CN114479989B - Antioxidant composition, preparation method thereof and lubricating oil composition - Google Patents
Antioxidant composition, preparation method thereof and lubricating oil composition Download PDFInfo
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Abstract
The invention provides an antioxidant composition, a preparation method thereof and a lubricating oil composition containing the antioxidant composition. The antioxidant composition comprises an ester compound and a multifunctional oiliness agent. The structure of the ester compound is shown as a formula (I):
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 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 naphthozole 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 a lubricating oil antioxidant extreme pressure antiwear agent with better performance.
US 6,184,262B1 discloses the use of alkyl-substituted methylene-dianiline-benzotriazole or alkyl benzotriazole with aromatic amine antioxidant complexing agents as stabilizers in polyether and polyester and polyurethane foams with good results in reducing discoloration and inhibiting scorching, curing, foaming of the polyol.
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.
According to the invention, 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 is R 0 Selected from C of n-valent 1～30 Straight-chain or branched alkyl, C 2～30 Straight-chain or branched heteroalkyl, preferably selected from n-valent C 1～20 Straight-chain or branched alkyl, C 2～20 Straight or branched heteroalkyl, more preferably C, selected from n-valent C 1～10 Straight-chain or branched alkyl, C 2～10 Linear or branched heteroalkyl; each R' group is independently selected from C 1～10 Linear or branched alkylene groups, preferably selected from C 1～5 Linear or branched alkylene groups, more preferably selected from C 1～3 Linear or branched alkylene; each R' group is independently selected from C 1～30 Linear or branched alkyl groups, preferably selected from C 1～20 Linear or branched alkyl groups, more preferably selected from C 1～10 Linear or branched alkyl; each R' "group is independently selected from C 1～30 Linear or branched alkyl groups, preferably selected from C 1～20 Linear or branched alkyl groups, more preferably selected from C 1～10 Linear or branched alkyl; each A group is selected from the group shown in formula (II), H, C 1～20 A linear or branched alkyl group, preferably selected from the group represented by formula (II), H, C 1～10 A linear or branched alkyl group, more preferably selected from the group represented by formula (II), H, C 1～5 A linear or branched alkyl group, and in which formula (I) at least one A group is selected from the 1-valent groups represented by 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 of 1 to 10, preferably 1 to 5More preferably an integer between 1 and 3; each R is I The radicals are each independently selected from H, C 1～16 Linear or branched alkyl groups, preferably selected from H, C 1～10 Linear or branched alkyl groups, more preferably selected from H, C 4～10 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 L in formula (II) I 、L II 、L III Each independently H, C 1～4 Alkyl, and L in different building blocks I 、L II 、L III A bonding end of bonding, a bonding end of bonding with a formula (I), and a 1-valent group shown in a formula (IV); in formula (II) only one L is present I 、L II Or L III Is a binding moiety bonded to formula (I);
delta in the 1-valent group represented by the formula (IV) represents a group represented by the formula (IV) and L I 、L II Or L III A bonded end;
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 is R 0 Selected from C of n-valent 1～30 Straight-chain or branched alkyl, C 2～30 Straight-chain or branched heteroalkyl, preferably selected from n-valent C 1～20 Straight-chain or branched alkyl, C 2～20 Straight or branched heteroalkyl, more preferably C, selected from n-valent C 1～10 Straight-chain or branched alkyl, C 2～10 Linear or branched heteroalkyl; each R' group is independently selected from C 1～10 Linear or branched alkylene groups, preferably selected from C 1～5 Linear or branched alkylene groups, more preferably selected from C 1～3 Linear or branched alkylene; each R' group is independently selected from C 1～30 Linear or branched alkyl groups, preferably selected from C 1～20 Linear or branched alkyl groups, more preferably selected from C 1～10 Linear or branched alkyl; each R' "group is independently selected from C 1～30 Linear or branched alkyl groups, preferably selected fromFrom C 1～20 Linear or branched alkyl groups, more preferably selected from C 1～10 Linear or branched alkyl.
According to the invention, preferably, in formula (II), L in said same structural unit I 、L II 、L III Are not bonded with each other.
According to the invention, in formula (II), when m=1, L I 、L II 、L III One of which 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 the formula (IV).
According to the present invention, in formula (II), when m=2, there are 2 structural units as shown in formula (III), L in 2 structural units I 、L II 、L III Can be bonded to each other (when they are both bonded binding ends), optionally only one L is present between each of the 2 building blocks I 、L II Or L III The mutual bonding, i.e. the formation of only one covalent bond between 2 different building blocks.
According to the invention, in formula (II), when m is greater than 2, there are m structural units of formula (III), L in the m structural units I 、L II 、L III (when they are all bonded ends) can be bonded to each other, further alternatively, the m structural units are sequentially bonded 1 end structural unit, (m-2) intermediate structural units and another 1 end structural unit, and only one L is present in each end structural unit I 、L II Or L III And L in the intermediate structural unit adjacent thereto I 、L II Or L III Bonding, there are 2L in each structural unit in the middle I 、L II Or L III L in each of the structural units adjacent thereto I 、L II Or L III Bonding, i.e. the formation of only one covalent bond between every two different building blocks that are linked.
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).
In accordance with the present invention, as an example of trimethylolpropane esters, examples of the ester compounds of the present invention include:
In the molecular structural formulas of the ester compounds P-1, P-2 and P-3, the group DPA represents a group (II), and the specific molecular structure of the group (II) is shown as above. Taking the group (II-1) as an example, the molecular structural formula of the ester compound formed therefrom can be exemplified 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 is 1 ' selected from H, C 1 ～C 12 Linear or branched alkyl, preferably C 1 ～C 8 Straight or branched chain alkyl groups, most preferably methyl.
According to the invention, the primary alkylamine is C 16 ～C 22 Primary alkylamines of the formula R 2 ’CH 2 NH 2 Wherein R is 2 ' C 15 ～C 21 Straight or branched alkyl of (a).
According to the invention, the primary alkylamine is preferably C 16 ～C 22 The mixed primary alkyl amine is a mixture of a linear primary amine and a branched primary amine.
According to the invention, the alkyl groups are divided in mole percent, based on the total moles of mixed primary alkyl amines: the C is 16 ～C 22 Comprising 55% to 90% of C 16 ～C 22 And 10 to 45 percent of C 16 ～C 22 Preferably comprising 55% to 80% C 16 ～C 22 Linear primary alkyl amine and 20-45% C 16 ～C 22 Branched alkyl primary amines of (a).
According to the invention, the carbon content is calculated as mole percent based on the total moles of mixed primary alkylamines: the C is 16 ～C 22 C in the mixed primary alkylamine of (C) 16 ～C 18 The content of primary alkyl amine is 45-85%, C 19 ～C 22 The content of primary alkylamines is 15 to 55%, preferably C 16 ～C 18 The content of primary alkyl amine is 55-75%, C 19 ～C 22 The content of the 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: at said C 16 ～C 22 C in the mixed primary alkylamine of (A) 16 ～C 18 The content of the linear primary amine is 40 to 70 percent, C 19 ～C 22 The content of the linear primary amine is 15 to 40 percent, C 16 ～C 18 The content of branched primary amine is 5% -35%, C 19 ～C 22 The content of branched primary amine is 5% -30%; excellent (excellent)Selecting C 16 ～C 18 The content of the linear primary amine is 45 to 60 percent, C 19 ～C 22 The content of the linear primary amine is 20 to 35 percent, C 16 ～C 18 The content of branched primary amine is 5-25%, C 19 ～C 22 The content of branched primary amine is 5% -30%.
According to the invention, the acid catalyst is preferably glacial acetic acid, sulfuric acid, hydrochloric acid, phosphoric acid, SO 3 And P 2 O 5 Preferably sulfuric acid and/or glacial acetic acid or an aqueous solution thereof, most preferably glacial acetic acid or acetic acid in an amount of 60% to 100% by mass.
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'):
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 is I The radicals are each independently selected from H, C 1～20 Linear or branched alkyl groups, preferably selected from H, C 1～12 Linear or branched alkyl groups, more preferably selected from H, C 4～12 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 L in the formula (II') I ’、L II ’、L III ' each independently H, C 1～4 Alkyl, and L in different building blocks I ’、L II ’、L III ' the binding end of the bond.
According to the present invention, preferably, in formula (II'), L in the same structural unit I ’、L II ’、L III ' are not bonded to each other.
According to the invention, in formula (II'), when m=1, L I ’、L II ’、L III ' each independently is H or C 1～4 An alkyl group.
According to the present invention, in formula (II '), when m=2, there are 2 structural units as shown in formula (III'), L in 2 structural units I ’、L II ’、L III ' when they are all bonded binding ends, can be bonded to each other, alternatively, only one L is present between 2 structural units I ’、L II ' or L III ' mutual bonding, i.e. the formation of only one covalent bond between 2 different building blocks.
According to the invention, in formula (II '), when m is greater than 2, there are m structural units represented by formula (III'), L in the m structural units I ’、L II ’、L III ' when they are all bonded ends, can be bonded to each other, further alternatively, the m structural units are sequentially bonded 1 terminal structural unit, (m-2) intermediate structural units and another 1 terminal structural unit,only one L is present in the structural unit of each end I ’、L II ' or L III ' and L in the intermediate building block adjacent thereto I ’、L II ' or L III 'bonding, there are 2L's in each structural unit in the middle I ’、L II ' or L III ' L in the structural units adjacent thereto respectively I ’、L II ' or L III ' bonding, i.e. the formation of only one covalent bond between each two different building blocks that are linked.
According to the present invention, examples of the amine compound 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, reduce the generation of sediment in the high-temperature oxidation process, 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 is R 0 Selected from C of n-valent 1～30 Straight-chain or branched alkyl, C 2～30 Straight-chain or branched heteroalkyl, preferably selected from n-valent C 1～20 Straight-chain or branched alkyl, C 2～20 Straight or branched heteroalkyl, more preferably C, selected from n-valent C 1～10 Straight-chain or branched alkyl, C 2～10 Linear or branched heteroalkyl; each R' groupThe radicals are each independently selected from C 1～10 Linear or branched alkylene groups, preferably selected from C 1～5 Linear or branched alkylene groups, more preferably selected from C 1～3 Linear or branched alkylene; each R' group is independently selected from C 1～30 Linear or branched alkyl groups, preferably selected from C 1～20 Linear or branched alkyl groups, more preferably selected from C 1～10 Linear or branched alkyl; each R' "group is independently selected from C 1～30 Linear or branched alkyl groups, preferably selected from C 1～20 Linear or branched alkyl groups, more preferably selected from C 1～10 Linear or branched alkyl;
in the formula (Y), each R I The radicals are each independently selected from H, C 1～10 Linear or branched alkyl groups, preferably selected from H, C 1～5 Linear or branched alkyl groups, more preferably selected 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.
According to the present invention, the compound represented by the formula (X) is preferably selected from C 1～18 Monohydric and/or polyhydric alcohols of (C) 3～20 Esterification product of fatty acid, said C 1～18 The polyol of (C) comprises one or more of ethylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol 3～20 Comprises one or more of valeric acid, isovaleric acid, caproic acid, heptanoic acid, caprylic acid, isooctanoic acid, 2-ethylhexanoic acid, pelargonic acid, 3, 5-trimethylhexanoic acid, capric acid, lauric acid, palmitic acid and oleic acid. The compound shown in the formula (X) is more preferably one or more of trimethylolpropane, pentaerythritol and dipentaerythritol and C 3～20 Further preferably, the range of kinematic viscosity at 100℃is (3.6-4.3) mm 2 One or more of trimethylolpropane ester, pentaerythritol ester and dipentaerythritol ester of/s.
According to the present invention, examples of the compound represented by the formula (X) include one or more of the following structural compounds:
according to the present invention, the molar ratio between the compound represented by formula (X) and the compound represented by 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 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 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, the compound represented by the formula (Y) may be selected from one or more of the following compounds: diphenylamine, diisooctyldiphenylamine, di-t-butyldiphenylamine, p-isooctyl, p-t-butyldiphenylamine, including but not limited to these alkyl diphenylamines.
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 is R 1 -O-O-R 2
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 is 1 、R 2 Each independently is one or more of an alkyl, aryl, alkyl-substituted aryl or aryl-substituted alkyl group having a total carbon number of between 2 and 10, preferably an alkyl and/or phenyl group having a total carbon number of 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 0.5 to 1.5 times the number of moles of the compound represented by formula (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 C 6 ～C 20 Alkanes, most preferably C 6 ～C 10 Alkanes, such as n-decane, n-heptane, cyclohexane.
According to the invention, the reaction product of the compound shown in the formula (X) and the compound shown in the formula (Y) can be a single ester compound, can be a mixture formed by a plurality of ester compounds, can be a mixture of one or more ester compounds and the amine compound, and can be a mixture of one or more ester compounds, the amine compound and the compound shown in the 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 amine compound. 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 preparation method, when the reaction product of the compound shown in the formula (X) and the compound shown in the formula (Y) is a mixture of one or more ester compounds and the amine compounds, the amine compounds can be separated; the amine compound may be used as a component of the antioxidant composition of the present invention without separating the amine compound.
According to the preparation method of the invention, the reaction product of the compound shown in the formula (X) and the compound shown in the formula (Y) can be a mixture of one or more ester compounds, the amine compounds and the compound shown in 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 preparation method of the invention, when the reaction product of the compound shown in the formula (X) and the compound shown in the formula (Y) is a mixture of one or more ester compounds, the amine compounds and the compound shown in the formula (X), the compound shown in 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 production method of 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 synthetic ester, more preferably C 1～10 Polyol of (C) and C 3～20 An ester of a fatty acid reaction of (C) 1～10 The polyhydric alcohol of (2) may be exemplified byExamples include one or more of trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol, the C 3～20 Examples of the fatty acid include one or more of valeric acid, isovaleric acid, caproic acid, heptanoic acid, caprylic acid, isooctanoic acid, 2-ethylhexanoic acid, nonanoic acid, 3, 5-trimethylhexanoic acid, capric acid, lauric acid. The lubricating base oil is more preferably one or more of trimethylolpropane, pentaerythritol and dipentaerythritol and C 3～20 Further preferably, the esterified product of saturated fatty acid of (C) is an ester having an kinematic viscosity of (3-12) mm at 100 DEG C 2 One or more of trimethylolpropane ester, pentaerythritol ester and dipentaerythritol ester of/s. 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 an infrared spectrum of the reaction product A1 and the reaction material VANLUBE V81 (diisooctyldiphenylamine) superimposed in example 1.
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 as 1 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, C 4 Straight chain alkyl (CH) 3 -CH 2 -CH 2 -CH 2 (-) is interrupted by a hetero group-O-, CH can be obtained 3 -O-CH 2 -CH 2 -CH 2 -、CH 3 -CH 2 -O-CH 2 -CH 2 -or CH 3 -CH 2 -CH 2 -O-CH 2 -C et al 4 Linear heteroalkyl radicals, interrupted by two hetero groups-S-can give CH 3 -S-CH 2 -S-CH 2 -CH 2 -、CH 3 -CH 2 -S-CH 2 -S-CH 2 -or CH 3 -S-CH 2 -CH 2 -S-CH 2 -C et al 4 Linear heteroalkyl groups interrupted by three hetero groups-S-can give CH 3 -S-CH 2 -S-CH 2 -S-CH 2 -C et al 4 A linear heteroalkyl group.
The percentages and ratios mentioned below are percentages by mass or mass unless otherwise specified.
The main raw materials used are as follows:
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
Vanlube V81, 4' -diisooctyl-diphenylamine, van der Waals
5-methylbenzotriazole, chemical purity in Shanghai chemical plant
C16-C22 alkyl primary amine monomer with purity >97%, purchased from the national institute of sciences
Tetrali trimethylolpropane saturated fatty acid ester, kinematic viscosity at 100 ℃ =3.8 mm 2 S, shandong Rui chemical Co., ltd,>98％
pentaerythritol ester, zhejiang quzhou chemical Co., ltd., kinematic viscosity at 100 ℃ =5.02 mm 2 /s，>98％
Seven-li dipentaerythritol ester, shandong Shangzhi chemical Co., ltd., 100℃kinematic viscosity=7.5 mm 2 /s，>98％
Trimethylolpropane oleate, shandong Shakui chemical Co., ltd., kinematic viscosity at 100 ℃ =8.5 mm 2 /s，>97％
Pentium trimethylol propane ester, chongqing division of Chinese petrochemical great wall lubricating oil, commodity code is great wall 5101 high-temperature synthetic lubricating oil, 100 ℃ kinematic viscosity=5.05 mm 2 /s，>98％
Di-tert-butyl peroxide, jiangsu-strongpoint functional chemical Co., ltd.
Example 1
117g of the starting material 4,4' -diisooctyl-diphenylamine are added to 117g of kinematic viscosity at 100℃=3.8 mm 2 Heating, stirring and dissolving the mixed system in the presence of nitrogen in/s trimethylolpropane saturated fatty acid ester, maintaining the mixed system at 145 ℃, adding 84g of di-tert-butyl peroxide into the reaction system, and reacting at 145 ℃ at constant temperatureAnd then carrying out reduced pressure distillation for 30min at 145 ℃ and below 1000Pa, increasing the vacuum degree to less than or equal to 0.005MPa, gradually heating to and maintaining at 175 ℃ for more than 40min, and cooling the product in a nitrogen environment after the reduced pressure distillation is finished, so as to finally obtain 225g of reaction product A1, wherein the reaction product A1 mainly comprises a compound of a structural formula P-1, a structural formula P-2 and a structural formula P-3, a smaller amount of a compound of a structural formula P-4, a structural formula P-5, a structural formula P-6 and a structural formula P-7, and a small amount of trimethylolpropane ester in the example.
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: c based on the total molar amount of primary alkylamines 16 ～C 18 The total of the mole percentages of primary amines is 65%, C 19 ～C 20 The molar percentage of primary amine is 35% in total, wherein C 16 ～C 18 、C 19 ～C 20 The mole percentage content of the linear primary amine is 50 percent and 20 percent in sequence, C 16 ～C 18 、C 19 ～C 20 The mole percentage of branched primary amine is 15% and 15% in turn. 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.
And uniformly stirring the reaction product A1 and the reaction product B1 at the temperature below 80 ℃ according to the mass ratio of 25:1 to 40:1 respectively, and preparing an antioxidant composition C1 and an antioxidant composition C2.
The reaction raw materials VANLUBE V81 and the product A1 are respectively sampled and subjected to infrared analysis and characterization, the superposition spectrograms of the two are shown in figure 1, the positions and the intensities of infrared absorption peaks are shown in table 1, and spectrogram analysis is performed.
Table 1 statistics of absorption peaks of infrared spectrogram
Infrared spectrum analysis of reaction product A1 (V81-2 spectrum in FIG. 1)
3052.5 and 2950.78cm exist in V81-2 infrared spectrogram -1 Is typically about 100cm from the absorption peak of the aromatic amine -1 The infrared band of (2) shows that after the reaction, the diphenylamine still keeps and presents the characteristic of aromatic secondary amine; 3398.82cm -1 (3450～3330cm -1 ) The moderate sharp band at the position is aromatic secondary amino group symmetrical telescopic vibration v (NH) absorption peak, 1605, 1511.4, 1467cm -1 Is typically benzene ring v C＝C Characteristic absorption peaks, indicating that the reaction product is still aromatic secondary amine structure;
the infrared spectrum of V81-2 is reduced compared with the number of the absorption peaks of the infrared spectrum of the monomer compound V81, the key characteristic peaks become wide and blunt, the key characteristic peaks are absorbed more, and the peak intensity is lower. Comparing V81-2 with V81 infrared spectrogram, the method has the following characteristics:
after the reaction raw material is chemically reacted, the infrared absorption peak of the secondary amino group on the molecule of the reaction raw material is 3416.7cm -1 Is obviously weakened and dulled, and the corresponding absorption peak on the molecule of the reaction product is 3398cm -1 Meanwhile, the product still has more secondary amino groups;
absorption peak band 1465-1610 cm -1 Is an important characteristic of an infrared spectrum of the aromatic compound, and the infrared absorption peak of the product is 1605cm -1 Obviously compared with the infrared absorption peak 1606cm of the raw material -1 The method is weakened, the morphology difference of absorption peak bands of the raw materials and the products is that electron clouds interact among a plurality of aromatic rings in the molecules of the products to form super-conjugated large pi bonds, the morphology difference of infrared spectrogram peak bands is caused, and the oligomeric reaction between the reaction raw materials is proved to occur to form an oligomeric compound with a plurality of aromatic rings; the presence of a large amount of aromatic secondary amine in the product confirms that the alkylated aromatic amine undergoes oligomerization with aromatic ring radical substitution.
The infrared spectrogram of the reaction product has a characteristic peak which indicates that secondary amino position ortho-position substitution exists on the benzene ring, namely 738cm of aromatic ring=C-H out-of-plane bending absorption peak -1 The method comprises the steps of carrying out a first treatment on the surface of the At the same time, R indicates that para-position of secondary amine group on benzene ring exists on benzene ring I Meta-substituted characteristic peak of alkyl-aromatic ring = C-H out-of-plane bend absorption bimodal 825cm -1 、731cm -1 The method comprises the steps of carrying out a first treatment on the surface of the Indicating that the aromatic ring in the product molecule is multi-substituted, such as P-6, P-7, etc.
1745.99cm in the V81-2 infrared Spectrometry -1 Is a strong absorption peak that occurs for typical ester groups. Indicating the presence of a large number of ester groups in the molecular structure of the product. The combination of the remarkable characteristics of the infrared spectrograms of the reaction products shows that the polymerization reaction does occur, and the target products, namely the oligomers of the alkyl diphenylamine and/or the copolymer and the ester thereof, such as P- (II-1) -1, P- (II-1) -2, P- (II-1) -3 and the like, are generated.
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 of the typical delta as (NH 3 + ) Characteristic absorption peak, 1546.05cm -1 Is of the typical delta s (NH 3 + ) Characteristic absorption peak, 2958.96-2164.40 cm -1 Is typically v NH (NH 3 + ) Broad and strong absorption band, especially at 2591cm -1 、2729cm -1 Near have v NH (NH 3 + ) The absorption is obvious, 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 v C＝C Is 3071.48cm -1 Is v on benzene ring ＝CH Characteristic absorption peaks, from which the presence of benzene rings can be judged; 1280.26cm -1 Is typically an aromatic primary amine v C-N Characteristic absorption peaks; and at 3500cm -1 Hydrogen v without nitrogen at position 1 of benzotriazole nearby N-H The characteristic absorption peaks of (2) and the spectrum shows that no primary amine exists in the liquid product, which indicates that the benzotriazole alkyl fatty amine salt is generated after the reaction of the benzotriazole.
Sampling reaction product B1Has been provided with 1 HNMR nuclear magnetic analysis characterization, nuclear magnetic spectrum is shown in figure 3.
As can be seen from FIG. 3, the liquid product, namely, an alkylbenzene triazole fatty amine salt 1 HNMR spectrum shows a brand new hydrogen proton chemical shift signal peak at delta 3.198, benzotriazole 1 HNMR spectra and alkyl fatty acid ammonium 1 The HNMR spectrum does not have the signal peak, and the signal peak is generated after the chemical shift of alpha-H on methylene adjacent to primary amine salt is moved, so that the reaction product is judged to contain primary amine salt with hydrogen proton. 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.
Nuclear magnetism hydrogen spectrum chart for analyzing liquid alkyl benzotriazole fatty amine salt 1 HNMR spectrum can find out the disappearance of chemical shift bands delta 12-delta 15 (delta 13.859) on the spectrum, which shows that the chemical shift signal of active hydrogen proton 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 alkylbenzene triazole fatty amine salt is generated.
Example 2
120g of 4,4' -diisooctyl-diphenylamine as starting material were added to 120g of kinematic viscosity at 100℃=5.02 mm 2 In the pentaerythritol ester/s, heating, stirring and dissolving a mixed system in the presence of nitrogen, maintaining the mixed system at 140 ℃, adding 88g of di-tert-butyl peroxide into the reaction system, reacting at 140 ℃ for 3h, then conducting reduced pressure distillation for 30min at 140 ℃ and below 1000Pa, then increasing the vacuum degree to be less than or equal to 0.005MPa, simultaneously gradually heating to and maintaining the temperature at 175 ℃ and conducting reduced pressure distillation for more than 40min, and after the reduced pressure distillation, cooling the product in a nitrogen environment to finally obtain 230g of a reaction product A2, wherein the reaction product A2 mainly comprises ester compounds with structures similar to the structural formulas P-1, P-2 and P-3 (the difference is that ester groups of the pentaerythritol esters in the ester compounds in the embodiment), and simultaneously comprises a smaller amount of compounds with the structural formulas P-4, P-5, P-6 and P-7 and a smaller amount of the pentaerythritol esters in the embodiment.
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: c based on the total molar amount of primary alkylamines 16 ～C 18 The total of the mole percentages of primary amines is 65%, C 19 ～C 20 The molar percentage of primary amine is 35% in total, wherein C 16 ～C 18 、C 19 ～C 20 The mole percentage of the linear primary amine is 45 percent and 25 percent in sequence; c (C) 16 ～C 18 、C 19 ～C 20 The mole percentage of branched primary amine is 20% and 10% in turn. 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;
and uniformly stirring the reaction product A2 and the reaction product B2 at the temperature below 80 ℃ according to the mass ratio of 25:1 to 40:1 respectively, and preparing an antioxidant composition C3 and an antioxidant composition C4.
Example 3
120g of the starting material 4,4' -diisooctyl-diphenylamine was added to 120g of kinematic viscosity=5 mm 2 Heating, stirring and dissolving a mixed system in the presence of nitrogen in/s mixed polyol saturated acid ester (wherein the mass ratio of trimethylolpropane ester to dipentaerythritol ester is 3:1), maintaining the mixed system at 150 ℃, adding 72g of di-tert-butyl peroxide into a reaction system, reacting at 150 ℃ for 4 hours, then distilling at 150 ℃ and below 1000Pa under reduced pressure for more than 40 minutes, and cooling the product in the nitrogen environment after the reduced pressure distillation is finished to finally obtain 235g of reaction product A3; the reaction product A3 mainly comprises compounds with structures similar to the structural formulas P-1, P-2 and P-3 (except that the ester group in the ester compound in the embodiment is a mixed polyol saturated acid esterEster groups of formula P-4, formula P-5, formula P-6, formula P-7), and minor amounts of the mixed polyol saturated acid esters of the present example.
A glacial acetic acid solution with the mass concentration of 70% is prepared. 0.15mol (17.85 g) of methylbenzotriazole and 0.1mol (32.3 g) of primary alkylamine are sequentially added into a three-necked flask, and stirred and heated, wherein the primary alkylamine comprises C based on the total molar weight of primary alkylamine 16 ～C 18 、C 19 ～C 20 The mole percentage of the linear primary amine is 40 percent and 25 percent in sequence; c (C) 16 ～C 18 、C 19 ～C 20 The mole percentage of branched primary amine is 25% and 10% in turn. When the temperature of the reaction mixture reached 75 ℃, 20g 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;
and uniformly stirring the reaction product A3 and the reaction product B3 at the temperature below 80 ℃ according to the mass ratio of 25:1 to 40:1 respectively, and preparing an antioxidant composition C5 and an antioxidant composition C6.
Evaluation of oxidation stability and high temperature Corrosion resistance
The antioxidant compositions C1 to C6 or the comparative antioxidants V81, T558, T534, T531 and the tricresyl phosphate (TCP) of the invention are added respectively into a mixture with kinematic viscosity at 100 ℃ of=5.02 mm 2 Examples 4-9 and comparative examples 1-4 of lubricating oil compositions were prepared by heating and stirring in/s pentaerythritol saturated acid ester lubricating base oil, wherein the mass percent of tricresyl phosphate was 2%. The formulation compositions of examples 4-9 and comparative examples 1-4 of the lubricating oil compositions of the present invention are shown in Table 2.
Table 2 lubricating oil compositions examples 4-9 and comparative examples 1-4
The lubricating oil compositions in Table 2 were subjected to corrosion and oxidation stability evaluation tests, respectively, using the test method FEDSTD-791-5308, which was the method specified in International oil Specification MIL-PRF-23699G. 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, titanium (magnesium) 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 oil sample (. DELTA.TAN/mgKOH.g) -1 ) The method comprises the steps of carrying out a first treatment on the surface of the Viscosity change at 40 ℃ (. DELTA.viscosityity%); 100mL test oil Deposit formation (Deposit/mg. Cnt. (100 mL) -1 ) The method comprises the steps of carrying out a first treatment on the surface of the 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 3.
Comparing the technical index requirements of the MIL-PRF-5308 evaluation method with the corrosion and oxidation stability evaluation results in Table 3, it is known that examples 4-9 of the 5 cSt grade lubricating oil composition added with the antioxidant composition of the present invention have significant advantages in terms of sheet metal quality change, total acid value change, viscosity change rate, deposit formation amount, compared with the lubricating oil composition of comparative examples, and the high temperature oxidation resistance is significantly better than that of comparative examples 1-4. The antioxidant composition can better control the change of total acid value, the change rate of viscosity and the deposit formation of lubricating oil before and after oxidation, and well meets the requirements of MIL-PRF-5308 corrosion and oxidation stability indexes. The antioxidant composition has excellent high-temperature oxidation resistance and deposit formation resistance, is obviously superior to a monomer aromatic amine antioxidant, and cannot meet the corrosion and oxidation stability technical index designated by the latest aviation engine oil specification MIL-PRF-23699G, namely the MIL-PRF-5308 evaluation method technical index.
TABLE 3 evaluation test results of high temperature Corrosion and Oxidation stability
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Claims (28)
1. An antioxidant composition comprises an ester compound and a multifunctional oiliness agent; 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 is R 0 Selected from C of n-valent 1～30 Straight-chain or branched alkyl, C 2～30 Linear or branched heteroalkyl; each R' group is independently selected from C 1～10 Linear or branched alkylene; each R' group is independently selected from C 1～30 Linear or branched alkyl; each R' "group is independently selected from C 1～30 Linear or branched alkyl; each A group is selected from the group shown in formula (II), H, C 1～20 A linear or branched alkyl group, and in which formula (I) at least one A group is selected from the 1-valent groups represented by 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 is I The radicals are each independently selected from H, C 1～16 Linear or branched alkyl; each x is independently selected from integers between 0 and 4;
each L in formula (II) I 、L II 、L III Each independently H, C 1～4 Alkyl, and L in different building blocks I 、L II 、L III A bonding end of bonding, a bonding end of bonding with a formula (I), and a 1-valent group shown in a formula (IV); in formula (II) only one L is present I 、L II Or L III Is a binding moiety bonded to formula (I);
delta in the 1-valent group represented by the formula (IV) represents a group represented by the formula (IV) and L I 、L II Or L III A bonded end;
in the formula (IV), n is an integer between 1 and 10; r is R 0 Selected from C of n-valent 1～30 Straight-chain or branched alkyl, C 2～30 Linear or branched heteroalkyl; each R' group is independently selected from C 1～10 Linear or branched alkylene; each R' group is independently selected from C 1～30 Linear or branched alkyl; each R' "group is independently selected from C 1～30 Linear 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 as claimed in claim 1, wherein,
in the formula (I), n is an integer between 1 and 5; r is R 0 Selected from C of n-valent 1～20 Straight-chain or branched alkyl, C 2～20 Linear or branched heteroalkyl; each R' group is independently selected from C 1～5 Linear or branched alkylene; each R' group is independently selected from C 1～20 Linear or branched alkyl; each R' "group is independently selected from C 1～20 Linear or branched alkyl; each A group is selected from the group shown in formula (II), H, C 1～10 Linear or branched alkyl;
In the formula (II), m is an integer between 1 and 5; each R is I The radicals are each independently selected from H, C 1～10 Linear or branched alkyl; each x is independently ofThe ground is selected from integers between 0 and 2;
in the formula (IV), n is an integer between 1 and 5; r is R 0 Selected from C of n-valent 1～20 Straight-chain or branched alkyl, C 2～20 Linear or branched heteroalkyl; each R' group is independently selected from C 1～5 Linear or branched alkylene; each R' group is independently selected from C 1～20 Linear or branched alkyl; each R' "group is independently selected from C 1～20 Linear or branched alkyl.
3. The antioxidant composition as claimed in claim 1, wherein,
in the formula (I), n is an integer between 1 and 3; r is R 0 Selected from C of n-valent 1～10 Straight-chain or branched alkyl, C 2～10 Linear or branched heteroalkyl; each R' group is independently selected from C 1～3 Linear or branched alkylene; each R' group is independently selected from C 1～10 Linear or branched alkyl; each R' "group is independently selected from C 1～10 Linear or branched alkyl; each A group is selected from the group shown in formula (II), H, C 1～5 Linear or branched alkyl;
in the formula (II), m is an integer between 1 and 3; each R is I The radicals are each independently selected from H, C 4～10 Linear or branched alkyl; each x is independently selected from 0 or 1;
In the formula (IV), n is an integer between 1 and 3; r is R 0 Selected from C of n-valent 1～10 Straight-chain or branched alkyl, C 2～10 Linear or branched heteroalkyl; each R' group is independently selected from C 1～3 Linear or branched alkylene; each R' group is independently selected from C 1～10 Linear or branched alkyl; each R' "group is independently selected from C 1～10 Linear or branched alkyl.
4. The antioxidant composition as claimed in claim 1, wherein in the formula (II), when m=1, L I 、L II 、L III One of them being a bond with formula (I)The other two are H, C 1～4 Alkyl or a 1-valent group represented by formula (IV); when m=2, there are 2 structural units represented by formula (III), and only one L exists between 2 structural units I 、L II Or L III Bonding each other; when m is greater than 2, there are m structural units represented by formula (III) m structural units being sequentially bonded 1 end structural unit, (m-2) intermediate structural units and another 1 end structural unit, only one L being present in each end structural unit I 、L II Or L III And L in the intermediate structural unit adjacent thereto I 、L II Or L III Bonding, there are 2L in each structural unit in the middle I 、L II Or L III L in each of the structural units adjacent thereto I 、L II Or L III And (5) bonding.
5. The antioxidant composition of claim 1, wherein the ester compound comprises one or more of the following structures:
wherein the group DPA represents a group represented by formula (II).
6. The antioxidant composition of claim 1, wherein the alkyl benzotriazole and/or benzotriazole has the structure:
wherein R is 1 ' selected from H, C 1 ～C 12 Linear or branched alkyl;
the primary alkyl amine is C 16 ～C 22 Primary alkylamines of the formula R 2 ’CH 2 NH 2 Wherein R is 2 ' C 15 ～C 21 Straight or branched alkyl of (a); the acid catalyst is glacial acetic acid, sulfuric acid, hydrochloric acid, phosphoric acid or SO 3 And P 2 O 5 An aqueous solution of one or more of these substances and mixtures thereof.
7. The antioxidant composition of claim 6, wherein R is 1 ' selected from C 1 ～C 8 Linear or branched alkyl.
8. The antioxidant composition of claim 1, wherein the primary alkyl amine is C 16 ～C 22 Primary amine of (a) is mixed.
9. The antioxidant composition of claim 8, wherein the antioxidant composition comprises, in mole percent, based on the total moles of primary mixed alkyl amines, as alkyl type: the C is 16 ～C 22 Comprising 55% to 90% of C 16 ～C 22 And 10 to 45 percent of C 16 ～C 22 Branched primary alkyl amines of (a); alternatively, the carbon content is in mole percent based on the total moles of mixed primary alkylamines: the C is 16 ～C 22 C in the mixed primary alkylamine of (C) 16 ～C 18 The content of primary alkyl amine is 45-85%, C 19 ～C 22 The content of alkyl primary amine is 15% -55%; alternatively, the carbon number and alkyl type are calculated in mole percent based on the total moles of mixed primary alkylamines: at said C 16 ～C 22 C in the mixed primary alkylamine of (A) 16 ～C 18 The content of the linear primary amine is 40 to 70 percent, C 19 ～C 22 The content of the linear primary amine is 15 to 40 percent, C 16 ～C 18 The content of branched primary amine is 5% -35%, C 19 ～C 22 The content of branched primary amine is 5% -30%.
10. According to claim 8An antioxidant composition characterized by comprising, in mole percent, based on the total moles of primary mixed alkyl amines, the following alkyl groups: the C is 16 ～C 22 Comprising 55% to 80% of C 16 ～C 22 Linear primary alkyl amine and 20-45% C 16 ～C 22 Branched primary alkyl amines of (a); alternatively, the carbon content is in mole percent based on the total moles of mixed primary alkylamines: the C is 16 ～C 22 C in the mixed primary alkylamine of (C) 16 ～C 18 The content of primary alkyl amine is 55-75%, C 19 ～C 22 The content of primary alkyl amine is 25% -45%; alternatively, the carbon number and alkyl type are calculated in mole percent based on the total moles of mixed primary alkylamines: at said C 16 ～C 22 C in the mixed primary alkylamine of (A) 16 ～C 18 The content of the linear primary amine is 45 to 60 percent, C 19 ～C 22 The content of the linear primary amine is 20 to 35 percent, C 16 ～C 18 The content of branched primary amine is 5-25%, C 19 ～C 22 The content of branched primary amine is 5% -30%.
11. 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 ℃.
12. The antioxidant composition according to claim 1, wherein the molar ratio between the alkylbenzene triazole and/or benzotriazole and the primary alkylamine is 1:0.8 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 ℃.
13. The antioxidant composition according to any one of claims 1 to 12, wherein the mass ratio between the ester compound and the multifunctional oily agent is 10 to 60:1.
14. the antioxidant composition according to any one of claims 1 to 12, wherein the mass ratio between the ester compound and the multifunctional oily agent is 15 to 50:1.
15. the antioxidant composition according to any one of claims 1 to 12, 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 is I The radicals are each independently selected from H, C 1～20 Linear or branched alkyl; each x is independently selected from integers between 0 and 4;
each L in the formula (II') I ’、L II ’、L III ' each independently H, C 1～4 Alkyl, and L in different building blocks I ’、L II ’、L III ' the binding end of the bond.
16. The antioxidant composition as set forth in claim 15, wherein in the formula (II'), m is an integer of 1 to 5; each R is I The radicals are each independently selected from H, C 1～12 Linear or branched alkyl; each x is independently selected fromFrom an integer between 0 and 2.
17. The antioxidant composition of claim 15, wherein in formula (II'), m is an integer between 1 and 3; each R is I The radicals are each independently selected from H, C 4～12 Linear or branched alkyl; each x is independently selected from 0 or 1.
18. The antioxidant composition as claimed in claim 15, wherein in the formula (II'), when m=1, L I ’、L II ’、L III ' each independently is H or C 1～4 An alkyl group; in formula (II '), when m=2, there are 2 structural units represented by formula (III'), and only one L exists between 2 structural units I ’、L II ' or L III ' bonding to each other; in the formula (II '), when m is greater than 2, there are m structural units as shown in the formula (III'), the m structural units are sequentially bonded 1 terminal structural unit, (m-2) intermediate structural units and another 1 terminal structural unit, and only one L is present in each terminal structural unit I ’、L II ' or L III ' and L in the intermediate building block adjacent thereto I ’、L II ' or L III 'bonding, there are 2L's in each structural unit in the middle I ’、L II ' or L III ' L in the structural units adjacent thereto respectively I ’、L II ' or L III 'bonding'.
19. The antioxidant composition as set forth in claim 15, wherein the mass ratio between the ester compound and the amine compound is 1:0.1 to 5.
20. The antioxidant composition as set forth in claim 15, wherein the mass ratio between the ester compound and the amine compound is 1:0.2 to 3.
21. 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 is R 0 Selected from C of n-valent 1～30 Straight-chain or branched alkyl, C 2～30 Linear or branched heteroalkyl; each R' group is independently selected from C 1～10 Linear or branched alkylene; each R' group is independently selected from C 1～30 Linear or branched alkyl; each R' "group is independently selected from C 1～30 Linear or branched alkyl;
in the formula (Y), each R I The radicals are each independently selected from H, C 1～10 Linear or branched alkyl; each x is independently selected from integers between 0 and 4.
22. The antioxidant composition of claim 21, wherein,
in the formula (X), n is an integer between 1 and 5; r is R 0 Selected from C of n-valent 1～20 Straight-chain or branched alkyl, C 2～20 Linear or branched heteroalkyl; each R' group is independently selected from C 1～5 Linear or branched alkylene; each R' group is independently selected from C 1～20 Linear or branched alkyl; each R' "group is independently selected from C 1～20 Linear or branched alkyl;
in the formula (Y), each R I The radicals are each independently selected from H, C 1～5 Linear or branched alkyl; each x is independently selected from integers between 0 and 2.
23. The antioxidant composition of claim 21, wherein,
in the formula (X), n is an integer between 1 and 3; r is R 0 Selected from C of n-valent 1～10 Straight or branched chain alkaneRadical, C 2～10 Linear or branched heteroalkyl; each R' group is independently selected from C 1～3 Linear or branched alkylene; each R' group is independently C 1～10 Linear or branched alkyl; each R' "group is independently selected from C 1～10 Linear or branched alkyl;
in the formula (Y), each R I The radicals are each independently selected from H, C 1～3 Linear or branched alkyl; each x is independently selected from 0 or 1.
24. A process for preparing an antioxidant composition as claimed in any one of claims 1 to 20, comprising the step of mixing said ester compound, a multifunctional oiliness agent and optionally an amine compound.
25. A lubricating oil composition comprising a lubricating base oil, an antioxidant composition as claimed in any one of claims 1 to 20 or an antioxidant composition prepared according to the method of claim 21.
26. Lubricating oil composition according to claim 25 wherein the lubricating base oil is selected from synthetic hydrocarbons and/or synthetic esters.
27. The lubricating oil composition of claim 25, wherein the lubricating base oil is selected from the group consisting of C 1～10 Polyol of (C) and C 3～20 An ester formed by the reaction of fatty acids.
28. 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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| CN202011166612X | 2020-10-27 | ||
| CN202011166612 | 2020-10-27 |
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