.84 mmol) of 1,4-diazabicyclo[2.2.2]octane and 44.15 grams of 1,2-dimethoxyethane, and stir rapidly to dissolve at room temperature; 25.02 grams (100.00 mmol) of diphenyl phosphate is dissolved in 49.09 grams of 1,2-dimethoxyethane and then slowly dripped into the three-necked flask; the temperature is raised to 85°C, and the temperature is controlled to reflux between 80-85°C for 4.5 hours. After the reaction is completed, the solvent is evaporated by reduced pressure distillation to obtain 30.48 grams of a white waxy product. The product is recorded as S1. The product structure was characterized by chromatography-mass spectrometry, and the molecular weight of the main product was measured to be 350.12. According to the analysis, the structure of the main product in S1 is shown as follows:

[0095]

[0096] Example 2

[0097] In a 250mL three-necked flask equipped with a magnetic stirrer, a thermometer, a condenser and a dropping funnel, add 5.60 grams (49.92 mmol) of 1,4-diazabicyclo[2.2.2]octane and 46.02 grams of 1,2-dimethoxyethane, and stir and dissolve rapidly at room temperature; 32.21 grams (99.90 mmol) of di(2-ethylhexyl) phosphate is slowly dripped into the three-necked flask, the temperature is raised to 85°C, and the temperature is controlled to reflux at 80-85°C for 4 hours. After the reaction is completed, the solvent is evaporated by reduced pressure distillation to obtain 37.32 grams of a white waxy product. The product is recorded as S2. The product structure was characterized by chromatography-mass spectrometry, and the molecular weight of the main product was measured to be 434.38. According to the analysis, the structure of the main product in S2 is shown as follows:

[0098]

[0099] Example 3

[0100] In a 250mL three-necked flask equipped with a magnetic stirrer, a thermometer, a condenser and a dropping funnel, add 5.61 grams (50.13 mmol) of 1,4-diazabicyclo[2.2.2]octane and 45.52 grams of 1,2-dimethoxyethane, and stir and dissolve rapidly at room temperature; 21.04 grams (100.01 mmol) of di-n-butyl phosphate are slowly dripped into the three-necked flask, the temperature is raised to 85°C, and the temperature is controlled to reflux at 80-85°C for 4 hours. After the reaction is completed, the solvent is evaporated by reduced pressure distillation to obtain 26.06 grams of a slightly yellow, clear, transparent oily liquid product. The product is recorded as S3. The product structure was characterized by chromatography-mass spectrometry, and the molecular weight of the main product was measured to be 321.99. According to the analysis, the structure of the main product in S3 is shown as follows:

[0101]

[0102] Comparative Example 1 Diphenyl phosphate lauryl amine salt antiwear agent

[0103] Commercially available diphenyl phosphate and lauryl amine are used as raw materials. Diphenyl phosphate is dissolved in 1,2-dimethoxyethane, wherein the mass ratio of diphenyl phosphate to 1,2-dimethoxyethane is 1:2. Lauryl amine is dissolved in 60-90°C petroleum ether, wherein the mass ratio of lauryl amine to petroleum ether is 1:1. Slowly drip the lauryl amine solution into the diphenyl phosphate solution under stirring, wherein the molar ratio of diphenyl phosphate to lauryl amine is 1:1. Heat to 85°C, control the temperature at 70-80°C and reflux for 4 hours. After the reaction is completed, the solvent is evaporated to obtain a product recorded as DS1, wherein the main component is diphenyl phosphate lauryl amine salt, and the structure is shown below:

[0104]

[0105] Comparative Example 2: Di(2-ethylhexyl) phosphate di-n-hexylamine salt antiwear agent

[0106] The raw materials used are commercially available di(2-ethylhexyl) phosphate and di-n-hexylamine. Dissolve di(2-ethylhexyl) phosphate in 60-90°C petroleum ether, wherein the mass ratio of di(2-ethylhexyl) phosphate to 60-90°C petroleum ether is 1:1. Slowly drip di-n-hexylamine into the di(2-ethylhexyl) phosphate solution under stirring, wherein the molar ratio of di(2-ethylhexyl) phosphate to di-n-hexylamine is 1:1. Heat to 85°C, control the temperature at 75-80°C and reflux for 4 hours. After the reaction is completed, evaporate the solvent and obtain a product recorded as DS2, wherein the main component is di(2-ethylhexyl) phosphate di-n-hexylamine salt, and the structure is shown below:

[0107]

[0108] Comparative Example 3: Di-n-butyl phosphate di-n-hexylamine salt anti-wear agent

[0109] The raw materials used are commercially available di-n-butyl phosphate and di-n-hexylamine. Di-n-butyl phosphate is dissolved in 60-90°C petroleum ether, wherein the mass ratio of di-n-butyl phosphate to 60-90°C petroleum ether is 1:1. Di-n-hexylamine is slowly dripped into the di-n-butyl phosphate solution under stirring, wherein the molar ratio of di-n-butyl phosphate to di-n-hexylamine is 1:1. Heat to 85°C, control the temperature at 75-80°C and reflux for 4 hours. After the reaction is completed, the solvent is evaporated and the product is recorded as DS3, wherein the main component is di-n-butyl phosphate di-n-hexylamine salt, and the structure is shown below:

[0110]

[0111] Examples 4 to 6 and Comparative Examples 4 to 6 of Hydraulic Oil Compositions

[0112] According to the formulations in Table 1, hydraulic oil compositions of Examples 4 to 6 and Comparative Examples 4 to 6 were prepared.

[0113] Table 1 Hydraulic oil composition formula

[0114]

[0115] The hydraulic oil composition was subjected to kinematic viscosity test (GB / T 265 standard method), four-ball friction and wear test (GB / T 0189 standard method, test conditions are 392N, 75°C, 60min, 1200rpm), SRV friction test (NB / SH / T 0847 method, test conditions are 80°C, stroke 1mm, reciprocating frequency 50Hz), copper corrosion test (GB / T 5096 standard method, test conditions are 100°C, 3h), liquid phase rust test (GB / T 11143 standard method B method), and rotating oxygen bomb test (GB / T0139 standard method). The measurement results are shown in Table 2.

[0116] It can be seen from Tables 1 and 2 that the hydraulic oil composition of the present invention has higher load-bearing performance, thermal oxidation stability and excellent copper corrosion resistance.

[0117] Table 2 Hydraulic oil evaluation test results

[0118]

[0119] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A hydraulic oil composition comprising the following components: (A) phosphate salt, accounting for 0.1% to 10% of the total weight of the composition; (B) a viscosity index improver, accounting for 0.5% to 30% of the total mass of the composition; (C) a pour point depressant, accounting for 0.1% to 3% of the total weight of the composition; (D) an antioxidant, accounting for 0.1% to 10% of the total weight of the composition; (E) rust inhibitor, accounting for 0.001% to 5% of the total mass of the composition; (F) metal deactivator, accounting for 0.01% to 5% of the total mass of the composition; (G) a defoaming agent, accounting for 0.001% to 0.1% of the total weight of the composition; (H) lubricating base oil, constituting the main component of the composition; The phosphate salt comprises a structural unit represented by formula (1) and at least one of the structural units represented by formula (2), formula (3) and formula (4), in, R1 and R2 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl or heteroalkyl; wherein X1 is selected from nitrogen or methine, R and R' are each independently selected from hydrogen or a C1-C4 hydrocarbon group; R3, R4 and R5 are each independently selected from a C1-C5 hydrocarbon group, and r1 and r2 are each independently 0 or 1; wherein R6, R7 and R8 are each independently selected from a C1-C5 hydrocarbon group, and r3 and r4 are each independently 0 or 1; Wherein, R" is selected from hydrogen or C1-C4 hydrocarbon group, R9, R 10 and R 11 r5 and r6 are each independently selected from a C1-C5 hydrocarbon group, and are each independently 0 or 1.

2. The hydraulic oil composition according to claim 1, characterized in that: In formula (1), R1 and R2 are not hydrogen at the same time; Preferably, R1 and R2 are each independently selected from a C4-C18 hydrocarbon group, a C4-C18 hydroxy-substituted hydrocarbon group or a C3-C20 heteroalkyl group; Preferably, the heteroatom in the heteroalkyl group is at least one of O, N and S, preferably O and / or S, and more preferably S.

3. The hydraulic oil composition according to claim 2, characterized in that: R1 and R2 are each independently selected from n-butyl, isobutyl, tert-butyl, n-hexyl, 2-ethylhexyl, n-octyl, 1-methylheptyl, 3,5,5-trimethylhexyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, 9-octadecenyl, 9,12-octadecadienyl, 12-hydroxy-9-octadecenyl, cyclohexyl, phenyl, benzyl, methylphenyl or dimethylphenyl.

4. The hydraulic oil composition according to claim 1, characterized in that: In formula (2) to formula (4), R3, R6, and R9 are each independently -(CH2) a -, wherein a is selected from 2-5; and / or, R4, R7, R 10 Each independently is -(CH2) b -, where b is 1-2; and / or, R5, R8, R 11 Each independently is -(CH2) c -, where c is 1-3.

5. The hydraulic oil composition according to claim 1, characterized in that: The preparation method of the phosphate salt comprises: The acidic phosphate having the structure shown in formula (5) is contacted with a nitrogen-containing organic substance having a bicyclic structure to react with a phosphate salt; wherein R1 and R2 are each independently selected from hydrogen, a hydrocarbon group, a substituted hydrocarbon group or a heteroalkyl group; The nitrogen-containing organic compound has at least one of the structures shown in formula (6), formula (7) and formula (8), wherein X1 is selected from nitrogen or methine, R and R' are each independently selected from hydrogen or a C1-C4 hydrocarbon group; R3, R4 and R5 are each independently selected from a C1-C5 hydrocarbon group, and r1 and r2 are each independently 0 or 1; wherein R6, R7 and R8 are each independently selected from a C1-C5 hydrocarbon group, and r3 and r4 are each independently 0 or 1; Wherein, R" is selected from hydrogen or C1-C4 hydrocarbon group, R9, R 10 and R 11 r5 and r6 are each independently selected from a C1-C5 hydrocarbon group, and are each independently 0 or 1.

6. The hydraulic oil composition according to claim 5, characterized in that: In formula (5), R1 and R2 are not hydrogen at the same time; Preferably, R1 and R2 are each independently selected from a C4-C18 hydrocarbon group, a C4-C18 hydroxy-substituted hydrocarbon group or a C3-C20 heteroalkyl group; Preferably, the heteroatom in the heteroalkyl group is at least one of O, N and S, preferably O and / or S, and more preferably S; Preferably, R1 and R2 are each independently selected from n-butyl, isobutyl, tert-butyl, n-hexyl, 2-ethylhexyl, n-octyl, 1-methylheptyl, 3,5,5-trimethylhexyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, 9-octadecenyl, 9,12-octadecadienyl, 12-hydroxy-9-octadecenyl, cyclohexyl, phenyl, benzyl, methylphenyl or dimethylphenyl.

7. The hydraulic oil composition according to claim 5, characterized in that: In formula (6) to formula (8), R3, R6, and R9 are each independently -(CH2) a -, wherein a is selected from 2-5; and / or, R4, R7, R 10 Each independently is -(CH2) b -, where b is 1-2; and / or, R5, R8, R 11 Each independently is -(CH2) c -, where c is 1-3.

8. The hydraulic oil composition according to claim 5, characterized in that: The molar ratio of the acidic phosphate to the nitrogen-containing organic matter is 1:0.1-10, preferably 1:0.4-5, more preferably 1:0.5-2; Preferably, the conditions for the reaction of the phosphate salt include: reaction temperature of 0-200°C, preferably 20-150°C, more preferably 60-120°C, reaction time of 0.1-24h, preferably 0.5-12h, more preferably 1-5h.

9. The hydraulic oil composition according to any one of claims 1 to 8, characterized in that: The viscosity index improver is selected from polymethacrylate and / or polyisobutylene; the pour point depressant is selected from polymethacrylate pour point depressant and / or polyα-olefin pour point depressant; the antioxidant is selected from one or more of alkylated diphenylamine, N-phenyl-α-naphthylamine, shielded phenol and phenol ester; the rust inhibitor is selected from one or more of alkenyl imidazoline alkenyl succinate, alkenyl succinate, petroleum sulfonate, cycloalkaneate and benzotriazole; the metal deactivator is selected from one or more of alkylaminomethylene benzotriazole, benzotriazole dialkylamine formaldehyde condensate, thiadiazole polysulfide and thiadiazole alkyl mercaptan hydroperoxide condensate; the defoamer is selected from one or more of dimethyl silicone oil, polyacrylate and composite antifoaming agent; the lubricating oil base oil is selected from one or more of API I, II, III, IV and V base oils.

10. The method for preparing the hydraulic oil composition according to any one of claims 1 to 9, comprising the step of mixing various additives therein with the base oil.

Images