CN115992028B - Antioxidant composition and preparation method thereof - Google Patents
Antioxidant composition and preparation method thereof Download PDFInfo
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- CN115992028B CN115992028B CN202111214912.5A CN202111214912A CN115992028B CN 115992028 B CN115992028 B CN 115992028B CN 202111214912 A CN202111214912 A CN 202111214912A CN 115992028 B CN115992028 B CN 115992028B
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- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 71
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- -1 ester compound Chemical class 0.000 claims abstract description 136
- 239000010687 lubricating oil Substances 0.000 claims abstract description 48
- 239000012964 benzotriazole Substances 0.000 claims abstract description 39
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- 238000005260 corrosion Methods 0.000 claims abstract description 21
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- 239000003377 acid catalyst Substances 0.000 claims abstract description 10
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- 125000004404 heteroalkyl group Chemical group 0.000 claims description 24
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Landscapes
- Lubricants (AREA)
Abstract
The invention provides an antioxidant composition and a preparation method thereof. The antioxidant composition comprises an ester compound and a multifunctional oiliness agent, wherein the structure of the ester compound is shown as a formula (I): At least one A group in formula (I) is selected from 1-valent groups represented by formula (II);
Description
Technical Field
The invention relates to an antioxidant composition, in particular to an antioxidant composition which can be used in aviation synthetic ester lubricating oil and has high-temperature antioxidant and anticorrosion performance.
Background
The high-temperature corrosion and oxidation stability of the aeroengine lubricating oil refers to the high-temperature oxidation resistance and the high-temperature deposition relieving capability of the lubricating oil in the use process, and is an important expression of the high-temperature oxidation resistance of the aeroengine lubricating oil. Under the induction of high-temperature oxygen and the catalysis of metal, the lubricating oil is subjected to a series of chemical changes such as oxidation, polymerization, alkylation, decomposition and the like in a short period, so that a great amount of sediments such as oil sludge are generated in engine oil, the sediments are attached to metal accessories, a piston is stuck to a ring, equipment is severely corroded, the service life of the equipment is shortened, and the normal working operation of an aeroengine is seriously influenced. The improvement of the high-temperature corrosion and oxidation stability of the oil of the aero-engine has important significance for improving the working efficiency and the service life of the lubricating system equipment.
With the development of the aviation industry and the increase of the aircraft flying speed, the turbojet engine lubricating oil main body use temperature is increased from 80 ℃ in the early stage to 220 ℃ at present, and the next generation of the turbojet engine lubricating oil main body temperature is expected to exceed 350 ℃. The environmental characteristics of high temperature, high speed and high load of the aeroengine put higher and higher requirements on the performance of the aeroengine lubricating oil. When the outlet temperature of the aeroengine is above 200 ℃, the oxidation speed of the common engine lubricating oil can be increased by times, so that the viscosity of the lubricating oil is increased, the total acid value is increased, the corrosiveness is strong, and a large amount of sediment is generated. To effectively alleviate these problems, it is necessary to improve the high temperature corrosion and oxidation stability properties of the aircraft engine oils, which are directly related to the length of service of the aircraft engine oils and the performance of the engine lubrication system components.
High temperature corrosion and oxidation stability of the aeroengine oil are closely related to the structure and high temperature performance of the base oil and the antioxidant. Therefore, the high-temperature corrosion and oxidation stability of the aircraft engine oil are effectively improved, and a high-temperature antioxidant corrosion inhibitor with excellent chemical structure and high-temperature antioxidant performance is required to be synthesized, so that the base oil is effectively protected, the generation of oxidation products is reduced, the oil solubility of the oxidation products is improved, the sediment is reduced, and the problems of oil quality deterioration and sediment of the aircraft engine lubricating oil under the high-temperature condition are effectively relieved.
The international famous aviation lubricating oil standard MIL-PRF-7808L standard shows that the 100 ℃ kinematic viscosity grade of four-centimeter (4 mm 2/s) aviation lubricating oil simultaneously requires good high-temperature oxidation resistance and low-temperature fluidity, thereby ensuring the rapid flight of the aircraft under high temperature, high rotating speed and high load, and ensuring the rapid take-off, flexible maneuver, high-speed cruising and safe landing of the aircraft in high-cold regions. The high-temperature antioxidant with excellent chemical structure and high-temperature antioxidant performance is required to be synthesized, so that the base oil can be effectively protected, the generation of oxidation products can be reduced, the sediment can be reduced, the problems of deterioration and deposition of the high-temperature oil of the aeroengine oil can be effectively relieved, and the high-temperature safe and stable operation of the aeroengine can be ensured. Meanwhile, the lubricating oil composition has smaller kinematic viscosity at low temperature, better low-temperature fluidity, meets the index requirement that the kinematic viscosity of MIL-PRF-7808L standard is less than or equal to 20000 (mm 2/s) at-51 ℃, is more beneficial to low-temperature lubrication service of lubricating oil and is beneficial to safely and quickly starting the aviation aircraft to fly in a low-temperature environment.
The application of oiliness agent aims at reducing friction, it is dissolved in lubricating oil, and forms firm directional adsorption film on the friction surface, so that it can reduce friction and abrasion between moving parts and improve friction property of lubricating oil. The oily agent is of various kinds, mainly animal and vegetable oils, higher fatty acids, higher fatty alcohols, amines, amides, esters, sulfurized fats and oils, etc. At present, common oily agents in China include vulcanized cottonseed oil, fatty acid esters, benzotriazole fatty acid amine salts and the like. The benzotriazole fatty acid amine salt has the performances of oil solubility, wear resistance, oxidation resistance, corrosion resistance, rust resistance and the like, is added into natural mineral oil and lubricating oil to be used as a rust inhibitor, an antioxidant, a metal passivating agent, an antiwear agent, a preservative and the like, achieves good effects, can be used in gear oil, hyperbolic gear oil, antiwear hydraulic oil, oil film bearing oil and lubricating grease, and can also be used as a rust inhibitor and a vapor phase corrosion inhibitor in rust-proof grease.
There are patents and literature describing processes for the preparation of benzotriazole derivatives, which are either strictly controlled or difficult to isolate and purify, and which have low yields.
The product produced by the original process is light yellow flocculent solid, has certain performances of oil solubility, wear resistance, oxidation resistance, corrosion resistance, rust resistance and the like, has the defects of poor oil solubility under low temperature conditions, easy precipitation, turbidity of the lubricating oil, long-term standing precipitation and adverse use performance of the oil under low temperature conditions. In addition, flocculent solid benzotriazole fatty ammonium salt is inconvenient for blending oil products in the actual production process of lubricating oil, and liquid benzotriazole fatty acid ammonium salt has obvious advantages in this aspect.
US 3,697,427 discloses the use of benzotriazole or certain alkyl benzotriazoles as metal deactivators in synthetic lubricating oil compositions. US 3,790,481 discloses the use of methyl bis-benzotriazole, alkyl benzotriazole, and naphthalene as copper deactivators in polyol ester lubricating oil compositions.
US 5,076,946 discloses the use of a methyldialkylbenzotriazole dimer derivative as a metal deactivator in a lubricating oil to improve the oxidative stability of the lubricating oil. US 6,743,759B2 discloses that methylene bis-di-tert-butyl-dithiocarbamic acid ester, alkyl benzotriazole and derivatives of diphenylamine are compounded in a certain proportion to form the lubricating oil antioxidant extreme pressure antiwear agent with better performance.
Disclosure of Invention
The invention provides an antioxidant composition, a preparation method thereof and a lubricating oil composition containing the antioxidant composition, which comprise the following aspects.
In a first aspect, the present invention provides an antioxidant composition.
The antioxidant composition comprises an ester compound and a multifunctional oiliness agent, wherein the structure of the ester compound is shown as a formula (I):
in formula (I), n is an integer between 1 and 10, preferably an integer between 1 and 5, more preferably an integer between 1 and 3; R 0 is selected from the group consisting of n-valent C 1～30 linear or branched alkyl, C 2～30 linear or branched heteroalkyl, preferably from the group consisting of n-valent C 1～20 linear or branched alkyl, A C 2～20 linear or branched heteroalkyl group, more preferably selected from the group consisting of an n-valent C 1～10 linear or branched alkyl group, a C 2～10 linear or branched heteroalkyl group; Each R' group is independently selected from C 1～10 linear or branched alkylene, preferably from C 1～5 linear or branched alkylene, more preferably from C 1～3 linear or branched alkylene; each R "group is independently selected from C 1～30 straight or branched alkyl, preferably from C 1～20 straight or branched alkyl, more preferably from C 1～10 straight or branched alkyl; Each R' "group is independently selected from C 1～30 straight or branched alkyl, preferably from C 1～20 straight or branched alkyl, more preferably from C 1～10 straight or branched alkyl; Each A group is selected from a 1-valent group represented by the formula (II), H, C 1～20 straight-chain or branched alkyl group, preferably selected from a group represented by the formula (II), H, C 1～10 straight-chain or branched alkyl group, more preferably selected from a group represented by the formula (II), H, C 1～5 straight-chain or branched alkyl group, and at least one A group in the formula (I) is selected from 1-valent groups shown in the formula (II);
The formula (II) is a 1-valent group formed by bonding m structural units shown in the formula (III),
In formula (II), m is an integer between 1 and 10, preferably an integer between 1 and 5, more preferably an integer between 1 and 3; each R I group is independently selected from H, C 1～10 linear or branched alkyl, preferably from H, C 1～5 linear or branched alkyl, more preferably from H, C 1～3 linear or branched alkyl; each x is independently selected from an integer between 0 and 4, preferably an integer between 0 and 2, more preferably 0 or 1; each R II group is independently selected from H, C 1～10 linear or branched alkyl, preferably from H, C 1～5 linear or branched alkyl, more preferably from H, C 1～3 linear or branched alkyl; each y is independently selected from integers between 0 and 2, preferably 0 or 1; each R III group is independently selected from H, C 1～10 linear or branched alkyl, preferably from H, C 1～5 linear or branched alkyl, more preferably from H, C 1～3 linear or branched alkyl; each z is independently selected from an integer between 0 and 3, preferably an integer between 0 and 2, more preferably 0 or 1;
Each L I、LII、LIII in formula (II) is independently H, C 1～4 alkyl, a binding end bonded to L I、LII、LIII in a different building block, a binding end bonded to formula (I), a 1-valent group represented by formula (IV); only one L I、LII or L III present in formula (II) is a binding end that is bonded to formula (I);
Delta in the 1-valent group represented by the formula (IV) represents a binding end bonded to L I、LII or L III;
In formula (IV), n' is an integer between 1 and 10, preferably an integer between 1 and 5, more preferably an integer between 1 and 3; r 0 is selected from the group consisting of n-valent C 1～30 linear or branched alkyl, C 2～30 linear or branched heteroalkyl, preferably from n-valent C 1～20 linear or branched alkyl, C 2～20 linear or branched heteroalkyl, more preferably from n-valent C 1～10 linear or branched alkyl, C 2～10 linear or branched heteroalkyl; each R' group is independently selected from C 1～10 linear or branched alkylene, preferably from C 1～5 linear or branched alkylene, more preferably from C 1～3 linear or branched alkylene; each R "group is independently selected from C 1～30 straight or branched alkyl, preferably from C 1～20 straight or branched alkyl, more preferably from C 1～10 straight or branched alkyl; each R' "group is independently selected from C 1～30 straight or branched alkyl, preferably from C 1～20 straight or branched alkyl, more preferably from C 1～10 straight or branched alkyl.
According to the invention, preferably, in formula (II), L I、LII、LIII in the same structural unit are not bonded to each other.
According to the present invention, in formula (II), when m=1, one of L I、LII、LIII is a binding end bonded to formula (I), and the other two are each independently H, C 1～4 alkyl or a 1-valent group represented by formula (IV).
According to the present invention, in formula (II), when m=2, there are 2 structural units as shown in formula (III), L I、LII、LIII of the 2 structural units (when they are both bonded binding ends) can be bonded to each other, and alternatively, there is only one L I、LII or L III each of the 2 structural units bonded to each other, that is, only one covalent bond is formed between 2 different structural units.
According to the present invention, in the formula (II), when m is greater than 2, there are m structural units as shown in the formula (III), L I、LII、LIII of the m structural units (when they are all bonded ends) are capable of bonding to each other, further alternatively, the m structural units are sequentially bonded 1 end structural unit, (m-2) middle structural units and another 1 end structural unit, only one L I、LII or L III is bonded to L I、LII or L III of the middle structural unit adjacent thereto in each end structural unit, and 2L I、LII or L III is bonded to L I、LII or L III of the structural unit adjacent thereto, respectively, in each middle structural unit, i.e., only one covalent bond is formed between each two different structural units connected thereto.
Examples of the group represented by the formula (II) according to the present invention include:
wherein represents the binding end to the bond of formula (I).
According to the present invention, examples of the ester compound include:
In the molecular structural formulas of the ester compounds P-1, P-2 and P-3, the group PAN represents a group (II), and the specific molecular structure of the group (II) is shown as above. Taking (II-1) as an example, the molecular structural formula of the ester compound formed by the method is shown as follows:
according to the invention, the multifunctional oiliness agent is a reaction product of alkyl benzotriazole and/or benzotriazole and mixed alkyl primary amine under the action of an acid catalyst.
According to the invention, the preparation method of the multifunctional oiliness agent comprises the following steps: in the presence of inert gas, alkyl benzotriazole and/or benzotriazole and alkyl primary amine react under the action of an acid catalyst, and the product is collected.
According to the invention, the structure of the alkyl benzotriazole and/or benzotriazole is:
Wherein R 1' is selected from H, C 1～C12 straight or branched chain alkyl, preferably C 1～C8 straight or branched chain alkyl, most preferably methyl.
According to the invention, the primary alkyl amine is a primary alkyl amine of C 16～C22 having the formula R 2'CH2NH2, wherein R 2' is a linear or branched alkyl of C 15～C21.
According to the invention, the primary alkylamine is preferably a mixed primary alkylamine of C 16～C22, which is a mixture of a primary linear chain amine and a primary branched chain amine.
According to the invention, the alkyl groups are divided in mole percent, based on the total moles of mixed primary alkyl amines: the mixed primary alkyl amine of C 16～C22 contains 55 to 90 percent of the linear primary alkyl amine of C 16～C22 and 10 to 45 percent of the branched primary alkyl amine of C 16～C22, preferably 55 to 80 percent of the linear primary alkyl amine of C 16～C22 and 20 to 45 percent of the branched primary alkyl amine of C 16～C22.
According to the invention, the carbon content is calculated as mole percent based on the total moles of mixed primary alkylamines: the content of C 16～C18 alkyl primary amine in the C 16～C22 mixed alkyl primary amine is 45% -85%, the content of C 19～C22 alkyl primary amine is 15% -55%, preferably the content of C 16～C18 alkyl primary amine is 55% -75%, and the content of C 19～C22 alkyl primary amine is 25% -45%.
According to the invention, the carbon number and the alkyl type are divided in mole percent based on the total number of moles of mixed primary alkylamines: of the mixed alkyl primary amines of C 16～C22, the content of the linear primary amine of C 16～C18 is 40-70%, the content of the linear primary amine of C 19～C22 is 15-40%, the content of the branched primary amine of C 16～C18 is 5-35%, and the content of the branched primary amine of C 19～C22 is 5-30%; preferably, the content of primary linear chain amines of C 16～C18 is 45-60%, the content of primary linear chain amines of C 19～C22 is 20-35%, the content of primary branched chain amines of C 16～C18 is 5-25%, and the content of primary branched chain amines of C 19～C22 is 5-30%.
According to the invention, the acidic catalyst is preferably one or more of glacial acetic acid, sulfuric acid, hydrochloric acid, phosphoric acid, SO 3 and P 2O5 or an aqueous solution of these substances and mixtures thereof, preferably sulfuric acid and/or glacial acetic acid or an aqueous solution thereof, most preferably glacial acetic acid or acetic acid with a mass percentage of 60-100%.
According to the invention, the molar ratio between the alkyl benzotriazoles and/or benzotriazoles and the alkyl primary amines is 1:0.5 to 1, preferably 1:0.8 to 1.
According to the invention, the mass ratio between the acid catalyst and the alkylbenzene triazole and/or the benzotriazole is 1:0.5 to 5, preferably 1:0.8 to 4.
According to the invention, the reaction temperature of the alkyl benzotriazoles and/or benzotriazoles, primary alkyl amines under the action of the acid catalyst is 60 to 100 ℃, preferably 80 to 100 ℃, and the longer the reaction time, the better the reaction time, the more generally, the 2 to 8 hours, preferably 3 to 6 hours.
According to the invention, in the antioxidant composition, the mass ratio between the ester compound and the multifunctional oily agent is 10-60: 1, preferably 15 to 50:1.
According to the present invention, an amine compound selected from the group consisting of compounds represented by formula (II') is optionally included in the antioxidant composition;
The formula (II ') is a compound formed by bonding m ' structural units shown as the formula (III '),
In formula (II '), m' is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3; each R I group is independently selected from H, C 1～10 linear or branched alkyl, preferably from H, C 1～5 linear or branched alkyl, more preferably from H, C 1～3 linear or branched alkyl; each x is independently selected from an integer between 0 and 4, preferably an integer between 0 and 2, more preferably 0 or 1; each R II group is independently selected from H, C 1～10 linear or branched alkyl, preferably from H, C 1～5 linear or branched alkyl, more preferably from H, C 1～3 linear or branched alkyl; each y is independently selected from integers between 0 and 2, preferably 0 or 1; each R III group is independently selected from H, C 1～10 linear or branched alkyl, preferably from H, C 1～5 linear or branched alkyl, more preferably from H, C 1～3 linear or branched alkyl; each z is independently selected from an integer between 0 and 3, preferably an integer between 0 and 2, more preferably 0 or 1;
Each L I"、LII"、LIII "in formula (II') is independently H, C 1～4 alkyl, a binding end that binds to L I"、LII"、LIII" in a different building block.
According to the invention, preferably, in formula (II '), L I"、LII"、LIII' in the same structural unit are not bonded to each other.
According to the invention, in formula (II '), when m' =1, each L I"、LII"、LIII "is independently H or C 1～4 alkyl.
According to the invention, in formula (II '), when m ' =2, there are 2 structural units as shown in formula (III '), L I"、LII"、LIII of the 2 structural units (when they are both bonded binding ends) can be bonded to each other, alternatively, there is only one L I"、LII "or L III" each of the 2 structural units bonded to each other, i.e., only one covalent bond is formed between 2 different structural units.
According to the present invention, in formula (II '), when m ' is greater than 2, there are m ' structural units as shown in formula (III '), L I"、LII"、LIII "of m ' structural units (when they are all bonded ends) capable of bonding to each other, further alternatively, m ' structural units are 1 end structural unit, (m ' -2) middle structural unit and another 1 end structural unit bonded in sequence, there is only one L I"、LII" or L III "in each end structural unit and L I"、LII" or L III "in the middle structural unit adjacent thereto, and 2L I"、LII" or L III "in each middle structural unit is bonded to L I"、LII" or L III "in the structural unit adjacent thereto, respectively, i.e., only one covalent bond is formed between each two different structural units connected thereto.
According to the present invention, examples of the compound represented by the formula (II') include:
According to the present invention, preferably, the mass ratio between the ester compound and the optional amine compound is 1:0.1 to 5, more preferably 1:0.2 to 3.
The antioxidant composition can obviously improve the oxidation stability and high-temperature corrosion resistance of lubricating oil, particularly synthetic lubricating oil, and is particularly suitable for aviation synthetic ester lubricating oil.
According to the present invention, the method for producing an ester compound comprises the step of reacting a compound represented by the formula (X) with a compound represented by the formula (Y);
In formula (X), n is an integer between 1 and 10, preferably an integer between 1 and 5, more preferably an integer between 1 and 3; r 0 is selected from the group consisting of n-valent C 1～30 linear or branched alkyl, C 2～30 linear or branched heteroalkyl, preferably from n-valent C 1～20 linear or branched alkyl, C 2～20 linear or branched heteroalkyl, more preferably from n-valent C 1～10 linear or branched alkyl, C 2～10 linear or branched heteroalkyl; each R' group is independently selected from C 1～10 linear or branched alkylene, preferably from C 1～5 linear or branched alkylene, more preferably from C 1～3 linear or branched alkylene; each R "group is independently selected from C 1～30 straight or branched alkyl, preferably from C 1～20 straight or branched alkyl, more preferably from C 1～10 straight or branched alkyl; each R' "group is independently selected from C 1～30 straight or branched alkyl, preferably from C 1～20 straight or branched alkyl, more preferably from C 1～10 straight or branched alkyl;
In formula (Y), each R I group is independently selected from H, C 1～10 linear or branched alkyl, preferably from H, C 1～5 linear or branched alkyl, more preferably from H, C 1～3 linear or branched alkyl; each x is independently selected from an integer between 0 and 4, preferably an integer between 0 and 2, more preferably 0 or 1; each R II group is independently selected from H, C 1～10 linear or branched alkyl, preferably from H, C 1～5 linear or branched alkyl, more preferably from H, C 1～3 linear or branched alkyl; each y is independently selected from integers between 0 and 2, preferably 0 or 1; each R III group is independently selected from H, C 1～10 linear or branched alkyl, preferably from H, C 1～5 linear or branched alkyl, more preferably from H, C 1～3 linear or branched alkyl; each z is independently selected from an integer between 0 and 3, preferably an integer between 0 and 2, more preferably 0 or 1.
According to the present invention, the mass ratio between the compound represented by the formula (X) and the compound represented by the formula (Y) is preferably 1:0.1 to 5, more preferably 1:0.3 to 3; the temperature at which the compound represented by the formula (X) and the compound represented by the formula (Y) react is preferably 110 to 200 ℃, more preferably 130 to 190 ℃; the absolute pressure of the reaction of the compound represented by the formula (X) with the compound represented by the formula (Y) is not particularly limited, but is preferably in the range of usually 0.01 to 0.15MPa, more preferably 0.01 to 0.12MPa.
According to the present invention, the time for the reaction of the compound represented by the formula (X) with the compound represented by the formula (Y) is preferably such that the reaction proceeds smoothly, and is usually preferably as long as 3 to 12 hours, more preferably 4 to 10 hours.
According to the invention, the compound of formula (X) is preferably selected from the esterification products of C 1～18 monohydric and/or polyhydric alcohols with C 3～20 fatty acids, the polyhydric alcohols of C 1～18 comprising one or more of ethylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol, and the fatty acids of C 3～20 comprising one or more of valeric acid, isovaleric acid, caproic acid, enanthic acid, caprylic acid, isooctanoic acid, 2-ethylhexanoic acid, pelargonic acid, 3, 5-trimethylhexanoic acid, capric acid, lauric acid, palmitic acid and oleic acid.
According to the present invention, the compound represented by the formula (X) is more preferably an esterification product of one or more of trimethylolpropane, pentaerythritol and dipentaerythritol with a saturated fatty acid of C 3～20, and still more preferably one or more of trimethylolpropane ester, pentaerythritol ester and dipentaerythritol ester having an kinematic viscosity in the range of (3.6-4.3) mm 2/s at 100 ℃.
According to the present invention, examples of the compound represented by the formula (X) include one or more of the following structural compounds:
Wherein each group is as defined in any one of the preceding aspects.
According to the present invention, preferably, the compound represented by formula (X) may be selected from one or more of the following compounds: trimethylolpropane saturated acid ester, pentaerythritol saturated acid ester, dipentaerythritol saturated acid ester and di-n-decanoic acid isooctanol ester.
According to the present invention, preferably, in the compound represented by the formula (Y), at least one hydrogen atom is present in the ortho position of each benzene ring to which the amine group is attached.
According to the present invention, preferably, the compound represented by the formula (Y) may be selected from one or more of the following compounds: p-tert-butyl-phenyl-1-naphthylamine, p-tert-octyl-phenyl-1-naphthylamine, p-phenethyl-phenyl-1-naphthylamine, phenyl-1-naphthylamine.
According to the present invention, it is preferable that the compound represented by the formula (X) is reacted with the compound represented by the formula (Y) in the presence of a peroxide. The peroxide is preferably an organic peroxide. The organic peroxide may be one or more of alkyl peroxide, acyl peroxide, ketal peroxide, and organic ester peroxide.
The alkyl peroxide has the structure that: r 1-O-O-R2
The structure of the acyl peroxide is as follows:
the structure of the ketal peroxide is as follows:
The structure of the organic peroxide is as follows:
wherein each R 1、R2 group is independently one or more of an alkyl, aryl, alkyl-substituted aryl or aryl-substituted alkyl group having a total number of carbon atoms between 2 and 10, preferably an alkyl and/or phenyl group having a total number of carbon atoms between 4 and 6, most preferably a tert-butyl and/or phenyl group.
According to the present invention, the organic peroxide is preferably one or more of organic peroxy ester t-butyl-2-ethyl peroxy caproate, peroxy ketal 2, 2-bis (t-butyl peroxy) butane, di-t-butyl peroxide, dihexyl peroxide and diphenyl peroxide, most preferably di-t-butyl peroxide.
According to the present invention, the amount of the peroxide is preferably 0.8 to 1.5 times the amount of the compound substance represented by (Y).
According to the present invention, the reaction of the compound represented by the formula (X) with the compound represented by the formula (Y) is preferably carried out under the protection of an inert gas, preferably nitrogen.
According to the present invention, a solvent may or may not be added to the reaction of the compound represented by the formula (X) with the compound represented by the formula (Y). The solvent is preferably a C 6～C20 alkane, most preferably a C 6～C10 alkane, such as n-decane, n-heptane, cyclohexane.
According to the present invention, the reaction product of the compound represented by formula (X) and the compound represented by formula (Y) may be a single ester compound, may be a mixture of a plurality of ester compounds, may be a mixture of one or more ester compounds and the compound represented by formula (II') in the second aspect, or may be a mixture of the compound represented by formula (X).
According to the present invention, the reaction product of the compound represented by the formula (X) and the compound represented by the formula (Y) may be a single ester compound or may be a mixture of a plurality of ester compounds, and these reaction products are all contemplated by the present invention, and the difference in the form of the reaction products does not affect the achievement of the effects of the present invention. Accordingly, these reaction products are collectively referred to herein, without distinction, as the ester compounds. In view of this, according to the present invention, there is no absolute necessity of further purifying the reaction product, or further separating an ester compound of a specific structure from the reaction product. Of course, this purification or isolation is preferred for further enhancement of the intended effect of the invention, but is not required for the invention. The purification or separation method may be, for example, a method of purifying or separating the reaction product by column chromatography or preparative chromatography.
According to the present invention, the reaction product of the compound represented by the formula (X) and the compound represented by the formula (Y) may be a mixture of one or more ester compounds and the compound represented by the formula (II') described in the second aspect, which is the antioxidant composition described in the second aspect of the present invention. In addition to the reaction with the compound shown in the formula (X), the compound shown in the formula (Y) can also undergo self intermolecular coupling reaction, and the self intermolecular coupling product is the compound with m larger than 1 in the compound shown in the formula (II'). Therefore, the compound shown in the formula (II ') comprises unreacted compound shown in the formula (Y) (namely, a compound with m equal to 1 in the compound shown in the formula (II ')) and a coupling product between self molecules of the compound shown in the formula (Y) (namely, a compound with m greater than 1 in the compound shown in the formula (II ').
According to the present invention, when the reaction product of the compound represented by the formula (X) and the compound represented by the formula (Y) is a mixture of one or more ester compounds and the compound represented by the formula (II ') in the second aspect, the compound represented by the formula (II') in the second aspect can be separated; the compound of the formula (II') of the second aspect may be used as an antioxidant composition of the present invention without being isolated.
According to the present invention, the reaction product of the compound represented by the formula (X) and the compound represented by the formula (Y) may be a mixture of one or more ester compounds with the compound represented by the formula (II') described in the second aspect, the compound represented by the formula (X). The reaction product may contain a compound represented by the formula (X), namely, an unreacted compound represented by the formula (X).
According to the present invention, when the reaction product of the compound represented by the formula (X) and the compound represented by the formula (Y) is a mixture of one or more ester compounds with the compound represented by the formula (II') described in the second aspect, the compound represented by the formula (X) can be separated; instead of separating the compound of formula (X), the compound of formula (X) may be used as an additional component. The compound represented by the formula (X) is an ester compound and can be used as a lubricating base oil, an antiwear agent or a friction modifier, and therefore can be used as an additional component.
According to the present invention, in the reaction of the compound represented by the formula (X) with the compound represented by the formula (Y), the reaction product may be subjected to a purification operation to improve the purity of the reaction product. Examples of the purification operation method include washing, recrystallization, and the like, and are not particularly limited.
In a second aspect, the present invention provides a method of preparing the antioxidant composition.
The preparation method of the antioxidant composition comprises the step of mixing the ester compound, the multifunctional oiliness agent and the optional amine compound.
In a third aspect, the present invention provides a lubricating oil composition.
The lubricating oil composition of the present invention comprises a lubricating base oil, an antioxidant composition as described in any one of the preceding aspects. The antioxidant composition of any of the preceding aspects comprises 1% to 20% of the total mass of the lubricating oil composition, preferably 3% to 15% of the total mass of the lubricating oil composition. The lubricating base oil is preferably a synthetic hydrocarbon and/or a synthetic ester, more preferably an ester of a C 1～10 polyol reacted with a C 3～20 fatty acid, examples of which C 1～10 polyol include one or more of trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol, and examples of which C 3～20 fatty acid include one or more of valeric acid, isovaleric acid, caproic acid, enanthic acid, caprylic acid, isooctanoic acid, 2-ethylhexanoic acid, pelargonic acid, 3, 5-trimethylcaproic acid, capric acid and lauric acid. The lubricating base oil is more preferably an esterification product of one or more of trimethylolpropane, pentaerythritol and dipentaerythritol with a saturated fatty acid of C 3～20, and further preferably one or more of trimethylolpropane ester, pentaerythritol ester and dipentaerythritol ester having an kinematic viscosity of (3-12) mm 2/s at 100 ℃. The lubricating oil composition of the present invention may also incorporate other types of additives such as viscosity index improvers, antiwear agents, pour point depressants, rust inhibitors, and the like.
The lubricating oil composition provided by the invention has excellent oxidation stability and high-temperature corrosion resistance.
In a fourth aspect, the present invention also provides a method of improving the antioxidant and corrosion resistance of a lubricating oil composition, the method comprising adding to a lubricating base oil the antioxidant composition of any of the preceding aspects.
Drawings
FIG. 1 is a superposition spectrum of the reaction starting material p-tert-octyl-phenyl-1-naphthylamine (L06) and of the reaction product A1.
FIG. 2 is an infrared spectrum of reaction product B1 (i.e., a liquid alkylbenzene triazole fatty amine salt).
FIG. 3 is a nuclear magnetic resonance spectrum of reaction product B1 (i.e., liquid alkylbenzene triazole fatty amine salt).
Detailed Description
In the context of the present specification, the expression "number +valence +group" or the like means a group obtained by removing the number of hydrogen atoms represented by the number from a basic structure (such as a chain, a ring, or a combination thereof, etc.) to which the group corresponds, preferably a group obtained by removing the number of hydrogen atoms represented by the number from carbon atoms (preferably saturated carbon atoms and/or non-identical carbon atoms) contained in the structure. For example, "3-valent linear or branched alkyl group" refers to a group obtained by removing 3 hydrogen atoms from a linear or branched alkane (i.e., the basic chain to which the linear or branched alkyl group corresponds), while "2-valent linear or branched heteroalkyl group" refers to a group obtained by removing 2 hydrogen atoms from a linear or branched heteroalkane (preferably from a carbon atom contained in the heteroalkane, or further from a non-identical carbon atom).
In the context of the present specification, the heteroalkyl group refers to a group obtained by breaking the carbon chain structure of the alkyl group with one or more (such as1 to 5,1 to 4, 1 to 3, 1 to 2 or 1) hetero groups selected from-Sx-, -O-and-NR "", where x is an integer between 1 and 5 (preferably an integer between 1 and 4, more preferably 1,2 or 3). From the viewpoint of structural stability, it is preferable that, in the case where a plurality of hetero groups are present, no direct bond is formed between any two of the hetero groups. It is evident that the hetero group is not at the carbon chain end of the hydrocarbon group. For convenience of description, the number of carbon atoms of the alkyl group before the interruption is still referred to as the number of carbon atoms of the heteroalkyl group after the interruption. Specifically, for example, a C 4 straight-chain alkyl group (CH 3-CH2-CH2-CH2 -) is interrupted by a hetero group-O-to give a C 4 straight-chain heteroalkyl group such as CH3-O-CH2-CH2-CH2-、CH3-CH2-O-CH2-CH2- or CH 3-CH2-CH2-O-CH2 -, C 4 straight-chain heteroalkyl such as CH3-S-CH2-S-CH2-CH2-、CH3-CH2-S-CH2-S-CH2- or CH 3-S-CH2-CH2-S-CH2 -can be obtained after being interrupted by two hetero groups-S-, and C 4 straight-chain heteroalkyl such as CH 3-S-CH2-S-CH2-S-CH2 -can be obtained after being interrupted by three hetero groups-S-.
The percentages and ratios mentioned below are percentages by mass or mass unless otherwise specified.
The main raw materials used are as follows:
Antioxidant L06, p-tert-octyl-phenyl-1-naphthylamine, pasteur company, purity > 98%
VANLUBEV81, van der Waals, america, purity > 98%
5-Methylbenzotriazole, chemical purity in Shanghai chemical plant
C 16～C22 alkyl primary amine monomer, purity >97%, purchased from the national institute of sciences
Antioxidant T534, antioxidant alkyldiphenylamine, xingpu, institute of petrochemistry and chemical industry
Antioxidant T501,2, 6-di-tert-butyl-4-methylphenol, liangyun gang Ningkang chemical Co., ltd
Antioxidant T558, dinonyl diphenylamine, liaoning Tianhe Fine chemical Co., ltd
Antioxidant T531, N-phenyl-1-naphthylamine, tianjin, ming's Chemie Co., ltd
Pentaerythritol ester, zhejiang quzhou chemical industry Co., ltd, has an kinematic viscosity of 5.02mm 2/s at 100 ℃.
The motion viscosity of the saturated acid ester of the four-centimeter polyol is 3.82mm 2/s at 100 ℃ and is available from Shandong Rui chemical industry Co.
Trimethylolpropane ester, china petrochemical great wall lubricating oil Chongqing division company, wherein the commodity code is great wall 5101 high-temperature synthetic lubricating oil, and the kinematic viscosity at 100 ℃ is 5.05mm 2/s.
Dipentaerythritol ester, shandong Rui Jie chemical Co., ltd, and has an kinematic viscosity of 7.0mm 2/s at 100 ℃.
Di-tert-butyl peroxide, jiangsu-strongpoint functional chemical Co., ltd.
Example 1
90G of P-tert-octyl-phenyl-1-naphthylamine as a raw material is added into 90g of tetracentis trimethylolpropane ester with the kinematic viscosity of 3.85mm 2/s at 100 ℃, the mixed system is heated and stirred in the presence of nitrogen, the mixed system is maintained at 145 ℃, di-tert-butyl peroxide 65g is added into the reaction system, the mixture is reacted for 4 hours at the constant temperature of 145+/-2 ℃, then the mixture is distilled for 30min at 145+/-2 ℃ under reduced pressure of less than or equal to 1000Pa, then the vacuum degree is increased to less than or equal to 500Pa, the mixture is gradually heated to and maintained at 175 ℃ under reduced pressure for more than 40min, the product is cooled and cooled in the nitrogen environment after the reduced pressure distillation, and finally 168g of reaction product A1 is obtained, wherein the reaction product A1 mainly comprises the compounds of the structural formula P-1, the structural formula P-2, the compound of the structural formula P-3, the compound of the structural formula (II '-1), the compound of the structural formula (II' -3) and the trimethylolpropane ester used in the embodiment in small amount.
The glacial acetic acid solution with the mass concentration of 90% is prepared. 0.3mol (35.7 g) of methylbenzotriazole and 0.2mol (64.6 g) of an alkyl primary amine were successively added to a three-necked flask, and stirred and heated, wherein the composition of the alkyl primary amine was as follows: based on the total molar amount of the alkyl primary amine, the molar percentage of the C 16～C18 primary amine is 65 percent, the molar percentage of the C 19～C20 primary amine is 35 percent, wherein the molar percentage of the C 16～C18、C19～C20 linear primary amine is 50 percent and 20 percent in sequence, and the molar percentage of the C 16～C18、C19～C20 branched primary amine is 15 percent and 15 percent in sequence. When the temperature of the reaction mixture reached 85 ℃, 20g of 90% acetic acid solution was initially added dropwise to the three-necked flask for 15min, and the reaction was carried out at 80℃to 85℃for 5 hours. After the reaction is finished, washing the upper liquid of the liquid reaction product by using distilled water at 80 ℃ until the upper liquid is neutral, shaking, standing, cooling and layering the mixed liquid, and performing temperature-control vacuum distillation on the obtained upper liquid to obtain 80g of completely transparent and bright orange liquid reaction product, namely the multifunctional oily agent B1.
Uniformly stirring the reaction product A1 and the reaction product B1 according to the mass ratio of 40:1 at the temperature below 80 ℃ to prepare the antioxidant composition C1.
The infrared analysis and characterization of the reaction raw material p-tert-octyl-phenyl-1-naphthylamine (L06) and the reaction product A1 are carried out, and the upper and lower superposition spectrograms of the two are shown in figure 1.
The spectral peak data in fig. 1 are tabulated below.
Infrared spectrogram absorption peak statistics comparison table of reaction raw materials and reaction products
In connection with fig. 1 and the above table, a spectrogram analysis was performed, as follows:
The typical absorption peak of the reaction raw material (L06) is 35; the reaction product (L06-2 polymer) typically has 17 absorption peaks; comparison shows that the infrared absorption peak is obviously reduced; the strong infrared absorption peak 3412cm -1 of the secondary amino group is obviously weakened, and accords with the typical characteristics of the infrared spectrum of the polymer and the infrared spectrum absorption peak of the monomer compound thereof, which shows that oligomerization reaction does occur and the corresponding oligomer is generated.
The infrared absorption peak band (2956.1-2866.32) cm -1 of the reaction raw material is obviously wider and duller, and the infrared absorption peak band corresponding to the reaction product is (2957.1-2863.2) cm -1; the 1586cm -1 absorption peak (medium intensity) and the 1464cm -1 absorption peak (medium intensity) in the reaction product are typical characteristic absorption peaks of aromatic ring v C＝C, and the main structure in the reaction product is determined to be an aromatic secondary amine structure;
The absorption peak of 1614cm -1 (medium intensity), 1578cm -1 (medium intensity) and 1477cm -1 in the reaction raw material L06 are typical characteristic absorption peaks of benzene ring v C＝C in the aromatic secondary amine structure; the key characteristic peak of the reaction product was relatively low in intensity as seen by the 1586cm -1 peak of the reaction product and the 1578 peak of the reaction feed, cm -1. Also, the key characteristic peak of the reaction product was relatively low in intensity as seen by comparing the 823cm -1 peak of the reaction product with the 823cm -1 peak of the reaction material.
The absorption peak band (1465-1610) cm -1 is an important characteristic of an infrared spectrogram of an aromatic compound, the infrared absorption peak 1586cm -1 of a reaction product is obviously weaker than the infrared absorption peak 1614cm -1、1578cm-1 of a reaction raw material, the difference of the absorption peak band morphology of the raw material and the product is the reason that a plurality of aromatic rings exist in the reaction product, and the oligomerization reaction of the reaction raw material is also proved to occur, so that an oligomeric compound with multiple aromatic rings is formed; the presence of a significant amount of aromatic secondary amine in the reaction product confirmed that the alkylated aromatic amine had undergone oligomerization with aromatic ring radical substitution.
The presence of 1745.94cm -1 in the infrared spectrum of the reaction product is a strong absorption peak of typical ester groups, indicating the presence of ester groups in the chemical structure of the synthetic product A1.
The reaction product B1 was sampled and characterized by infrared analysis, and the infrared spectrum is shown in FIG. 2.
As can be seen from fig. 2, 1628.47cm -1 is typical delta as(NH3 +) characteristic absorption peak, 1546.05cm -1 is typical delta s(NH3 +) characteristic absorption peak, 2958.96-2164.40 cm -1 is typical v NH(NH3 +) wide and strong absorption band, particularly v NH(NH3 + near 2591cm -1、2729cm-1 is obvious in absorption, and the spectrogram proves that the reaction product contains a large amount of primary amine salt; 1623.26cm -1、1595.28cm-1、1508.09cm-1 is a characteristic absorption peak of v C＝C, 3071.48cm -1 is a characteristic absorption peak of v ＝CH on a benzene ring, and therefore the existence of the benzene ring can be judged; 1280.26cm -1 is a characteristic absorption peak of a typical aromatic primary amine v C-N; and the characteristic absorption peak of hydrogen v N-H on nitrogen at the 1 position of the benzotriazole is not found in the vicinity of 3500cm -1, and the spectrogram proves that no primary amine exists in the liquid product, so that the benzotriazole alkyl fatty amine salt is generated after the reaction of the benzotriazole.
The reaction product B1 is sampled and subjected to 1 HNMR nuclear magnetic analysis characterization, and a nuclear magnetic spectrum is shown in figure 3.
As can be seen from FIG. 3, a completely new peak of hydrogen proton chemical shift signal appears in 1 HNMR spectrum of the liquid product of the alkylbenzotriazole fatty amine salt at delta 3.198, and no peak exists in both the benzotriazole 1 HNMR spectrum and the alkyl fatty acid ammonium 1 HNMR spectrum, wherein the peak is generated after the chemical shift of alpha-H on methylene adjacent to primary amine salt is shifted, so that the reaction product is judged to contain primary amine salt with hydrogen protons. 1 In HNMR spectra, delta 1.152-delta 1.245 and delta 0.977-delta 1.108 respectively represent the chemical shift signal peaks of methyl and methylene hydrogen protons on the alkyl chain of the reaction product.
The nuclear magnetic resonance spectrum 1 HNMR spectrum of the liquid alkyl benzotriazole fatty amine salt is analyzed, and the disappearance of the chemical shift bands delta 12-delta 15 (delta 13.859) on the spectrum can be found, which shows that the chemical shift signal of active hydrogen protons on benzotriazole-NH-is disappeared, and the active hydrogen on nitrogen at the 1-position of benzotriazole is subjected to chemical reaction, so that the liquid alkyl benzotriazole fatty amine salt is generated.
Example 2
90G of raw material P-tert-octyl-phenyl-1-naphthylamine is added into 90g of pentaerythritol ester with kinematic viscosity of 5.02mm 2/s at 100 ℃, the mixed system is heated, stirred and dissolved in the presence of nitrogen, 65g of di-tert-butyl peroxide is added into the reaction system, the reaction is carried out at 140 ℃ +/-2 ℃ for 3h, then the mixture is distilled under reduced pressure at 140 ℃ +/-2 ℃ and less than or equal to 1000Pa for 30min, the vacuum degree is increased to less than or equal to 500Pa, the mixture is gradually heated and maintained at 175 ℃ for more than 40min, the reduced pressure distillation is finished, the product is cooled and cooled under the nitrogen environment, and finally 165g of reaction product A2 is obtained, wherein the compound with the structure similar to the structural formula P-1, the structural formula P-2 and the structural formula P-3 (the ester group is the ester group of pentaerythritol ester), and the compound with the structural formula (II '-2), the compound with the structural formula (II' -3) and the pentaerythritol ester used in the embodiment are contained in the mixture.
The glacial acetic acid solution with the mass concentration of 90% is prepared. 0.3mol (35.7 g) of methylbenzotriazole and 0.1mol (64.6 g) of an alkyl primary amine were successively added to a three-necked flask, and stirred and heated, wherein the alkyl primary amine had the composition: based on the total molar amount of the alkyl primary amine, the molar percentage of the C 16～C18 primary amine is 65 percent, the molar percentage of the C 19～C20 primary amine is 35 percent, and the molar percentage of the C 16～C18、C19～C20 linear primary amine is 45 percent and 25 percent in sequence; the mole percentage of the C 16～C18、C19～C20 branched primary amine is 20 percent and 10 percent in sequence. When the temperature of the reaction mixture reached 85 ℃, 20g of 90% acetic acid solution was initially added dropwise to the three-necked flask for 20min, and the reaction was carried out at 80℃to 85℃for 5 hours. After the reaction is finished, washing the upper liquid of the liquid reaction product by using distilled water at 80 ℃ until the upper liquid is neutral, standing and layering the mixed liquid, and performing temperature-controlled vacuum distillation on the obtained upper liquid to obtain 77.5g of completely transparent bright orange liquid reaction product, namely the multifunctional oily agent B2;
reaction product A2 and reaction product B2 are mixed according to a mass ratio of 40:1 is evenly stirred at the temperature of below 80 ℃ and is blended to prepare the antioxidant composition C2.
Example 3
130G of raw material P-tert-octyl-phenyl-1-naphthylamine is added into 150g of pentaerythritol ester with kinematic viscosity of 4.6mm 2/s at 100 ℃, the mixed system is heated and stirred under nitrogen environment, the temperature of the system is maintained at 140+/-2 ℃, 80g of di-tert-butyl peroxide is added into the reaction system, the temperature is maintained at 150+/-2 ℃ for 3 hours, then the mixture is subjected to reduced pressure distillation for more than 40 minutes at 150+/-2 ℃ and less than or equal to 1000Pa, the product is cooled and cooled under nitrogen environment after the reduced pressure distillation, and finally 270g of reaction product A2 is obtained, wherein the reaction product A2 mainly comprises compounds with similar structures as the structural formula P-1, the structural formula P-2 and the structural formula P-3 (wherein ester groups are ester groups of pentaerythritol ester), and simultaneously comprises smaller amounts of the compounds of the structural formula (II ' -1), the structural formula (II ' -3) and the structural formula (II ' -4) and smaller amounts of pentaerythritol ester in the embodiment.
The glacial acetic acid solution with the mass concentration of 90% is prepared. 0.15mol (17.85 g) of methylbenzotriazole and 0.1mol (32.3 g) of an alkyl primary amine were successively added to a three-necked flask, and stirred and heated, wherein the composition of the alkyl primary amine was as follows: based on the total molar weight of the alkyl primary amine, the molar percentage content of the C 16～C18、C19～C20 linear primary amine is 40 percent and 25 percent in sequence; the mole percentage of the branched primary amine of C 16～C18、C19～C20 is 25 percent and 10 percent in turn. When the temperature of the reaction mixture reached 75 ℃,20 g of 90% acetic acid solution was initially added dropwise to the three-necked flask for 15 minutes, and the reaction was carried out at 70℃to 75℃for 5 hours. After the reaction is finished, washing the upper liquid of the liquid reaction product by using distilled water at 70 ℃ until the upper liquid is neutral, standing and layering the mixed liquid, and performing temperature-control vacuum distillation on the obtained upper liquid to obtain 36.27g of completely transparent bright orange liquid reaction product, namely the multifunctional oily agent B3;
reaction product A3 and reaction product B3 are mixed according to a mass ratio of 40:1 is evenly stirred at the temperature of below 80 ℃ and is blended to prepare the antioxidant composition C3.
Example 4
150G of raw material p-tert-octyl-phenyl-1-naphthylamine is added into 150g of mixed polyol saturated acid ester (wherein the mass ratio of trimethylolpropane ester to dipentaerythritol ester is 3:1), the mixed system is heated, stirred and dissolved in the presence of nitrogen, the mixed system is maintained at 150+/-2 ℃, 90g of di-tert-butyl peroxide is added into the reaction system, the reaction is carried out for 4 hours at 150 ℃, then the reaction is carried out for reduced pressure distillation for more than 40 minutes at 150+/-2 ℃ and less than or equal to 1000Pa, after the reduced pressure distillation is finished, the product is cooled down in the nitrogen environment, and 286g of reaction product A4 is finally obtained; the reaction product A4 mainly contains a compound having a structure similar to the structures P-1, P-2 and P-3 (except that the ester group is an ester group of a saturated acid ester of a mixed polyol), and also contains a smaller amount of the compounds of the structures (II '-1), II' -2, II '-3 and II' -4) and a smaller amount of the saturated acid ester of a mixed polyol used in this example.
Reaction product A4, reaction product B2 (prepared in example 2) were mixed according to a mass ratio of 40:1 is evenly stirred at the temperature of below 80 ℃ and is blended to prepare the antioxidant composition C4.
Evaluation of oxidation stability and high temperature Corrosion resistance
The reaction products or compositions C1 to C4 of the invention and comparative antioxidants V81, T558, T534, T531 and tricresyl phosphate (TCP) were added to pentaerythritol saturated acid ester lubricating base oil having an kinematic viscosity of 100℃of=5.02 mm 2/s, respectively, and heated and stirred to prepare examples 5 to 12 and comparative examples 1 to 4 of lubricating oil compositions. The formulation compositions of examples 5-8 and comparative examples 1-4 of the lubricating oil compositions of the present invention are shown in Table 1.
Evaluation of high temperature Corrosion and Oxidation stability
The lubricating oil compositions in Table 1 were subjected to corrosion and oxidation stability evaluation tests, respectively, using the test methods specified by International oil Specification MIL-PRF-23699G, methods FEDSTD-791-5308. The experimental conditions are as follows: introducing dry air at a constant temperature of 204 ℃ for oxidation for 72 hours; the oxygen flow is 50-83 mL/min; the metal test pieces were steel, silver, titanium (copper), aluminum (Al) and titanium (Mg) of specific specifications, and the total acid value change of the lubricating oil before and after oxidation at 25℃and the viscosity change rate at 40℃were examined, and the formation amount of 100mL of oil deposit was examined.
The evaluation index of the method is as follows: change in total acid number before and after oxidation of the oil sample (. DELTA.TAN/mgKOH.g -1); viscosity change rate at 40 ℃ (. DELTA. Viscosity%); 100mL test oil deposit formation (Deposit/mg. Cndot. (100 mL) -1); the mass change of the unit area of the metal test piece such as metal copper, steel, silver, aluminum, titanium and the like. According to the invention, the experimental result is evaluated by the quality change data of the copper sheet. The test results are shown in Table 2.
Table 1 lubricating oil compositions examples 5-8 and comparative examples 1-4
Comparing the technical index requirements of FED-STD-791-5308 and GJB563 method evaluation methods with the corrosion and oxidation stability evaluation data results in Table 2, it is known that the 5 cSt grade lubricating oil composition examples 5-8 added with the antioxidant composition of the invention have significant advantages in terms of sheet metal quality change, total acid value change, viscosity change rate and deposit formation amount compared with the lubricating oil composition of comparative examples, and meet the technical index requirements of FED-STD-791-5308 and GJB563 method corrosion and oxidation stability. Therefore, the antioxidant composition has excellent high-temperature oxidation resistance and deposit formation resistance, can better control the total acid value change, the viscosity change rate and the deposit formation of oil products before and after the oxidation of lubricating oil, and well meets the corrosion and oxidation stability index requirements of FED-STD-791-5308 and GJB563 methods.
TABLE 2 evaluation test results of high temperature Corrosion and Oxidation stability
Claims (29)
1. An antioxidant composition comprises an ester compound and a multifunctional oiliness agent, wherein the structure of the ester compound is shown as a formula (I):
in the formula (I), n is an integer between 1 and 10; r 0 is selected from the group consisting of n-valent C 1～30 linear or branched alkyl, C 2～30 linear or branched heteroalkyl; each R' group is independently selected from C 1～10 straight or branched chain alkylene; each R "group is independently selected from C 1～30 straight or branched alkyl; each R' "group is independently selected from C 1～30 straight or branched alkyl; each A group is selected from a 1-valent group shown in a formula (II), H, C 1～20 is a straight chain or branched chain alkyl group, and at least one A group in the formula (I) is selected from a 1-valent group shown in the formula (II);
The formula (II) is a 1-valent group formed by bonding m structural units shown in the formula (III),
In the formula (II), m is an integer between 1 and 10; each R I group is independently selected from H, C 1～10 straight or branched alkyl; each x is independently selected from integers between 0 and 4; each R II group is independently selected from H, C 1～10 straight or branched alkyl; each y is independently selected from integers between 0 and 2; each R III group is independently selected from H, C 1～10 straight or branched alkyl; each z is independently selected from integers between 0 and 3;
Each L I、LII、LIII in formula (II) is independently H, C 1～4 alkyl, a binding end bonded to L I、LII、LIII in a different building block, a binding end bonded to formula (I), a 1-valent group represented by formula (IV); only one L I、LII or L III present in formula (II) is a binding end that is bonded to formula (I);
Delta in the 1-valent group represented by the formula (IV) represents a binding end bonded to L I、LII or L III;
In the formula (IV), n' is an integer between 1 and 10; r 0 is selected from the group consisting of n-valent C 1～30 linear or branched alkyl, C 2～30 linear or branched heteroalkyl; each R' group is independently selected from C 1～10 straight or branched chain alkylene; each R "group is independently selected from C 1～30 straight or branched alkyl; each R' "group is independently selected from C 1～30 straight or branched alkyl;
The preparation method of the multifunctional oiliness agent comprises the following steps: in the presence of inert gas, alkyl benzotriazole and/or benzotriazole and alkyl primary amine react under the action of an acid catalyst, and the product is collected.
2. The antioxidant composition according to claim 1, wherein in formula (I), n is an integer between 1 and 5; r 0 is selected from the group consisting of n-valent C 1～20 linear or branched alkyl, C 2～20 linear or branched heteroalkyl; each R' group is independently selected from C 1～5 straight or branched chain alkylene; Each R "group is independently selected from C 1～20 straight or branched alkyl; each R' "group is independently selected from C 1～20 straight or branched alkyl; each A group is selected from the group shown in formula (II), H, C 1～10 straight-chain or branched alkyl; In the formula (II), m is an integer between 1 and 5; each R I group is independently selected from H, C 1～5 straight or branched alkyl; each x is independently selected from integers between 0 and 2; each R II group is independently selected from H, C 1～5 straight or branched alkyl; Each y is independently selected from 0 or 1; each R III group is independently selected from H, C 1～5 straight or branched alkyl; each z is independently selected from integers between 0 and 2; in the formula (IV), n' is an integer between 1 and 5; r 0 is selected from the group consisting of n-valent C 1～20 linear or branched alkyl, C 2～20 linear or branched heteroalkyl; Each R' group is independently selected from C 1～5 straight or branched alkylene; each R "group is independently selected from C 1～20 straight or branched alkyl; each R' "group is independently selected from C 1～20 straight or branched alkyl.
3. The antioxidant composition according to claim 2, wherein in formula (I), n is an integer between 1 and 3; r 0 is selected from the group consisting of n-valent C 1～10 linear or branched alkyl, C 2～10 linear or branched heteroalkyl; each R' group is independently selected from C 1～3 straight or branched chain alkylene; Each R "group is independently selected from C 1～10 straight or branched alkyl; each R' "group is independently selected from C 1～10 straight or branched alkyl; each A group is selected from the group shown in formula (II), H, C 1～5 straight-chain or branched alkyl; In the formula (II), m is an integer between 1 and 3; each R I group is independently selected from H, C 1～3 straight or branched alkyl; each x is independently selected from 0 or 1; each R II group is independently selected from H, C 1～3 straight or branched alkyl; Each R III group is independently selected from H, C 1～3 straight or branched alkyl; each z is independently selected from 0 or 1; in the formula (IV), n' is an integer between 1 and 3; r 0 is selected from the group consisting of n-valent C 1～10 linear or branched alkyl, C 2～10 linear or branched heteroalkyl; Each R' group is independently selected from C 1～3 straight or branched chain alkylene; each R "group is independently selected from C 1～10 straight or branched alkyl; each R' "group is independently selected from C 1～10 straight or branched alkyl.
4. The antioxidant composition as claimed in claim 1, wherein,
In formula (II), when m=1, one of L I、LII、LIII is a binding end bonded to formula (I), and the other two are each independently H, C 1～4 alkyl or a 1-valent group represented by formula (IV);
in formula (II), when m=2, there are 2 structural units represented by formula (III), and only one L I、LII or L III each exists between the 2 structural units;
In formula (II), when m is greater than 2, there are m structural units as shown in formula (III), m structural units are 1 end structural units, (m-2) intermediate structural units and another 1 end structural unit bonded in this order, only one L I、LII or L III is bonded to L I、LII or L III in the intermediate structural unit adjacent thereto in each end structural unit, and 2L I、LII or L III is bonded to L I、LII or L III in the structural unit adjacent thereto, respectively, in each intermediate structural unit.
5. The antioxidant composition of claim 1, wherein the group of formula (II) comprises:
wherein represents the binding end to the bond of formula (I).
6. The antioxidant composition of claim 1, wherein the ester compound comprises:
The group PAN represents a group represented by formula (II).
7. The antioxidant composition of claim 1, wherein the alkyl benzotriazole and/or benzotriazole has the structure:
Wherein R 1' is selected from H, C 1～C12 straight or branched alkyl;
The primary alkyl amine is C 16～C22 primary alkyl amine, and has a structural formula of R 2'CH2NH2, wherein R 2' is C 15～C21 straight-chain or branched-chain alkyl;
The acidic catalyst is one or more of glacial acetic acid, sulfuric acid, hydrochloric acid, phosphoric acid, SO 3 and P 2O5 or an aqueous solution of the substances and the mixture thereof.
8. The antioxidant composition of claim 7, wherein R 1' is selected from the group consisting of C 1～C8 straight or branched alkyl.
9. The antioxidant composition of claim 7, wherein R 1' is selected from methyl.
10. The antioxidant composition of claim 1, wherein the primary alkyl amine is a mixed primary alkyl amine of C 16～C22.
11. The antioxidant composition as set forth in claim 10, wherein,
Based on the total moles of mixed primary alkylamines, the alkyl groups are in mole percent: the mixed primary alkyl amine of C 16～C22 contains 55-90% of the linear primary alkyl amine of C 16～C22 and 10-45% of the branched primary alkyl amine of C 16～C22; or alternatively
Based on the total mole number of the mixed primary alkylamines, the carbon content is calculated in mole percent: the content of C 16～C18 alkyl primary amine in the C 16～C22 mixed alkyl primary amine is 45-85%, and the content of C 19～C22 alkyl primary amine is 15-55%; or alternatively
Based on the total mole number of mixed primary alkylamines, the carbon number and alkyl type are calculated in mole percent: of the mixed alkyl primary amines of C 16～C22, the content of the linear primary amine of C 16～C18 is 40-70%, the content of the linear primary amine of C 19～C22 is 15-40%, the content of the branched primary amine of C 16～C18 is 5-35%, and the content of the branched primary amine of C 19～C22 is 5-30%.
12. The antioxidant composition as set forth in claim 10, wherein,
Based on the total moles of mixed primary alkylamines, the alkyl groups are in mole percent: the mixed alkyl primary amine of C 16～C22 comprises 55-80% of linear alkyl primary amine of C 16～C22 and 20-45% of branched alkyl primary amine of C 16～C22; or alternatively
Based on the total mole number of the mixed primary alkylamines, the carbon content is calculated in mole percent: the content of the C 16～C18 alkyl primary amine in the C 16～C22 mixed alkyl primary amine is 55-75%, and the content of the C 19～C22 alkyl primary amine is 25-45%; or alternatively
Based on the total mole number of mixed primary alkylamines, the carbon number and alkyl type are calculated in mole percent: of the mixed alkyl primary amines of C 16～C22, the content of the linear primary amine of C 16～C18 is 45-60%, the content of the linear primary amine of C 19～C22 is 20-35%, the content of the branched primary amine of C 16～C18 is 5-25%, and the content of the branched primary amine of C 19～C22 is 5-30%.
13. The antioxidant composition according to claim 1, wherein the molar ratio between the alkylbenzene triazole and/or benzotriazole and the primary alkylamine is 1:0.5 to 1; the mass ratio of the acid catalyst to the alkyl benzotriazole and/or the benzotriazole is 1:0.5 to 5; the reaction temperature of the alkyl benzotriazole and/or the benzotriazole and the alkyl primary amine under the action of the acid catalyst is 60-100 ℃.
14. The antioxidant composition of claim 13, wherein the molar ratio between the alkyl benzotriazole and/or benzotriazole and the alkyl primary amine is 1:0.8 to 1; the mass ratio of the acid catalyst to the alkyl benzotriazole and/or the benzotriazole is 1:0.8 to 4; the reaction temperature of the alkyl benzotriazole and/or the benzotriazole and the alkyl primary amine under the action of the acid catalyst is 80-100 ℃.
15. The antioxidant composition according to any one of claims 1 to 14, wherein the mass ratio between the ester compound and the multifunctional oily agent is 10 to 60:1.
16. The antioxidant composition according to any one of claims 1 to 14, wherein the mass ratio between the ester compound and the multifunctional oily agent is 15 to 50:1.
17. The antioxidant composition according to any one of claims 1 to 14, further comprising an amine compound having a structure represented by formula (II'):
The formula (II ') is a compound formed by bonding m ' structural units shown as the formula (III '),
In formula (II '), m' is an integer of 1 to 10; each R I group is independently selected from H, C 1～10 straight or branched alkyl; each x is independently selected from integers between 0 and 4; each R II group is independently selected from H, C 1～10 straight or branched alkyl; each y is independently selected from integers between 0 and 2; each R III group is independently selected from H, C 1～10 straight or branched alkyl; each z is independently selected from integers between 0 and 3;
Each L I"、LII"、LIII "in formula (II') is independently H, C 1～4 alkyl, a binding end that binds to L I"、LII"、LIII" in a different building block.
18. The antioxidant composition as set forth in claim 17, wherein in the formula (II '), m' is an integer of 1 to 5; each R I group is independently selected from H, C 1～5 straight or branched alkyl; each x is independently selected from integers between 0 and 2; each R II group is independently selected from H, C 1～5 straight or branched alkyl; each y is independently selected from 0 or 1; each R III group is independently selected from H, C 1～5 straight or branched alkyl; each z is independently selected from integers between 0 and 2.
19. The antioxidant composition as set forth in claim 18, wherein in the formula (II '), m' is an integer of 1 to 3; each R I group is independently selected from H, C 1～3 straight or branched alkyl; each x is independently selected from 0 or 1; each R II group is independently selected from H, C 1～3 straight or branched alkyl; each R III group is independently selected from H, C 1～3 straight or branched alkyl; each z is independently selected from 0 or 1.
20. The antioxidant composition of claim 17, wherein,
In formula (II '), when m' =1, each L I"、LII"、LIII "is independently H or C 1～4 alkyl; in formula (II '), when m ' =2, there are 2 structural units represented by formula (III '), and only one L I"、LII "or L III" exists between the 2 structural units, respectively, to be bonded to each other;
In the formula (II '), when m' is greater than 2, there are m 'structural units as shown in the formula (III'), m 'structural units are 1 end structural units, (m' -2) intermediate structural units and another 1 end structural unit which are sequentially bonded, only one L I"、LII "or L III" is bonded to L I"、LII "or L III" in the intermediate structural unit adjacent thereto in each end structural unit, and 2L I"、LII "or L III" is bonded to L I"、LII "or L III" in the structural unit adjacent thereto, respectively, in each intermediate structural unit.
21. The antioxidant composition as set forth in claim 17, wherein the mass ratio between the ester compound and the compound represented by the formula (II') is 1:0.1 to 5.
22. The antioxidant composition as set forth in claim 1, wherein the method for producing the ester compound comprises the step of reacting the compound represented by the formula (X) with the compound represented by the formula (Y);
In the formula (X), n is an integer between 1 and 10; r 0 is selected from the group consisting of n-valent C 1～10 linear or branched alkyl, C 2～10 linear or branched heteroalkyl; each R' group is independently selected from C 1～3 straight or branched chain alkylene; each R "group is independently selected from C 1～10 straight or branched alkyl; each R' "group is independently selected from C 1～10 straight or branched alkyl;
In formula (Y), each R I group is independently selected from H, C 1～10 straight or branched alkyl; each x is independently selected from integers between 0 and 4; each R II group is independently selected from H, C 1～10 straight or branched alkyl; each y is independently selected from integers between 0 and 2; each R III group is independently selected from H, C 1～10 straight or branched alkyl; each z is independently selected from integers between 0 and 3.
23. The antioxidant composition of claim 22, wherein,
In the formula (X), n is an integer between 1 and 5; r 0 is selected from the group consisting of n-valent C 1～20 linear or branched alkyl, C 2～20 linear or branched heteroalkyl; each R' group is independently selected from C 1～5 straight or branched chain alkylene; each R "group is independently selected from C 1～20 straight or branched alkyl; each R' "group is independently selected from C 1～20 straight or branched alkyl;
In formula (Y), each R I group is independently selected from H, C 1～5 straight or branched alkyl; each x is independently selected from integers between 0 and 2; each R II group is independently selected from H, C 1～5 straight or branched alkyl; each y is independently selected from 0 or 1; each R III group is independently selected from H, C 1～5 straight or branched alkyl; each z is independently selected from integers between 0 and 2.
24. The antioxidant composition of claim 23, wherein,
In the formula (X), n is an integer between 1 and 3; r 0 is selected from the group consisting of n-valent C 1～10 linear or branched alkyl, C 2～10 linear or branched heteroalkyl; each R' group is independently selected from C 1～3 straight or branched chain alkylene; each R "group is independently selected from C 1～10 straight or branched alkyl; each R' "group is independently selected from C 1～10 straight or branched alkyl;
In formula (Y), each R I group is independently selected from H, C 1～3 straight or branched alkyl; each x is independently selected from 0 or 1; each R II group is independently selected from H, C 1～3 straight or branched alkyl; each R III group is independently selected from H, C 1～3 straight or branched alkyl; each z is independently selected from 0 or 1.
25. A process for preparing an antioxidant composition as claimed in any one of claims 1 to 24, comprising the step of mixing said ester compound, a multifunctional oiliness agent and optionally an amine compound.
26. A lubricating oil composition comprising a lubricating base oil, an antioxidant composition according to any one of claims 1 to 24.
27. Lubricating oil composition according to claim 26, characterised in that the lubricating base oil is selected from synthetic hydrocarbons and/or synthetic esters.
28. The lubricating oil composition of claim 26, wherein the lubricating base oil is selected from the group consisting of esters of the C 1～10 polyols reacted with C 3～20 fatty acids.
29. A method of improving the antioxidant and corrosion resistance of a lubricating oil composition, which comprises adding the antioxidant composition of any one of claims 1 to 24 to a lubricating base oil.
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