CN114478266A

CN114478266A - Amine compound, ester amine compound, preparation method and application thereof, and antioxidant composition

Info

Publication number: CN114478266A
Application number: CN202111207978.1A
Authority: CN
Inventors: 唐红金; 梁宇翔; 尹开吉; 阎欢; 韩天昊
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2020-10-26
Filing date: 2021-10-18
Publication date: 2022-05-13

Abstract

The invention provides an amine compound, an ester amine compound, a preparation method and application thereof, and an antioxidant composition. The structure of the amine compound is shown as the formula (I):

the formula (I) is m structural units shown as the formula (II) which mutually pass through R₀' an amine compound formed by bonding groups;

Description

Amine compound, ester amine compound, preparation method and application thereof, and antioxidant composition

Technical Field

The invention relates to an amine compound or an ester amine compound, in particular to an amine compound or an ester amine compound which can be used in aviation synthetic ester lubricating oil and has high-temperature oxidation and corrosion resistance.

Background

The high-temperature corrosion and oxidation stability of the aircraft engine lubricating oil are important manifestations of the high-temperature oxidation resistance of the aircraft engine oil. Under the induction of high-temperature oxygen and the catalytic action of metals, lubricating oil undergoes a series of chemical changes in a short period of time, so that engine oil generates a large amount of sediments such as oil sludge and the like, the sediments are attached to metal accessories and severely corrode equipment, the service life of the equipment is shortened, and the normal working operation of the aeroengine is seriously influenced. The improvement of the high-temperature corrosion and oxidation stability of the aircraft engine oil has important significance for improving the working efficiency and the service life of lubricating system equipment.

With the development of the aviation industry and the improvement of the flight speed of airplanes, the environmental characteristics of high temperature, high speed and high load of the aero-engine put forward higher and higher requirements on the performance of the aero-engine lubricating oil. When the outlet temperature of the aircraft engine is more than 200 ℃, the oxidation speed of the common engine lubricating oil is multiplied, so that the viscosity of the lubricating oil is increased, the total acid value is increased, the corrosivity is strong, and a large amount of sediments are generated. To effectively alleviate these problems, it is necessary to improve the high temperature corrosion and oxidation stability of aircraft engine lubricating oils.

The high-temperature corrosion and oxidation stability of the aircraft engine oil are closely related to the structures and high-temperature properties of the base oil and the antioxidant. Therefore, the high-temperature corrosion and oxidation stability of the aircraft engine oil is effectively improved, and a high-temperature oxidation and corrosion inhibitor with excellent chemical structure and high-temperature oxidation resistance needs 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 solved.

Four centistokes (4 mm) with a kinematic viscosity rating of four centistokes at 100 ℃ in the international famous aviation lubricant specification MIL-PRF-7808L specification²And/s) the aircraft engine 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 maneuvering, high-speed cruising and safe landing of the aircraft in alpine regions. The high-temperature antioxidant with excellent chemical structure and high-temperature antioxidant performance needs to be synthesized, so that the base oil can be effectively protected, the generation of oxidation products is reduced, the sediment is reduced, the deterioration and the sediment problems of the high-temperature oil of the aircraft engine oil are effectively relieved, and the high-temperature safe and stable operation of the aircraft engine is ensured. Meanwhile, the lubricating oil composition has lower kinematic viscosity and better low-temperature fluidity at low temperature, and the kinematic viscosity is less than or equal to 20000 (mm) at the temperature of-51 ℃ in accordance with the MIL-PRF-7808L specification²The index requirement of/s) is more favorable for the low-temperature lubrication service of lubricating oil and the safe and quick start and flight of the aviation aircraft in a low-temperature environment.

US 3,697,427 discloses the use of benzotriazole or certain alkylphenotriazoles as metal deactivators in synthetic lubricating oil compositions. US 3,790,481 discloses the use of methyl bis-benzotriazole, alkylbenzotriazole, naphthoxazole as copper passivators in polyol ester lubricating oil compositions.

US 5,076,946 discloses the use of a dimer derivative of methyl bis-alkyl benzotriazole as a metal deactivator in lubricating oils to improve the oxidation stability of the lubricating oils. US 6,743,759B2 discloses a lubricating oil antioxidant extreme pressure antiwear agent with good performance formed by compounding methylene bis-di-tert-butyl-dithiocarbamate with derivatives of alkylbenzene triazole and diphenylamine according to a certain proportion.

US 6,184,262B1 discloses that alkyl substituted methylene-dianilino-benzotriazole or alkyl benzotriazole and arylamine antioxidant complexing agent is used as a stabilizer in polyether, polyester and polyurethane foam, and has good effects of reducing stain and inhibiting coking, curing and foaming of polyol.

Disclosure of Invention

The invention provides an amine compound, an ester amine compound, a preparation method and an application thereof, and an antioxidant composition, comprising the following contents.

In a first aspect, the present invention provides an amine compound.

The structure of the amine compound is shown as the formula (I):

in the formula (I), m is an integer between 1 and 20, preferably an integer between 2 and 10, and more preferably an integer between 2 and 8; each R is_IEach independently selected from H, C_1～10Straight or branched chain alkyl, preferably selected from H, C_1～5Straight or branched chain alkyl, more preferably selected from H, C_1～3A linear or branched alkyl group; 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 is_IIEach independently selected from H, C_1～10Straight or branched chain alkyl, preferably selected from H, C_1～5Straight or branched chain alkyl, more preferably selected from H, C_1～3A linear or branched alkyl group; each y is independently selected from an integer between 0 and 2, preferably 0 or 1; each R is_IIIEach independently selected from H, C_1～10Straight or branched chain alkyl, preferably selected from H, C_1～5Straight or branched chain alkyl, more preferably selected from H, C_1～3A linear or branched alkyl group; each z is independently selected from an integer between 0 and 3, preferably an integer between 0 and 2, more preferably 0 or 1;

when m is>When 1, m structural units shown as formula (II) in formula (I) are mutually communicated with R₀' Amines formed by bonding of groups, R₀' the groups are each independently selected from C_1～6A linear or branched alkylene group;

each L in the formula (I)_I、L_II、L_IIIEach independently is H, C_1～4Alkyl, and R₀' bonding end of group bonding (for use with L in different building blocks_I、L_IIOr L_IIIBy reacting with R respectively₀' group bonding to bond different structural units to each other), a 1-valent group represented by the formula (III) (preferably H, C)_1～4Alkyl, and C_1～4The binding end of the linear or branched alkylene linkage, the 1-valent group represented by formula (III), more preferably H, C_1～4Alkyl, and C_1～2A binding end of an alkylene bond, a 1-valent group represented by formula (III);

when m is>1, at least one L is present per structural unit in the formula (I)_I、L_IIOr L_IIIIs a reaction with R₀' combination end of group bonding (for L in different structural units)_I、L_IIOr L_IIIBy reacting with R respectively₀' group bonding to bond different structural units to each other);

the formula (III) is a 1-valent group formed by bonding m' structural units shown as the formula (IV) with each other,

in the formula (III), m' is an integer of 1 to 10, preferably 1 to 5More preferably an integer of 1 to 3; each R is_IIIEach independently selected from H, C_1～10Straight or branched chain alkyl, preferably selected from H, C_1～5Straight or branched chain alkyl, more preferably selected from H, C_1～3A linear or branched alkyl group; each z is independently selected from an integer between 0 and 4, preferably an integer between 0 and 3, more preferably 0, 1 or 2;

each L in the formula (III)_I’、L_II’、L_III' independently of each other is H, C_1～4Alkyl, L in a different structural unit from that in formula (III)_I’、L_II’、L_III' bonded binding end, with L in formula (I)_I、L_IIOr L_IIIA bonded bonding end; in the formula (III), only one L is present_I’、L_II' or L_III' is a compound represented by the formula (I)_I、L_IIOr L_IIIA bonded bonding end;

in the formula (I) there are m' L_I、L_IIOr L_IIIIs a 1-valent group shown in the formula (III), and m' is an integer between 0 and 5 (preferably an integer between 1 and 3);

when m is 1, in formula (I), L_I、L_II、L_IIIOne of them is a 1-valent group of the formula (III), and the other two are each independently H, C_1～4An alkyl group.

According to the invention, preferably, in formula (I), L in the same structural unit_I、L_II、L_IIIAre not mutually passed through R₀' group bonding. According to the present invention, preferably, in formula (I), when m is 2, there are 2 structural units as shown in formula (II), L in different structural units_I、L_II、L_III(when they are all L in different structural units_I、L_IIOr L_IIIBy R₀' when the bonding end of the group bonding) can mutually pass through R₀' group bonding, optionally, there is only one L each between 2 building blocks_I、L_IIOr L_IIIThrough each other by R₀' radical bonding, i.e. only between 2 structural unitsThrough an R₀' group bonding.

According to the invention, preferably, in formula (I), when m is greater than 2, there are m structural units represented by formula (II), L of the m structural units_I、L_II、L_III(when they are all L in different structural units_I、L_IIOr L_IIIBy R₀'bonding end of group bonding)' capable of mutually passing through R₀' group bonding, further alternatively, m building blocks are sequentially R₀' group-bonded 1 terminal structural unit, (m-2) intermediate structural units and the other 1 terminal structural unit, only one L being present in each terminal structural unit_I、L_IIOr L_IIIAnd L in the intermediate structural unit adjacent thereto_I、L_IIOr L_IIIBy R₀' group bonding, 2L in each structural unit in the middle_I、L_IIOr L_IIIL in the structural units adjacent to each other_I、L_IIOr L_IIIBy R₀' radical bonding, i.e. by only one R between two different structural units which are connected₀' group bonding.

According to the invention, preferably, in formula (III), L in the same structural unit_I’、L_II’、L_III' are not bonded to each other.

According to the present invention, preferably, in formula (III), when m' is 1, L is_I’、L_II’、L_IIIOne of' is a group represented by the formula (I)_I、L_IIOr L_IIIThe bonding ends of the bonds, the other two being independently H, C_1～4An alkyl group.

According to the present invention, preferably, in formula (III), when m' is 2, there are 2 structural units as shown in formula (IV), L of the 2 structural units_I’、L_II’、L_III' (when they are both bonded binding ends) can be bonded to each other, optionally with only one L each between 2 building blocks_I’、L_II' or L_IIIInter-bonding, i.e. only one covalent bond is formed between 2 different building blocks.

According to the invention, preferably, in formula (III), when m ' is greater than 2, there are m ' structural units as shown in formula (IV), L of m ' structural units_I’、L_II’、L_III' (when they are both bonded binding ends) can be bonded to each other, and further alternatively, the m ' structural units are 1 end structural unit, (m ' -2) middle structural unit and the other 1 end structural unit which are bonded in sequence, 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 being 2L in each structural unit in the middle_I’、L_II' or L_III' L in the respective structural units adjacent thereto_I’、L_II' or L_III' bonding, i.e.the formation of only one covalent bond between each two different building blocks.

According to the present invention, examples of the amine compound include:

the amine compound can be used as a component of a high-temperature antioxidant or an efficient compound antioxidant of ester-based lubricating oil, and can remarkably improve the high-temperature corrosion-resistant and oxidation-resistant performance and stability of the ester-based lubricating oil.

In a second aspect, the present invention provides an esteramine compound.

The structure of the ester amine compound is shown as the formula (I'):

in the formula (I'), n is an integer of 1 to 10, preferably an integer of 1 to 5, more preferablySelecting an integer between 1 and 3; r₀Selected from the group consisting of n-valent C_1～30Straight or branched alkyl, C_2～30Straight-chain or branched heteroalkyl, preferably selected from the group consisting of n-valent C_1～20Straight or branched alkyl, C_2～20A linear or branched heteroalkyl radical, more preferably selected from the group consisting of n-valent C_1～10Straight or branched alkyl, C_2～10A linear or branched heteroalkyl group; each R' group is independently selected from C_1～10Straight-chain or branched alkylene, preferably selected from C_1～5Straight or branched alkylene, more preferably selected from C_1～3A linear or branched alkylene group; each R' group is independently selected from C_1～30Straight or branched alkyl, preferably selected from C_1～20Straight or branched alkyl, more preferably selected from C_1～10A linear or branched alkyl group; each R' "group is independently selected from C_1～30Straight or branched alkyl, preferably selected from C_1～20Straight or branched alkyl, more preferably selected from C_1～10A linear or branched alkyl group; each A group is selected from the group consisting of a 1-valent group represented by the formula (II'), H, C_1～20A linear or branched alkyl group, preferably selected from the group consisting of the 1-valent group represented by the formula (II'), H, C_1～10A linear or branched alkyl group, more preferably selected from the group consisting of the 1-valent group represented by the formula (II'), H, C_1～5A linear or branched alkyl group, and at least one A group present in formula (I ') is selected from the group consisting of the 1-valent group represented by formula (II '), wherein the 1-valent group represented by formula (II ') is represented by R₀'group is bonded to formula (I'), R₀' group is selected from C_1～6A linear or branched alkylene group;

in the formula (II'), m is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 8; each R is_IEach independently selected from H, C_1～10Straight or branched chain alkyl, preferably selected from H, C_1～5Straight or branched chain alkyl, more preferably selected from H, C_1～3A linear or branched alkyl group; each x is independently selected from an integer of 0 to 4, preferably 0 to up2, more preferably 0 or 1; each R is_IIEach independently selected from H, C_1～10Straight or branched chain alkyl, preferably selected from H, C_1～5Straight or branched chain alkyl, more preferably selected from H, C_1～3A linear or branched alkyl group; each y is independently selected from an integer between 0 and 2, preferably 0 or 1; each R is_IIIEach independently selected from H, C_1～10Straight or branched chain alkyl, preferably selected from H, C_1～5Straight or branched chain alkyl, more preferably selected from H, C_1～3A linear or branched alkyl group; each z is independently selected from an integer between 0 and 3, preferably an integer between 0 and 2, more preferably 0 or 1;

in the formula (II'), when m>1, formula (II ') is m structural units shown as formula (III') mutually pass through R₀' the 1-valent group formed by bonding the groups,

each L in the formula (II')_I”、L_II”、L_III"independently of one another is H, C_1～4Alkyl, and L in different structural units_I”、L_II"or L_IIIBy R₀' bonding end of group bonding (for use with L in different building blocks_I”、L_II"or L_IIIBy reacting respectively with R₀' radical bonding to bond different structural units to each other), by R₀' bonding end of group bonded to 1-valent group represented by formula (IV '), 1-valent group represented by formula (V '), via R₀'the binding end to which the group is bonded to formula (I'); r₀' the groups are each independently selected from C_1～6A linear or branched alkylene group; in the formula (II ') there are m' L_I”、L_II"or L_III"is a 1-valent group represented by the formula (V'), and m" is an integer of 0 to 5 (preferably an integer of 1 to 3); in the formula (II') only one L is present_I”、L_II"or L_IIIIs "through R₀'combination of a group bonded to formula (I')A terminal;

in formula (II'), when m is 1, L_I”、L_II”、L_IIIOne of "is through R₀' the bonding end of the group to which the formula (I) is bonded, the other two being each independently H, C_1～4Alkyl radical, by R₀' a bonding end to which a group is bonded to a 1-valent group represented by the formula (IV '), a 1-valent group represented by the formula (V ');

delta in the 1-valent group represented by the formula (IV ') represents a group represented by the formula (IV') with L_I”、L_II"or L_IIIBy R₀' bonding end of group bonding;

in formula (IV'), n is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3; r₀Selected from the group consisting of n-valent C_1～30Straight or branched alkyl, C_2～30Straight-chain or branched heteroalkyl, preferably selected from the group consisting of n-valent C_1～20Straight or branched alkyl, C_2～20A linear or branched heteroalkyl radical, more preferably selected from the group consisting of n-valent C_1～10Straight or branched alkyl, C_2～10A linear or branched heteroalkyl group; each R' group is independently selected from C_1～10Straight-chain or branched alkylene, preferably selected from C_1～5Straight or branched alkylene, more preferably selected from C_1～3A linear or branched alkylene group; each R' group is independently selected from C_1～30Straight or branched alkyl, preferably selected from C_1～20Straight or branched alkyl, more preferably selected from C_1～10A linear or branched alkyl group; each R' "group is independently selected from C_1～30Straight or branched alkyl, preferably selected from C_1～20Straight or branched alkyl, more preferably selected from C_1～10A linear or branched alkyl group;

the formula (V ') is a 1-valent group formed by bonding m ' structural units shown as the formula (VI '),

in formula (V '), 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_IIIEach independently selected from H, C_1～10Straight or branched chain alkyl, preferably selected from H, C_1～5Straight or branched chain alkyl, more preferably selected from H, C_1～3A linear or branched alkyl group; each z is independently selected from an integer between 0 and 4, preferably an integer between 0 and 3, more preferably 0, 1 or 2;

each L in the formula (V')_I’、L_II’、L_III' independently of each other is H, C_1～4Alkyl, L in a different structural unit from that in formula (V')_I’、L_II’、L_III'bonded binding end, with L in formula (II')_I”、L_II"or L_III"bonded binding end; in the formula (V'), only one L is present_I’、L_II' or L_III'is a group represented by the formula (II') and L_I”、L_II"or L_III"bonded binding end.

According to the invention, preferably, in formula (II'), L in the same structural unit_I”、L_II”、L_III"do not pass through R each other₀' group bonding.

According to the invention, in formula (II'), when m ═ 1, L_I”、L_II”、L_IIIOne of which is a 1-valent group of the formula (V'), and one is represented by the formula R₀'the bonding end of the group bonded to formula (I'), the other being H, C_1～4Alkyl radical, by R₀'the bonding end to which the group is bonded to the 1-valent group represented by formula (IV').

According to the invention, in formula (II '), when m is 2, there are 2 structural units as shown in formula (III'), of different structural unitsL_I”、L_II”、L_III"(when they are all L in different structural units_I”、L_II”、L_IIIBy R₀'bonding end of group bonding)' capable of mutually passing through R₀' group bonding, optionally, there is only one L each between 2 building blocks_I”、L_II”、L_III"through each other by R₀' radical bonding, i.e. by only one R between 2 structural units₀' group bonding.

According to the invention, in formula (II '), when m is greater than 2, there are m structural units represented by formula (III'), L among the m structural units_I”、L_II”、L_III"(when they are all L in different structural units_I”、L_II”、L_IIIBy R₀'bonding end of group bonding)' capable of mutually passing through R₀' group bonding, further alternatively, m structural units are sequentially joined by R₀' group-bonded 1 terminal structural unit, (m-2) intermediate structural units and the other 1 terminal structural unit, only one L being present in each terminal structural unit_I”、L_II”、L_IIIAnd L in the intermediate structural unit adjacent thereto_I”、L_II”、L_IIIBy R₀' group bonding, 2L in each structural unit in the middle_I”、L_II”、L_III"L in each of the structural units adjacent thereto_I”、L_II”、L_IIIBy R₀' radical bonding, i.e. by only one R between two different structural units which are connected₀' group bonding.

According to the invention, preferably, in formula (V'), L in said same structural unit_I’、L_II’、L_III' are not bonded to each other.

According to the invention, in formula (V '), when m' is 1, L_I’、L_II’、L_III'one of them is a group represented by the formula (II') and L_I”、L_II"or L_III"bonded ends, two others independently of each other H, C_1～4An alkyl group.

According to the present invention, in formula (V '), when m ' is 2, there are 2 structural units represented by formula (VI '), L among the 2 structural units_I’、L_II’、L_III' (when they are both bonded binding ends) can be bonded to each other, optionally with only one L each between 2 building blocks_I’、L_II' or L_III' bonding to each other, i.e.only one covalent bond is formed between 2 different building blocks.

According to the invention, in formula (V '), when m ' is greater than 2, there are m ' structural units represented by formula (VI '), L among the m ' structural units_I’、L_II’、L_III' (when they are both bonded binding ends) can be bonded to each other, and further alternatively, the m ' structural units are 1 end structural unit, (m ' -2) middle structural unit and the other 1 end structural unit which are bonded in sequence, 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 being 2L in each structural unit in the middle_I’、L_II' or L_III' L in the respective structural units adjacent thereto_I’、L_II' or L_III' bonding, i.e.the formation of only one covalent bond between each two different building blocks.

According to the invention, examples which may be mentioned of the radicals of the formula (II') include:

wherein represents by R₀'the bonding end of the group bonded to formula (I').

According to the present invention, the group represented by the formula (II ') may contain a group represented by the formula (V'), and examples thereof include:

wherein represents by R₀'the bonding end of the group bonded to formula (I').

According to the present invention, examples of the esteramine-based compound include:

in the molecular structural formula of the ester amine compounds P-1, P-2 and P-3, wherein the group DPNA represents a group represented by the formula (II '), such as the group (II' -1), (II '-2), (II' -3), (II '-4), (II' -5), (II '-6), (II' -7), (II '-V' -1), (II '-V' -2), (II '-V' -3), (II '-V' -4), (II '-V' -5), (II '-V' -6) and (II '-V' -7) shown above. Taking (II '-V' -1) group as an example, the molecular structural formula of the formed ester amine compound is shown as follows:

the ester amine compound has excellent oxidation resistance and corrosion resistance, can obviously improve the high-temperature corrosion resistance and oxidation resistance stability of lubricating oil, particularly ester lubricating oil, can obviously improve the solubility and stability of the arylamine antioxidant additive in the ester base oil, obviously improve the solubility and dispersibility of consumed additive residues in the base oil, reduce the generation of sediments of the ester oil in a high-temperature environment, and ensure that the ester lubricating oil keeps better low-temperature fluidity and low-temperature viscosity.

In a third aspect, the present invention provides an antioxidant composition.

The antioxidant composition of the present invention comprises the amine compound of the first aspect and the ester amine compound of the second aspect.

According to the present invention, preferably, the mass ratio between the amine-based compound of the first aspect and the ester-amine-based compound of the second aspect is 1: 1 to 0.1, more preferably 1: 0.8 to 0.2.

The antioxidant composition can be used as a high-temperature antioxidant of ester-based lubricating oil, can obviously improve the high-temperature corrosion-resistant and oxidation-resistant performance and stability of the ester-based lubricating oil, can obviously improve the solubility and stability of an additive in ester base oil, obviously improves the solubility and dispersibility of consumed additive residues in the base oil, obviously reduces the generation of deposits of the ester oil in a high-temperature environment, and enables the ester lubricating oil to keep better low-temperature fluidity and low-temperature viscosity.

In a fourth aspect, the present invention provides the use of the amine compound, the ester amine compound and the antioxidant composition described in any one of the preceding aspects.

The amine compound can be used as a component of an (ester-based lubricating oil) high-temperature antioxidant and an efficient compound antioxidant, can remarkably improve the high-temperature corrosion-resistant and oxidation-resistant performance and stability of the ester-based lubricating oil, can remarkably improve the solubility and stability of an additive in ester base oil, remarkably improves the solubility and dispersibility of consumed additive residues in the base oil, remarkably reduces the generation of deposits of the ester oil in a high-temperature environment, and enables the ester lubricating oil to keep better low-temperature fluidity and low-temperature viscosity.

The ester amine compound in the second aspect can be used as a component of an (ester-based lubricating oil) high-temperature antioxidant and an efficient composite antioxidant, can remarkably improve the high-temperature corrosion-resistant and antioxidant stability of the ester-based lubricating oil, can remarkably improve the solubility and stability of an additive in ester base oil, remarkably improves the solubility and dispersibility of consumed additive residues in the base oil, remarkably reduces the generation of deposits in a high-temperature environment of the ester oil, and can simultaneously keep better low-temperature fluidity and low-temperature viscosity of the ester lubricating oil.

The antioxidant composition of the third aspect can be used as a component of a high-temperature antioxidant and a high-efficiency composite antioxidant of (ester-based lubricating oil), can remarkably improve the high-temperature corrosion-resistant and oxidation-resistant performance and stability of the ester-based lubricating oil, can remarkably improve the solubility and stability of an additive in ester-based base oil, remarkably improves the solubility and dispersibility of consumed additive residues in the base oil, remarkably reduces the generation of sediments of the ester-based oil in a high-temperature environment, and enables the ester-based lubricating oil to maintain good low-temperature fluidity and low-temperature viscosity.

In a fourth aspect, the present invention provides a lubricating oil composition.

The lubricating oil composition comprises lubricating base oil, the amine compound, the ester amine compound or the antioxidant composition. The amine compound, ester amine compound or antioxidant composition of any one of the preceding aspects accounts for 1-12% of the total mass of the lubricating oil composition, preferably 3-8% of the total mass of the lubricating oil composition. The lubricating base oil is preferably a synthetic hydrocarbon and/or a synthetic ester. Other types of additives may also be added to the lubricating oil compositions of the present invention, such as viscosity index improvers, anti-wear agents, pour point depressants, rust inhibitors, and the like.

The lubricating oil composition has excellent high-temperature corrosion resistance, oxidation resistance, stability, sediment generation inhibiting performance and low-temperature performance.

In a fifth aspect, the invention provides a preparation method of an amine compound and/or an ester amine compound.

The preparation method of the amine compound and/or ester amine compound comprises the following steps:

step (1): reacting a compound of formula (α), a compound of formula (β) and/or a polymer thereof, and optionally a compound of formula (ε) to obtain an intermediate product;

in the formula (. alpha.), each R_IEach independently selected from H, C_1～10Straight or branched chain alkyl, preferably selected from H, C_1～5Straight or branched chain alkyl, more preferably selected from H, C_1～3A linear or branched alkyl group; 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 is_IIEach independently selected from H, C_1～10Straight or branched chain alkyl, preferably selected from H, C_1～5Straight or branched chain alkyl, more preferably selected from H, C_1～3A linear or branched alkyl group; each y is independently selected from an integer between 0 and 2, preferably 0 or 1; each R is_IIIEach independently selected from H, C_1～10Straight or branched chain alkyl, preferably selected from H, C_1～5Straight or branched chain alkyl, more preferably selected from H, C_1～3A linear or branched alkyl group; each z is independently selected from an integer between 0 and 3, preferably an integer between 0 and 2, more preferably 0 or 1;

in the formula (. beta.), R₀The "` group is selected from H, C_1～20A linear or branched alkyl group;

in the formula (epsilon), n is an integer of 1-10, preferably an integer of 1-5, and more preferably an integer of 1-3; r₀Selected from the group consisting of n-valent C_1～30Straight or branched alkyl, C_2～30Straight or branched heteroalkyl, preferably selected from the group consisting of n-valent C_1～20Straight or branched alkyl, C_2～20A linear or branched heteroalkyl radical, more preferably selected from the group consisting of n-valent C_1～10Straight or branched alkyl, C_2～10A linear or branched heteroalkyl group; each R' group is independently selected from C_1～10Straight-chain or branched alkylene, preferably selected from C_1～5Straight or branched alkylene, more preferably selected from C_1～3A linear or branched alkylene group; each R' group is independently selected from C_1～30Straight or branched alkyl, preferably selected from C_1～20Straight or branched alkyl, more preferably selected from C_1～10A linear or branched alkyl group; each R' "radicalEach independently selected from C_1～30Straight or branched alkyl, preferably selected from C_1～20Straight or branched alkyl, more preferably selected from C_1～10A linear or branched alkyl group;

step (2): reacting the intermediate product in the step (1) with a compound shown as a formula (gamma), and collecting a reaction product;

in the formula (. gamma.), each R_IIIEach independently selected from H, C_1～10Straight or branched chain alkyl, preferably selected from H, C_1～5Straight or branched chain alkyl, more preferably selected from H, C_1～3A linear or branched alkyl group; each z is independently selected from an integer of 0 to 3, preferably 0 to 2, and more preferably 0 or 1.

According to the production method of the present invention, in the step (1), the molar ratio between the compound represented by the formula (α), the compound represented by the formula (β), and/or the polymer thereof is preferably 1: 0.3 to 1.5, more preferably 1: 0.5 to 1.2; the mass ratio between the optional compound of formula (epsilon) and the sum of the masses of the compound of formula (alpha) and the compound of formula (gamma) is preferably 1: 0.3 to 3, more preferably 1: 0.5 to 1.5; the temperature for the reaction of the compound represented by the formula (alpha), the compound represented by the formula (beta) and/or the polymer thereof, and the optional compound represented by the formula (epsilon) is preferably 50-150 ℃, and more preferably 65-135 ℃; the absolute pressure at which the compound represented by the formula (. alpha.), the compound represented by the formula (. beta.), and/or the polymer thereof, and optionally the compound represented by the formula (. epsilon.) are reacted is not particularly limited, but is preferably 0.01 to 0.12MPa, more preferably 0.01 to 0.10 MPa.

According to the preparation method of the present invention, in the step (1), the compound represented by the formula (α), the compound represented by the formula (β) and/or the polymer thereof, and optionally the compound represented by the formula (e) are reacted for a time period which is preferably as long as the reaction proceeds smoothly, and is preferably 1 to 10 hours, more preferably 2 to 6 hours.

According to the production method of the present invention, in the step (1), the reaction by-product can be removed by a conventional method such as distillation or extraction, and is not particularly limited.

According to the preparation method of the present invention, in step (1), a catalyst, preferably an acidic catalyst, may be added. The acidic catalyst can be glacial acetic acid, sulfuric acid, hydrochloric acid, phosphoric acid, SO₃And P₂O₅Preferably sulfuric acid and/or glacial acetic acid or an aqueous solution thereof, most preferably glacial acetic acid or an acetic acid solution with a mass percentage of 60% to 100%. The catalyst can be removed by vacuum distillation, extraction or alkali washing and water washing.

According to the production method of the present invention, preferably, in the compound represented by the formula (α), a hydrogen atom is present in at least one of the ortho positions of the benzene ring to which the amine group is attached, and each of the carbon atoms para and para to the amine group on the naphthalene ring to which the amine group is attached contains a hydrogen atom.

According to the preparation method of the present invention, optionally, the compound represented by formula (α) may be selected from one or more of the following compounds: n-p-tert-butyl-phenyl-1-naphthylamine, N-p-tert-octyl-phenyl-1-naphthylamine, N-p-phenethyl-phenyl-1-naphthylamine, N-phenyl-1-naphthylamine.

According to the preparation method of the present invention, optionally, the compound represented by formula (β) may be selected from one or more of the following compounds: one or more of formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and paraformaldehyde.

According to the preparation process of the present invention, optionally, the optional compound of formula (. epsilon.) is preferably selected from C_1～10With C_3～20Esterification products of fatty acids, said C_1～10The polyhydric alcohol of (A) includes one or more of trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol, and C_3～20The fatty acid of (a) includes one or more of valeric acid, isovaleric acid, caproic acid, enanthic acid, caprylic acid, isooctanoic acid, 2-ethylhexanoic acid, pelargonic acid, 3,5, 5-trimethylhexanoic acid, capric acid, lauric acid. The compound represented by the formula (. epsilon.) is more preferably trihydroxyOne or more of methyl propane, pentaerythritol and dipentaerythritol and C_3～20Further preferably an esterification product of a saturated fatty acid having a kinematic viscosity of (3.65-4.2) mm at 100 ℃²One or more of trimethylolpropane ester, pentaerythritol ester and dipentaerythritol ester per second.

According to the production method of the present invention, examples of the optional compound represented by the formula (. epsilon.) include one or more compounds of the following structures: one or more of trimethylolpropane ester, pentaerythritol ester and dipentaerythritol ester.

According to the production method of the present invention, in the step (2), the mass ratio between the compound represented by the formula (γ) and the compound represented by the formula (α) in the step (1) is preferably 1: 0.2 to 3, more preferably 1: 0.3 to 2; the temperature of the reaction between the compound shown in the formula (gamma) and the intermediate product in the step (1) is preferably 80-200 ℃, and more preferably 120-180 ℃; the absolute pressure at which the compound represented by the formula (. gamma.) is reacted with the intermediate product in the step (1) is not particularly limited, but is preferably 0.02 to 0.12MPa, more preferably 0.01 to 0.10 MPa.

According to the preparation method of the invention, in the step (2), the time for the compound represented by the formula (gamma) to react with the intermediate product in the step (1) is preferably as long as the reaction proceeds smoothly, and is usually as long as the reaction proceeds, preferably 2 to 12 hours, and more preferably 3 to 8 hours.

According to the preparation method of the present invention, preferably, in the compound represented by the formula (γ), at least one tertiary carbon hydrogen atom is present in the ortho position of each benzene ring to which the amine group is attached.

According to the preparation method of the present invention, optionally, the compound represented by formula (γ) may be selected from one or more of the following compounds: diisooctyldiphenylamine, di-tert-butyldiphenylamine, p-isooctyl, p-tert-butyldiphenylamine, dinonyldiphenylamine and diphenylamine.

According to the production method of the present invention, the reaction of step (2) is preferably carried out in the presence of a peroxide. The peroxide is preferably an organic peroxide. The organic peroxide may be one or more of an alkyl peroxide, an acyl peroxide, a peroxyketal, and a peroxyorganic ester.

The alkyl peroxide has the structure: r¹-O-O-R²

The structure of acyl peroxides is: (R)¹)²-C-(O-O-R²)²

The structure of the peroxyketal is:

the peroxide organic ester has the structure:

wherein each R₁、R₂Each group is independently one or more of alkyl, aryl, alkyl substituted aryl or aryl substituted alkyl with the total number of carbon atoms between 2 and 10, preferably alkyl and/or phenyl with the total number of carbon atoms between 4 and 6, most preferably tert-butyl and/or phenyl.

According to the preparation method of the present invention, the organic peroxide is preferably one or more of tert-butyl-2-ethylperoxyhexanoate, peroxy ketal 2, 2-bis (tert-butylperoxy) butane, di-tert-butyl peroxide, dihexyl peroxide and diphenyl peroxide, and most preferably di-tert-butyl peroxide.

According to the production method of the present invention, the amount of the peroxide is preferably 0.6 to 1.2 times the molar amount of the compound represented by the formula (. gamma.) in the step (2).

According to the preparation method of the present invention, the reaction of step (2) is preferably carried out under the protection of an inert gas, preferably nitrogen.

According to the preparation method of the present invention, a solvent may or may not be added in the reactions of step (1) and step (2). The solvent is preferably C₆～C₂₀Alkanes, most preferably C₆～C₁₀Alkanes, such as n-decane, n-heptane, cyclohexane.

According to the preparation method of the invention, the prepared reaction product can be a single amine compound or a single ester amine compound, and can also be a mixture consisting of a plurality of amine compounds and/or a plurality of ester amine compounds. These reaction products are all intended for the present invention, and the difference in the form of their existence does not affect the achievement of the effects of the present invention. Therefore, the reaction products are collectively referred to as the amine compound or the ester amine compound without distinction in the context of the present specification. In view of this, according to the present invention, there is no absolute necessity to further purify the reaction product, or to further separate an amine compound or an ester amine compound of a specific structure from the reaction product. Of course, such purification or isolation is preferable for further improvement of the intended effect of the present invention, but is not essential to the present invention. As the purification or separation method, for example, the reaction product may be purified or separated by a column chromatography method, a preparative chromatography method or the like.

According to the preparation method of the invention, the reaction product can be purified to improve the purity of the reaction product. Examples of the purification method include washing, recrystallization, and the like, and are not particularly limited.

According to the production method of the present invention, the reaction product may be one or more of the amine compounds described in the first aspect.

According to the preparation method of the present invention, in the step (1), when the optional compound represented by the formula (epsilon) is not added, the amine compound of the present invention is included in the reaction product, and the unreacted compound represented by the formula (alpha) may be included in the reaction product, and the compound represented by the formula (alpha) may be separated; it is also possible to use the compound of the formula (. alpha.) as an additional component without isolating it. Since the compound represented by the formula (. alpha.) can be used as an antioxidant by itself, it can be used as an additional component.

According to the preparation method of the invention, in the step (1), when an optional compound shown as the formula (epsilon) is added to participate in the reaction, the reaction product comprises the ester amine compound and the amine compound, the ester amine compound and the amine compound can be separated from each other, or can be directly used as a mixture, and the mixture is the antioxidant composition of the third aspect of the invention. The reaction product may further comprise unreacted compound of formula (α) and/or unreacted compound of formula (γ), wherein the compound of formula (α) and the unreacted compound of formula (γ) may be separated; it is also possible to use the compound of the formula (. alpha.) and the unreacted compound of the formula (. gamma.) as additional components without separating them. Since the compounds of the formula (. alpha.) and the compounds of the formula (. gamma.) can be used as antioxidants themselves, they can be used as additional components. The reaction product may also contain unreacted compound of formula (epsilon), from which the compound of formula (epsilon) may be isolated; it is also possible to use the compounds of the formula (. epsilon.) as additional components without isolation. Since the compound represented by the formula (. epsilon.) can be used as a lubricating base oil or an antiwear agent, a friction modifier, by itself, it can be used as an additional component.

In a seventh aspect, the present invention also provides a method for improving oxidation and corrosion resistance of a lubricating oil composition, which comprises adding the amine compound, the ester amine compound or the antioxidant composition of any one of the preceding aspects to a lubricating base oil.

Drawings

FIG. 1 is a high performance liquid chromatography mass spectrum of reaction product B1.

Detailed Description

In the context of the present specification, the expression "number + valence + group" or the like refers to a group obtained by removing the number of hydrogen atoms represented by the number from the basic structure (such as a chain, a ring, a combination thereof, or the like) to which the group corresponds, and preferably refers to a group obtained by removing the number of hydrogen atoms represented by the number from a carbon atom (preferably a saturated carbon atom and/or a non-identical carbon atom) contained in the structure. For example, "3-valent straight or branched alkyl" refers to a group obtained by removing 3 hydrogen atoms from a straight or branched alkane (i.e., the base chain to which the straight or branched alkyl corresponds), and "2-valent straight or branched heteroalkyl" refers to a group obtained by removing 2 hydrogen atoms from a straight or branched heteroalkane (preferably from a carbon atom contained in the heteroalkane, or further, from a non-identical carbon atom).

The percentages and ratios mentioned below are percentages by mass or ratios by mass unless otherwise stated.

The raw materials used were as follows:

antioxidant L-06, N- (p-tert-octylphenyl) -1-naphthylamine, basf-Ciba Fine Ltd, chemical purity

Antioxidant PNA, n-phenyl-1-naphthylamine, institute of petrochemical institute, Xinpu corporation, chemical purity

Antioxidant AO-150, chemical Limited of King chemical, Mixed alkyl Diphenylamine

Antirust agent 5-methyl benzotriazole, Shanghai chemical plant, chemical purity

VANLUBEV81, 4, 4' -diisooctyl diphenylamine, Van der Bill Ltd

Saturated fatty acid ester of trimethylolpropane in a viscosity of 3.8mm at 100 deg.C²(s), Shaandong Rijie chemical Co., Ltd.,>98％

pentaerythritol ester, Zhejiang Quzhou chemical Co., Ltd., kinematic viscosity at 100 ℃ of 5.02mm²/s，>98％

Heptalis dipentaerythritol ester, shariki chemical limited of Shandong, kinematic viscosity at 100 ═ 7mm²/s，>98 percent; trimethylolpropane oleate, Shanto Ruijie chemical Co., Ltd., kinematic viscosity at 100 ℃ of 8.5mm²/s，>97％

Penricus trimethylolpropane ester, Chongqing Brand of China petrochemical great wall lubricating oil, great wall 5101 high temperature synthetic lubricating oil with kinematic viscosity of 5.05mm at 100 ℃²/s,>98％

Example 1

66.2g of N- (p-tert-octylphenyl) -1-naphthylamine are added to a kinematic viscosity of 3.8mm at 100 ℃²Adding 7.2g of paraformaldehyde into 150g of trimethylolpropane saturated fatty acid ester/s mixed system; under nitrogen environmentHeating and stirring the mixed reaction system, maintaining the mixed reaction system within the range of 80 ℃, and adding 18g of glacial acetic acid into the reaction system; carrying out reaction at 100 ℃ for 3h, carrying out reduced pressure distillation on the mixed reaction system at 110 ℃ and the vacuum degree of less than 500Pa for 60mins, continuously carrying out full reduced pressure distillation at the temperature of no more than 160 ℃ and the vacuum degree of less than 500Pa for 30 mins-180 mins, and cooling to 60 ℃ to obtain 215g of a reaction product A1;

adding 78.6g of 4,4 ' -diisooctyl-diphenylamine into 215g of reaction product A1, heating the reaction system, heating, stirring and dissolving the mixed system in the presence of nitrogen, maintaining the mixed system at 145 ℃, adding 125g of di-tert-butyl peroxide into the reaction system, reacting for 4 hours at the constant temperature of 145 ℃, distilling under reduced pressure at 145 ℃ and 0.02MPa for 30 minutes, increasing the vacuum degree to be less than or equal to 0.005MPa, gradually increasing the temperature to be more than 175 ℃, distilling under reduced pressure for more than 40 minutes, cooling the product in the nitrogen environment after the distillation under reduced pressure is finished, and finally obtaining 288g of reaction product B1, wherein the reaction product B1 mainly comprises (II ' -V ' -1) groups, (II ' -V ' -2) groups, (II ' -V ' -3) groups, (II ' -V ' -4) groups, The (II '-V' -5) group, the (II '-V' -6) group, the (II '-V' -7) group and the trimethylolpropane saturated fatty acid ester react to generate an ester amine compound with a main structure shown as a structural formula P-1, a structural formula P-2 and a structural formula P-3, and simultaneously comprises a small amount of the compound (II-V-1), the compound (II-V-2), the compound (II-V-3), the compound (II-V-4), the compound (II-V-5), the compound (II-V-6) and the compound (II-V-7), a small amount of the trimethylolpropane saturated fatty acid ester in the example, a small amount of the trimethylolpropane saturated fatty acid ester formed by the (II '-1) group, the (II' -2) group, the trimethylolpropane saturated fatty acid ester, The main structure generated by the reaction of the (II ' -3) group, the (II ' -4) group, the (II ' -5) group, the (II ' -6) group and the (II ' -7) group with trimethylolpropane saturated fatty acid ester is the ester amine compound shown as the structural formula P-1, the structural formula P-2 and the structural formula P-3.

A sample of reaction product B1 was taken for HPLC mass spectrometry and the spectrum obtained was shown in FIG. 1.

In FIG. 1, 332.5 can be seen as the mass-to-charge ratio peak of the reaction starting material N- (p-tert-octylphenyl) -1-naphthylamine; 523.8549.5 and 597.7 are mass-to-charge ratio peaks of part of polyol ester in the polyol ester solvent oil, which indicate that the product still has a small amount of unreacted raw material components which are still effective for the antioxidant composition and do not need to be separated; 662. 786.5 mass-to-charge ratio peaks of N- (p-tert-octylphenyl) -1-naphthylamine and aromatic amine dimeric oligomer of alkyl diphenylamine respectively, 675, 892.9 and 941.9 mass-to-charge ratio peaks of aromatic amine (i.e. N- (p-tert-octylphenyl) -1-naphthylamine, the same below) bimolecular polycondensate, aromatic amine-ester molecular polycondensate 1, aromatic amine-ester molecular polycondensate 2, 1068 and 1129 mass-to-charge ratio peaks of aromatic amine bimolecular polycondensate and alkyl diphenylamine oligomer, 1129 mass-to-charge ratio peaks of oligomer obtained by further reacting aromatic amine molecules and alkyl diphenylamine bimolecular oligomer, 1285 mass-to-charge ratio peaks of oligomer obtained by further reacting aromatic amine-ester molecular polycondensate 1 and alkyl diphenylamine molecule, 1333 mass-to-charge ratio peaks of oligomer obtained by further reacting aromatic amine-ester molecular polycondensate 2 and alkyl diphenylamine molecule, the 1459 mass to charge peak is the oligomer of the further reaction of the aromatic amine bimolecular polycondensate with the alkyl diphenylamine bimolecular oligomer.

In addition, there are many other polycondensate molecules and mass-to-charge ratio peaks of oligomer molecules in fig. 1, which well illustrates that condensation-oligomerization of formaldehyde occurs between the reaction raw materials to form the aromatic amine oligomer composition of the present invention.

The mass to charge ratios for some synthetic aromatic amine formaldehyde condensation polymers are exemplified as follows:

(331.4*2-2+1)/1＝662.0；(393.6*2-2+1)/1＝786.5；(331.4*2+14-2+1)/1＝675.8；(331.4+548.5+14-2+1)/1＝892.9；

(331.4+597.6+14-2+1)/1＝941.9；

(331.4*2+14+393.6-4+1)/1＝1068.4；(331.4+393.6*2+14-4+1)/1＝1129.6；

(331.4+548.5+14+393.6-4+1)/1＝1285；

(331.4+597.6+14+393.6-4+1)/1＝1333；

(331.4*2+14+393.6*2-6+1)/1＝1459.0……

example 2

100g of N- (p-tert-octylphenyl) -1-naphthylamine is added into 216g of mixed polyol saturated fatty acid ester (wherein, 162g of trimethylolpropane ester and 54g of dipentaerythritol ester) and 10g of paraformaldehyde is added into the mixed system; heating, stirring and dissolving the mixed reaction system in a nitrogen environment, maintaining the mixed system within the range of 80 ℃, and adding 24g of reaction catalyst glacial acetic acid into the reaction system; carrying out reaction at 110 ℃ for 3h, carrying out reduced pressure distillation on the mixed reaction system at 120 ℃ and under the vacuum degree of less than 500Pa for 60mins, continuously carrying out full reduced pressure distillation at the temperature of no more than 160 ℃ and under the vacuum degree of less than 500Pa for 120mins, and cooling to 60 ℃ to obtain 320g of reaction product A2;

adding 108g of 4,4 ' -diisooctyl-diphenylamine into 320g of reaction product A2, heating a reaction system, heating, stirring and dissolving the mixed system in the presence of nitrogen, maintaining the mixed system at 145 ℃, adding 165g of di-tert-butyl peroxide into the reaction system, reacting for 4 hours at the constant temperature of 145 ℃, distilling under reduced pressure at 145 ℃ and 0.02MPa for 30 minutes, raising the vacuum degree to be less than or equal to 0.005MPa, gradually raising the temperature to be more than 175 ℃, distilling under reduced pressure for more than 40 minutes, cooling and cooling the product in a nitrogen environment after the distillation under reduced pressure is finished, and finally obtaining 418g of reaction product B2, wherein the reaction product B2 mainly comprises (II ' -V ' -1) groups, (II ' -V ' -2) groups, (II ' -V ' -3) groups and (II ' -V ' -4) groups, The (II '-V' -5) group, the (II '-V' -6) group and the (II '-V' -7) group react with the mixed polyol saturated fatty acid ester to generate an ester amine compound, the main structure of which is similar to that of the compounds of the structural formula P-1, the structural formula P-2 and the structural formula P-3 (the difference is that the ester group is the ester group of the mixed polyol saturated fatty acid ester), and a small amount of the compound (II-V-1), the compound (II-V-2), the compound (II-V-3), the compound (II-V-4), the compound (II-V-5), the compound (II-V-6) and the compound (II-V-7), a small amount of the mixed polyol saturated fatty acid ester in the embodiment, the ester amine compound generated by the reaction of the (II ' -1) group, (II ' -2) group, (II ' -3) group, (II ' -4) group, (II ' -5) group, (II ' -6) group and (II ' -7) group with the mixed polyalcohol saturated fatty acid ester has a main structure similar to that of the compound with the structural formula P-1, the structural formula P-2 and the structural formula P-3 (the difference is that the ester group in the compound is the ester group of the mixed polyalcohol saturated fatty acid ester).

Example 3

120g of N- (p-tert-octylphenyl) -1-naphthylamine were added to 330g of dipentaerythritol ester (kinematic viscosity at 100 ℃ 7.5 mm)²In/s), adding 15g of paraformaldehyde into the mixed system; heating, stirring and dissolving the mixed reaction system in a nitrogen environment, maintaining the mixed system within the range of 90 ℃, and adding 30g of reaction catalyst glacial acetic acid into the reaction system; carrying out reaction at 110 ℃ for 4h, carrying out reduced pressure distillation on the mixed reaction system at 120 ℃ and under the vacuum degree of less than 500Pa for 60mins, continuously carrying out full reduced pressure distillation at the temperature of no more than 160 ℃ and under the vacuum degree of less than 500Pa for 120mins, and cooling to 60 ℃ to obtain 4580g of a reaction product A3;

adding 200g of 4,4 ' -diisooctyl-diphenylamine into 458g of reaction product A3, heating a reaction system, heating, stirring and dissolving the mixed system in the presence of nitrogen, maintaining the mixed system at 145 ℃, adding 165g of di-tert-butyl peroxide into the reaction system, reacting for 4 hours at the constant temperature of 145 ℃, distilling at the reduced pressure of 145 ℃ and 0.02MPa for 30 minutes, raising the vacuum degree to be less than or equal to 0.005MPa, gradually raising the temperature to be more than 175 ℃, distilling at the reduced pressure for more than 40 minutes, cooling the product after the reduced pressure distillation is finished in a nitrogen environment to obtain 648g of reaction product B3, wherein the reaction product B3 mainly comprises (II ' -V ' -1) groups, (II ' -V ' -2) groups, (II ' -V ' -3) groups and (II ' -V ' -4) groups, The main structure of the ester amine compound generated by the reaction of the (II '-V' -5) group, (II '-V' -6) group and (II '-V' -7) group with dipentaerythritol ester is similar to that of the compounds with the structural formula P-1, the structural formula P-2 and the structural formula P-3 (the difference is that the ester group is the ester group of dipentaerythritol ester), and simultaneously comprises a small amount of the compound (II-V-1), the compound (II-V-2), the compound (II-V-3), the compound (II-V-4), the compound (II-V-5), the compound (II-V-6) and the compound (II-V-7), a small amount of the dipentaerythritol ester in the example, relatively small amounts of the esteramine compounds formed by reacting the (II ' -1) group, (II ' -2) group, (II ' -3) group, (II ' -4) group, (II ' -5) group, (II ' -6) group, (II ' -7) group with dipentaerythritol ester have a main structure similar to that of the compounds of the formula P-1, P-2, P-3 (with the difference that the ester group is the ester group of dipentaerythritol ester)

Example 4

150g of N- (p-tert-octylphenyl) -1-naphthylamine were added to 360g of pentaerythritol saturated fatty acid ester (kinematic viscosity at 100 ℃ 5.02 mm)²In/s), adding 18g of paraformaldehyde into the mixed system; heating, stirring and dissolving the mixed reaction system in a nitrogen environment, maintaining the mixed system within the range of 80 ℃, and adding 38g of reaction catalyst glacial acetic acid into the reaction system; carrying out reaction at 110 ℃ for 3h, carrying out reduced pressure distillation on the mixed reaction system at 120 ℃ and under the vacuum degree of less than 500Pa for 60mins, continuously carrying out full reduced pressure distillation at the temperature of no more than 160 ℃ and under the vacuum degree of less than 500Pa for 120mins, and cooling to 60 ℃ to obtain 525g of a reaction product A4;

adding 200g of 4,4 ' -diisooctyl-diphenylamine into 525g of reaction product A4, heating a reaction system, heating, stirring and dissolving the mixed system in the presence of nitrogen, maintaining the mixed system at 140 ℃, adding 200g of di-tert-butyl peroxide into the reaction system, reacting for 8 hours at the constant temperature of 140 ℃, distilling under reduced pressure at 155 ℃ and 0.02MPa for 30 minutes, raising the vacuum degree to be less than or equal to 0.005MPa, gradually raising the temperature to be more than 175 ℃, distilling under reduced pressure for more than 60 minutes, cooling and cooling the product in a nitrogen environment after the distillation is finished, and finally obtaining 715g of reaction product B4, wherein the reaction product B4 mainly comprises (II ' -V ' -1) groups, (II ' -V ' -2) groups, (II ' -V ' -3) groups and (II ' -V ' -4) groups, The (II '-V' -5) group, the (II '-V' -6) group, and the (II '-V' -7) group react with pentaerythritol saturated fatty acid ester to form an ester amine compound, which has a main structure similar to that of the compounds of the structural formula P-1, P-2, and P-3 (except that the ester group is an ester group of pentaerythritol saturated fatty acid ester) and contains a small amount of the compound (II-V-1), the compound (II-V-2), the compound (II-V-3), the compound (II-V-4), the compound (II-V-5), the compound (II-V-6), the compound (II-V-7), and a small amount of the pentaerythritol saturated fatty acid ester in the present example, the ester amine compound generated by the reaction of the (II ' -1) group, (II ' -2) group, (II ' -3) group, (II ' -4) group, (II ' -5) group, (II ' -6) group and (II ' -7) group with pentaerythritol saturated fatty acid ester has a main structure similar to that of the compound with the structural formula P-1, the structural formula P-2 and the structural formula P-3 (the difference is that the ester group is the ester group of pentaerythritol saturated fatty acid ester).

Example 5

99.3g of N- (p-tert-octylphenyl) -1-naphthylamine were added to 270g of trimethylolpropane oleate (kinematic viscosity at 100 ℃ C. of 8.5 mm)²S), adding 12g of paraformaldehyde into the mixed system; heating, stirring and dissolving the mixed reaction system in a nitrogen environment, maintaining the mixed system within the range of 85 ℃, and adding 25g of reaction catalyst glacial acetic acid into the reaction system; carrying out reaction at 110 ℃ for 4h, carrying out reduced pressure distillation on the mixed reaction system at 120 ℃ and under the vacuum degree of less than 500Pa for 60mins, continuously carrying out full reduced pressure distillation at the temperature of no more than 160 ℃ and under the vacuum degree of less than 500Pa for 100mins, and cooling to 60 ℃ to obtain 378g of a reaction product A5;

adding 175g of 4,4 ' -diisooctyl-diphenylamine into 378g of reaction product A5, heating a reaction system, heating, stirring and dissolving the mixed system in the presence of nitrogen, maintaining the mixed system at 145 ℃, adding 180g of di-tert-butyl peroxide into the reaction system, reacting for 4 hours at the constant temperature of 145 ℃, distilling under reduced pressure at 145 ℃ and 0.02MPa for 30 minutes, raising the vacuum degree to be less than or equal to 0.005MPa, gradually raising the temperature to be more than 175 ℃, distilling under reduced pressure for more than 40 minutes, cooling and cooling the product in a nitrogen environment after the distillation under reduced pressure is finished, and finally obtaining 550g of reaction product B5, wherein the reaction product B5 mainly comprises (II ' -V ' -1) groups, (II ' -V ' -2) groups, (II ' -V ' -3) groups and (II ' -V ' -4) groups, The (II '-V' -5) group, the (II '-V' -6) group, and the (II '-V' -7) group are reacted with trimethylolpropane oleate to produce an ester amine compound, which has a main structure similar to that of the compounds of the structural formulae P-1, P-2, and P-3 (except that the ester group is an ester group of trimethylolpropane oleate) and contains a small amount of the compound (II-V-1), the compound (II-V-2), the compound (II-V-3), the compound (II-V-4), the compound (II-V-5), the compound (II-V-6), the compound (II-V-7), and a small amount of the trimethylolpropane oleate in this example, the main structure of the amine-ester compounds produced by reacting the (II ' -1) group, (II ' -2) group, (II ' -3) group, (II ' -4) group, (II ' -5) group, (II ' -6) group, (II ' -7) group with trimethylolpropane oleate is similar to the compounds of the structural formula P-1, P-2 and P-3 (except that the ester group is the ester group of trimethylolpropane oleate).

Comparative antioxidant

The comparative antioxidant used in the invention is a high-temperature antioxidant commonly used in the field of lubricating oil, and is respectively: v81, L06, T558, T534, T531.

Evaluation of oxidation stability and high temperature corrosion resistance

Adding the reaction products B1-B5 of the invention or the comparative antioxidants V81, L06, T558, T534 and T531 and tricresyl phosphate (TCP) into the mixture respectively, wherein the kinematic viscosity of the mixture is 3.8mm at 100 DEG C²Examples 6 to 10 and comparative examples 1 to 5, in which the lubricating oil compositions were prepared by heating and stirring/s trimethylolpropane saturated acid ester base oil, wherein the tricresyl phosphate was 1% by mass, and the formulation composition thereof is shown in Table 1.

TABLE 1 examples 6-10 and comparative examples 1-5 of lubricating oil compositions

The lubricating oil compositions in Table 1 were analyzed and evaluated by ASTM D4636 corrosion and oxidation stability testing method specified in MIL-PRF-7808L specification for 4 centi aviation lubricating oil high temperature corrosion and oxidation stability evaluation, respectively, under the following test conditions: the temperature is 220 ℃, the time is 40h, the air flow is 50mL/min, and the usage amount of the oil sample is 100 mL.

The evaluation indexes of the method are as follows: the change of total acid value (delta TAN/mgKOH. g) before and after oil sample oxidation^-1) (ii) a Viscosity change at 40 ℃ (Δ Viscosity%); 100mL test oil sample Deposit formation (Deposit/mg (100mL)^-1) (ii) a The mass per unit area of the metal test piece such as copper, steel, silver, aluminum, titanium and the like. The invention uses the copper sheet quality change data toThe experimental results were evaluated.

The results of the tests carried out on the above lubricating oil compositions are shown in tables 2 and 3.

TABLE 2 evaluation test results of high temperature corrosion and oxidation stability

TABLE 3 evaluation test results of high temperature corrosion and oxidation stability

Comparing the MIL-PRF-7808L specification index requirements with the results of corrosion and oxidation stability evaluation data in tables 2 and 3, it can be seen that the lubricating oil compositions of examples 6 to 10 of 4 centistokes grade to which the ester compound of the present invention is added have significant advantages over the lubricating oil compositions of comparative examples in terms of sheet metal mass change, total acid value change, viscosity change rate, and deposit formation before and after oxidation, and the high temperature oxidation resistance is significantly superior to that of comparative examples 1 to 4. The ester compound can better control the change of the total acid value of the oil product, the viscosity change rate and the generation amount of sediments before and after the oxidation of the lubricating oil, and well meets the index requirements of MIL-PRF-7808L on corrosion and oxidation stability. Example 10 also had better antioxidant properties, but its corrosion and oxidation stability did not meet the MIL-PRF-7808L requirements. The data of example 9 show that the antioxidant synthesized from the base oil of saturated acid ester of heptacentistokes dipentaerythritol also has good high-temperature oxidation resistance and deposit formation resistance, but the kinematic viscosity of the 4 centistokes lubricating oil composition prepared from the antioxidant at-51 ℃ is more than or equal to 25000 (mm)²S) not conforming to MIL-PRF-7808L, and has a kinematic viscosity of 20000 (mm) or less at-51 deg.C²S) requirement.

Kinematic viscosity at-51 ℃ of the lubricating oil compositions of examples 6 to 9. ltoreq.19000 (mm)²S) meets the requirement of MIL-PRF-7808L, namely the kinematic viscosity at-51 ℃ is less than or equal to-20000 (mm)²S); comparative examples 5-6 lubricating oil compositions of 4 centistokes rating having a kinematic viscosity at-51 deg.CDegree is more than or equal to 21000 (mm)²S) and kinematic viscosity at-51 ℃ not more than 20000 (mm) which does not meet the requirements of MIL-PRF-7808L²/s)；

The 4 centistokes lubricating oil composition prepared by blending the ester compound of the invention has better high-temperature oxidation resistance and sediment formation resistance, and is obviously superior to the monomer arylamine antioxidant. Meanwhile, the low-temperature-resistant high-temperature-resistant rubber has smaller kinematic viscosity at low temperature and better low-temperature fluidity, and the kinematic viscosity is less than or equal to 20000 (mm) at the temperature of-51 ℃ in accordance with the specification of MIL-PRF-7808L²The index requirement of/s) is more favorable for the low-temperature lubricating property of the lubricating oil and the low-temperature quick start of the engine.

Claims

1. The structure of the amine compound is shown as the formula (I):

when m is>When 1, the formula (I) is m structural units shown as the formula (II)The elements passing each other with R₀' Amines formed by bonding of groups, R₀' the groups are each independently selected from C_1～6A linear or branched alkylene group;

when m is>1, at least one L is present per structural unit in the formula (I)_I、L_IIOr L_IIIIs a reaction with R₀' bonding end of group bonding (for use with L in different building blocks_I、L_IIOr L_IIIBy reacting with R respectively₀' group bonding to bond different structural units to each other);

in the formula (III), m' is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3An integer of (d) m; each R is_IIIEach independently selected from H, C_1～10Straight or branched chain alkyl, preferably selected from H, C_1～5Straight or branched chain alkyl, more preferably selected from H, C_1～3A linear or branched alkyl group; each z is independently selected from an integer between 0 and 4, preferably an integer between 0 and 3, more preferably 0, 1 or 2; each L in the formula (III)_I’、L_II’、L_III' independently of each other is H, C_1～4Alkyl, L in a different structural unit from that in formula (III)_I’、L_II’、L_III' bonded binding end, with L in formula (I)_I、L_IIOr L_IIIA bonded bonding end; in the formula (III), only one L is present_I’、L_II' or L_III' is a compound represented by the formula (I)_I、L_IIOr L_IIIA bonded bonding end;

in the formula (I) there are m' L_I、L_IIOr L_IIIIs a 1-valent group represented by the formula (III), and m' is an integer between 0 and 5 (preferably an integer between 1 and 3);

2. The amine compound according to claim 1,

in formula (I), when m is 2, there are 2 structural units represented by formula (II), and only one L exists between each of the 2 structural units_I、L_IIOr L_IIIThrough each other by R₀' group bonding;

in the formula (I), when m is more than 2, m structural units shown as the formula (II) exist, and the m structural units are sequentially arranged through R₀' group-bonded 1 terminal structural unit, (m-2) intermediate structural units and the other 1 terminal structural unit, only one L being present in each terminal structural unit_I、L_IIOr L_IIIAnd L in the intermediate structural unit adjacent thereto_I、L_IIOr L_IIIBy R₀' group bonding, 2L in each structural unit in the middle_I、L_IIOr L_IIIL in the structural units adjacent to each other_I、L_IIOr L_IIIBy R₀' group bonding;

in formula (III), when m' is 1, L_I’、L_II’、L_IIIOne of' is a group represented by the formula (I)_I、L_IIOr L_IIIThe bonding ends of the bonds, the other two being independently H, C_1～4An alkyl group;

in formula (III), when m' is 2, there are 2 structural units represented by formula (IV), and only one L exists between each of the 2 structural units_I’、L_II' or L_IIIBonding with each other;

in the formula (III), when m 'is greater than 2, m' structural units represented by the formula (IV) exist, m 'structural units are 1 end structural unit, (m' -2) middle structural unit and the other 1 end structural unit which are sequentially bonded, and only one L exists 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 being 2L in each structural unit in the middle_I’、L_II' or L_III' L in the respective structural units adjacent thereto_I’、L_II' or L_III' bonding.

3. The amine compound of claim 1, wherein the amine compound comprises:

4. the structure of the ester amine compound is shown as the formula (I'):

in the formula (I'), n is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3; r₀Selected from the group consisting of n-valent C_1～30Straight or branched alkyl, C_2～30Straight-chain or branched heteroalkyl, preferably selected from the group consisting of n-valent C_1～20Straight or branched alkyl, C_2～20A linear or branched heteroalkyl radical, more preferably selected from the group consisting of n-valent C_1～10Straight or branched alkyl, C_2～10A linear or branched heteroalkyl group; each R' group is independently selected from C_1～10Straight-chain or branched alkylene, preferably selected from C_1～5Straight or branched alkylene, more preferably selected from C_1～3A linear or branched alkylene group; each R' group is independently selected from C_1～30Straight or branched alkyl, preferably selected from C_1～20Straight or branched alkyl, more preferably selected from C_1～10A linear or branched alkyl group; each R' "group is independently selected from C_1～30Straight or branched alkyl, preferably selected from C_1～20Straight or branched alkyl, more preferably selected from C_1～10A linear or branched alkyl group; each A group is selected from the group consisting of a 1-valent group represented by the formula (II'), H, C_1～20A linear or branched alkyl group, preferably selected from the group consisting of the 1-valent group represented by the formula (II'), H, C_1～10A linear or branched alkyl group, more preferably selected from the group consisting of the 1-valent group represented by the formula (II'), H, C_1～5A linear or branched alkyl group, and at least one A group present in formula (I ') is selected from the group consisting of the 1-valent group represented by formula (II '), wherein the 1-valent group represented by formula (II ') is represented by R₀'group is bonded to formula (I'), R₀' group is selected from C_1～6A linear or branched alkylene group;

in the formula (II'), m is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 8; each one ofR is_IEach independently selected from H, C_1～10Straight or branched chain alkyl, preferably selected from H, C_1～5Straight or branched chain alkyl, more preferably selected from H, C_1～3A linear or branched alkyl group; each x is independently selected from an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1; each R is_IIEach independently selected from H, C_1～10Straight or branched chain alkyl, preferably selected from H, C_1～5Straight or branched chain alkyl, more preferably selected from H, C_1～3A linear or branched alkyl group; each y is independently selected from an integer between 0 and 2, preferably 0 or 1; each R is_IIIEach independently selected from H, C_1～10Straight or branched chain alkyl, preferably selected from H, C_1～5Straight or branched chain alkyl, more preferably selected from H, C_1～3A linear or branched alkyl group; 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 in the formula (II')_I”、L_II”、L_III"independently of one another is H, C_1～4Alkyl, and L in different structural units_I”、L_II"or L_IIIBy R₀' bonding end of group bonding (for use with L in different building blocks_I”、L_II"or L_IIIBy reacting respectively with R₀' radical bonding to bond different structural units to each other), by R₀' bonding end of group bonded to 1-valent group represented by formula (IV '), 1-valent group represented by formula (V '), via R₀'the binding end to which the group is bonded to formula (I'); r₀' the groups are each independently selected from C_1～6A linear or branched alkylene group; in the formula (II ') there are m' L_I”、L_II"or L_III"is a 1-valent group represented by the formula (V'), and m" is an integer of 0 to 5 (preferably an integer of 1 to 3); in the formula (II') only one L is present_I”、L_II"or L_IIIIs "through R₀'the binding end to which the group is bonded to formula (I');

in formula (II'), when m is 1, L_I”、L_II”、L_IIIOne of "is through R₀' the bonding end of the group to which formula (I) is bonded, the other two being each independently H, C_1～4Alkyl radical, by R₀' a bonding end to which a group is bonded to a 1-valent group represented by the formula (IV '), a 1-valent group represented by the formula (V ');

in formula (IV'), n is an integer of 1 to 10, preferably 1 to 5, and more preferably 1 to 3; r₀Selected from the group consisting of n-valent C_1～30Straight or branched alkyl, C_2～30Straight-chain or branched heteroalkyl, preferably selected from the group consisting of n-valent C_1～20Straight or branched alkyl, C_2～20A linear or branched heteroalkyl radical, more preferably selected from the group consisting of n-valent C_1～10Straight or branched alkyl, C_2～10A linear or branched heteroalkyl group; each R' group is independently selected from C_1～10Straight-chain or branched alkylene, preferably selected from C_1～5Straight or branched alkylene, more preferably selected from C_1～3A linear or branched alkylene group; each R' group is independently selected from C_1～30Straight or branched alkyl, preferably selected from C_1～20Straight or branched alkyl, more preferably selected from C_1～10A linear or branched alkyl group; each R' "group is independently selected from C_1～30Straight or branched alkyl, preferably selected from C_1～20Straight or branched alkyl, more preferablyIs selected from C_1～10A linear or branched alkyl group;

in formula (V '), 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_IIIEach independently selected from H, C_1～10Straight or branched chain alkyl, preferably selected from H, C_1～5Straight or branched chain alkyl, more preferably selected from H, C_1～3A linear or branched alkyl group; each z is independently selected from an integer of 0 to 4, preferably 0 to 3, more preferably 0, 1 or 2;

5. The esteramine-based compound according to claim 4,

in formula (II'), when m is 1, L_I”、L_II”、L_IIIOne of which is a 1-valent group of the formula (V'), and one is represented by the formula R₀'the bonding end of the group bonded to formula (I'), the other being H, C_1～4Alkyl radical, throughR₀'a bonding end to which a group is bonded to the 1-valent group represented by formula (IV');

in formula (II '), when m is 2, there are 2 structural units represented by formula (III'), and only one L exists between each of the 2 structural units_I”、L_II”、L_III"through each other by R₀' group bonding;

in formula (II '), when m is greater than 2, m structural units represented by formula (III') are present, and m structural units are sequentially arranged through R₀' group-bonded 1 terminal structural unit, (m-2) intermediate structural units and the other 1 terminal structural unit, only one L being present in each terminal structural unit_I”、L_II”、L_IIIAnd L in the intermediate structural unit adjacent thereto_I”、L_II”、L_IIIBy R₀' group bonding, 2L in each structural unit in the middle_I”、L_II”、L_III"L in each of the structural units adjacent thereto_I”、L_II”、L_IIIBy R₀' group bonding;

in formula (V '), when m' is 1, L_I’、L_II’、L_III'one of them is a group represented by the formula (II') and L_I”、L_II"or L_III"bonded ends, two others independently of each other H, C_1～4An alkyl group;

in formula (V '), when m ' is 2, there are 2 structural units represented by formula (VI '), and only one L exists between each of the 2 structural units_I’、L_II' or L_III' bonding to each other;

in the formula (V '), when m' is greater than 2, m 'structural units represented by the formula (VI') are present, m 'structural units are 1 end structural unit, (m' -2) middle structural unit and the other 1 end structural unit which are bonded in sequence, 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 being 2L in each structural unit in the middle_I’、L_II' or L_III' L in the respective structural units adjacent thereto_I’、L_II' or L_III' bonding.

6. The esteramine compound according to claim 4, wherein the group represented by formula (II') comprises:

wherein represents by R₀'the bonding end of the group bonded to formula (I').

7. The esteramine-based compound according to claim 4, characterized in that the esteramine-based compound comprises:

wherein the group DPNA represents a group of formula (II').

8. An antioxidant composition comprising the amine compound according to any one of claims 1 to 3 and the esteramine compound according to any one of claims 4 to 7.

9. Use of the amine compound according to any one of claims 1 to 3 or the ester amine compound according to any one of claims 4 to 7 or the antioxidant composition according to claim 8 as a high temperature antioxidant.

10. A lubricating oil composition comprising a lubricating base oil, the amine compound according to any one of claims 1 to 3 or the ester amine compound according to any one of claims 4 to 7 or the antioxidant composition according to claim 8.

11. The preparation method of the amine compound and/or the ester amine compound comprises the following steps:

step (1): reacting a compound of formula (α), a compound of formula (β) and/or a polymer thereof, and optionally a compound of formula (e) to obtain an intermediate product;

in the formula (epsilon), n is an integer of 1-10, preferably an integer of 1-5, and more preferably an integer of 1-3; r₀Selected from the group consisting of n-valent C_1～30Straight or branched alkyl, C_2～30Straight-chain or branched heteroalkyl, preferably selected from the group consisting of n-valent C_1～20Straight or branched alkyl, C_2～20A linear or branched heteroalkyl radical, more preferably selected from the group consisting of n-valent C_1～10Straight or branched alkyl, C_2～10A linear or branched heteroalkyl group; each R' group is independently selected from C_1～10Straight-chain or branched alkylene, preferably selected from C_1～5Straight or branched alkylene, more preferably selected from C_1～3A linear or branched alkylene group; each R' group is independently selected from C_1～30Straight or branched alkyl, preferably selected from C_1～20Straight or branched alkyl, more preferably selected from C_1～10A linear or branched alkyl group; each R' "group is independently selected from C_1～30Straight or branched alkyl, preferably selected from C_1～20Straight or branched alkyl, more preferably selected from C_1～10A linear or branched alkyl group;

12. The production method according to claim 11, wherein in step (1), the molar ratio between the compound represented by the formula (α), the compound represented by the formula (β) and/or the polymer thereof is 1: 0.3 to 1.5; the mass ratio between the optional compound of formula (epsilon) and the sum of the masses of the compound of formula (alpha) and the compound of formula (gamma) is 1: 0.3 to 3; the temperature for the reaction of the compound represented by the formula (alpha), the compound represented by the formula (beta) and/or the polymer thereof and the optional compound represented by the formula (epsilon) is 50-150 ℃; in the step (2), the mass ratio of the compound represented by the formula (γ) to the compound represented by the formula (α) in the step (1) is 1: 0.2 to 3; the temperature for the reaction of the compound shown in the formula (gamma) and the intermediate product in the step (1) is 80-200 ℃.

13. The process according to claim 11, wherein a catalyst (preferably an acidic catalyst) is added in step (1).

14. The process according to claim 11, wherein in the compound represented by the formula (α), a hydrogen atom is present in at least one of the ortho positions of the benzene ring to which the amine group is bonded, and each of the carbon atoms para and para to the amine group on the naphthalene ring to which the amine group is bonded comprises a hydrogen atom; in the compound of formula (γ), there is at least one tertiary carbon hydrogen atom in the ortho position of each phenyl ring to which the amine group is attached.

15. The process according to claim 11, wherein the compound represented by the formula (α) is selected from one or more of the following compounds: n-p-tert-butyl-phenyl-1-naphthylamine, N-p-tert-octyl-phenyl-1-naphthylamine, N-p-phenethyl-phenyl-1-naphthylamine, N-phenyl-1-naphthylamine; the compound represented by the formula (β) is selected from one or more of the following compounds: one or more of formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and paraformaldehyde; the compound represented by the formula (gamma) is selected from one or more of the following compounds: diisooctyldiphenylamine, di-tert-butyldiphenylamine, p-isooctyl, p-tert-butyldiphenylamine, dinonyldiphenylamine and diphenylamine.

16. The process according to claim 11, wherein the optional compound of formula (ε) is selected from the group consisting of C_1～10With C_3～20Esterification products of fatty acids, said C_1～10The polyhydric alcohol of (A) includes one or more of trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol, and C_3～20The fatty acid includes valeric acid, isovaleric acid, caproic acid, enanthic acid, caprylic acid, isovaleric acidOne or more of caprylic acid, 2-ethylhexanoic acid, pelargonic acid, 3,5, 5-trimethylhexanoic acid, capric acid and lauric acid (the compound shown by the formula (epsilon) is preferably one or more of trimethylolpropane, pentaerythritol and dipentaerythritol and C_3～20More preferably a kinematic viscosity of (3.65-4.2) mm at 100 ℃ of the esterification product of a saturated fatty acid of (C)²One or more of trimethylolpropane ester, pentaerythritol ester and dipentaerythritol ester per second).

17. The process according to claim 11, wherein the reaction of step (2) is carried out in the presence of a peroxide (the peroxide is preferably an organic peroxide).

18. The process according to claim 11, wherein the reaction in the step (2) is carried out under an inert gas atmosphere.

19. A method for improving oxidation and corrosion resistance of a lubricating oil composition, which comprises adding the amine compound of any one of claims 1 to 3, the ester amine compound of any one of claims 4 to 7, the antioxidant composition of claim 8, or the amine compound and/or the ester amine compound prepared by the method of any one of claims 11 to 18 into lubricating base oil.