CN114478289A - Ester compound, preparation method and application thereof, and antioxidant composition - Google Patents

Ester compound, preparation method and application thereof, and antioxidant composition Download PDF

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CN114478289A
CN114478289A CN202111208336.3A CN202111208336A CN114478289A CN 114478289 A CN114478289 A CN 114478289A CN 202111208336 A CN202111208336 A CN 202111208336A CN 114478289 A CN114478289 A CN 114478289A
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formula
group
straight
branched
preferably selected
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唐红金
梁宇翔
尹开吉
景一川
王玉睿涵
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/40—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino groups bound to carbon atoms of at least one six-membered aromatic ring and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/42—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino groups bound to carbon atoms of at least one six-membered aromatic ring and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton with carboxyl groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by saturated carbon chains
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/12—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Lubricants (AREA)

Abstract

The invention provides an ester compound and a preparation method and application thereof. The structure of the ester compound is shown as the formula (I):
Figure DDA0003307755900000011
in formula (I), at least one A group is selected from 1-valent groups shown in formula (II);

Description

Ester compound, preparation method and application thereof, and antioxidant composition
Technical Field
The invention relates to an ester compound, in particular to an ester 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. The lubricating oil is subjected to a series of chemical changes under the action of high-temperature oxygen induction and metal catalysis for a long time, so that a large amount of sediments such as oil sludge and the like are generated, and the normal working operation of the aero-engine 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 flying speed of airplanes, the use temperature of a main body of the turbojet engine lubricating oil is increased from 80 ℃ in the early stage to 220 ℃ at present, when the outlet temperature of the aero engine oil 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 problems of oil quality deterioration and deposition 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.
Disclosure of Invention
The invention provides an ester compound, a preparation method and application thereof, which comprise the following contents.
In a first aspect, the present invention provides an ester compound.
The structure of the ester compound is shown as the formula (I):
Figure RE-GDA0003504642600000021
in the formula (I), n is an integer between 1 and 10, preferably an integer between 1 and 5, and more preferably an integer between 1 and 3; r0Selected from the group consisting of n-valent C1～30Straight or branched alkyl, C2～30Straight-chain or branched heteroalkyl, preferably selected from the group consisting of n-valent C1～20Straight or branched alkyl, C2～20A linear or branched heteroalkyl radical, more preferably selected from the group consisting of n-valent C1～10Straight or branched alkyl, C2～10A linear or branched heteroalkyl group; each R' group is independently selected from C1～10Straight-chain or branched alkylene, preferably selected from C1～5Straight or branched alkylene, more preferably selected from C1～3A linear or branched alkylene group; each R' group is independently selected from C1～30Straight or branched alkyl, preferably selected from C1～20Straight or branched alkyl, more preferably selected from C1～10A linear or branched alkyl group; each R' "group is independently selected from C1～30Straight or branched alkyl, preferably selected from C1～20Straight or branched alkyl, more preferably selected from C1～10A linear or branched alkyl group; each A group is selected from the group represented by formula (II), H, C1～20A linear or branched alkyl group, preferably selected from the group represented by formula (II), H, C1～10A linear or branched alkyl group, more preferably selected from the group represented by the formula (II), H, C1～5A linear or branched alkyl group, and at least one A group in formula (I) is selected from the group consisting of 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 C1～6A linear or branched alkylene group;
Figure RE-GDA0003504642600000022
the formula (II) is that m structural units shown as the formula (III) mutually pass through R0' group bonding to form a 1-valent radical, wherein R is present0' the groups are each independently selected from C1～6Straight-chain or branched alkylene, preferably selected from C1～4Straight or branched alkylene, more preferably selected from C1～3A linear or branched alkylene group;
Figure RE-GDA0003504642600000031
in the formula (II), m is an integer between 1 and 10, preferably an integer between 1 and 5, and more preferably an integer between 1 and 3; each R isIEach independently selected from H, C1～10Straight or branched chain alkyl, preferably selected from H, C1～5Straight or branched chain alkyl, more preferably selected from H, C1～3A 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 isIIEach independently selected from H, C1～10Straight or branched chain alkyl, preferably selected from H, C1～5Straight or branched chain alkyl, more preferably selected from H, C1～3A linear or branched alkyl group; each y is independently selected from an integer between 0 and 4, preferably an integer between 0 and 2, more preferably 0 or 1; each R isIIIEach independently selected from H, C1～10Straight or branched chain alkyl, preferably selected from H, C1～5Straight or branched chain alkyl, more preferably selected from H, C1～3A linear or branched alkyl group; each z 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、LII、LIIIEach independently is H, C1～10Alkyl, and L in different structural unitsI、LIIOr LIIIBy R0' bonding end of group bonding, through R0' bonding end of group to formula (I), 1-valent group represented by formula (IV) (preferably H, C)1～4Alkyl, and L in different structural unitsI、 LIIOr LIIIBy R0' bonding end of group bonding, through R0' the bonding end of the group bonded to formula (I), a 1-valent group represented by formula (IV); in which each R present0' the groups are each independently selected from C1～6Straight-chain or branched alkylene, preferably selected from C1～4Straight or branched alkylene, more preferably selected from C1～3A linear or branched alkylene group;
in formula (II) onlyA LI、LIIOr LIIIThrough reaction with R0' A group is bonded to formula (I), R0One end of the group is bonded to the naphthalene ring in the structural unit in which it is located, and the other end is bonded to formula (I);
Figure RE-GDA0003504642600000032
in the 1-valent group represented by the formula (IV), represents and LI、LIIOr LIIIA bonded bonding end;
in the formula (IV), n is an integer between 1 and 10, preferably an integer between 1 and 5, and more preferably an integer between 1 and 3; r0Selected from the group consisting of n-valent C1～30Straight or branched alkyl, C2～30Straight-chain or branched heteroalkyl, preferably selected from the group consisting of n-valent C1～20Straight or branched alkyl, C2～20A linear or branched heteroalkyl radical, more preferably selected from the group consisting of n-valent C1～10Straight or branched alkyl, C2～10A linear or branched heteroalkyl group; each R is0' the groups are each independently selected from C1～6Straight-chain or branched alkylene, preferably selected from C1～4Straight or branched alkylene, more preferably selected from C1～3A linear or branched alkylene group; each R' group is independently selected from C1～10Straight-chain or branched alkylene, preferably selected from C1～5Straight or branched alkylene, more preferably selected from C1～3A linear or branched alkylene group; each R' group is independently selected from C1～30Straight or branched alkyl, preferably selected from C1～20Straight or branched alkyl, more preferably selected from C1～10A linear or branched alkyl group; each R' "group is independently selected from C1～30Straight or branched alkyl, preferably selected from C1～20Straight or branched alkyl, more preferably selected from C1～10Straight or branched chain alkyl.
According to the invention, preferably, in formula (II), L in the same structural unitI、LII、LIIIAre not mutually passed through R0' group bonding.
According to the invention, in formula (II), when m is 1, LI、LII、LIIIIs through R0' the bonding end of the group to which the formula (I) is bonded, the other two being each independently H, C1～4Alkyl or a 1-valent group of the formula (IV)0' one end of the group is bonded to the naphthalene ring in the structural unit in which it is located, and the other end is bonded to formula (I).
According to the invention, in formula (II), when m is 2, there are 2 structural units as shown in formula (III), L among the different structural unitsI、LII、LIII(when they are all L in different structural unitsI、LIIOr LIIIBy R0'bonding end of group bonding)' capable of mutually passing through R0' group bonding, optionally, there is only one L each between 2 building blocksI、LIIOr LIIIThrough 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 of the m structural unitsI、LII、LIII(when they are all L in different structural unitsI、 LIIOr LIIIBy 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 unitI、LIIOr LIIIAnd L in the intermediate structural unit adjacent theretoI、LIIOr LIIIBy R0' group bonding, 2L in each structural unit in the middleI、LIIOr LIIIL in the structural units adjacent to each otherI、LIIOr LIIIBy R0' radical bonding, i.e. only communication between each two different structural units linkedTo one R0' group bonding.
According to the invention, examples which may be mentioned of the radicals of the formula (II) include:
Figure RE-GDA0003504642600000051
wherein denotes by R0' the bonding end of the group bonded to formula (I).
According to the present invention, examples of the ester compound include:
Figure RE-GDA0003504642600000061
in the molecular structural formulas of the ester compounds P-1, P-2 and P-3, the group AN represents a group (II), and the specific molecular structure of the group (II) is shown as above. Taking (II-1) as an example, the molecular structural formula of the formed ester compound is shown as follows:
Figure RE-GDA0003504642600000062
Figure RE-GDA0003504642600000071
the ester 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-based 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 simultaneously can ensure that the ester lubricating oil keeps better low-temperature fluidity and low-temperature viscosity.
In a second aspect, the present invention provides an antioxidant composition.
The antioxidant composition comprises an ester compound as described in any one of the preceding aspects and a compound represented by formula (II');
Figure RE-GDA0003504642600000072
the formula (II ') is m structural units shown as the formula (III') mutually pass through R0' the compound formed by bonding the groups,
Figure RE-GDA0003504642600000073
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 isIEach independently selected from H, C1～10Straight or branched chain alkyl, preferably selected from H, C1～5Straight or branched chain alkyl, more preferably selected from H, C1～3A 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 isIIEach independently selected from H, C1～10Straight or branched chain alkyl, preferably selected from H, C1～5Straight or branched chain alkyl, more preferably selected from H, C1～3A linear or branched alkyl group; each y is independently selected from an integer between 0 and 4, preferably an integer between 0 and 2, more preferably 0 or 1; each R isIIIEach independently selected from H, C1～10Straight or branched chain alkyl, preferably selected from H, C1～5Straight or branched chain alkyl, more preferably selected from H, C1～3A linear or branched alkyl group; each z 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’、LII’、LIII' independently of each other is H, C1～4Alkyl, and L in different structural unitsI’、LII’、LIIIBy R0' bonding end of group linkage.
According to the invention, preferably, in formula (II'), L in said same structural unitI’、LII’、 LIII' do not pass through R each other0' group bonding.
According to the invention, in formula (II'), when m ═ 1, LI’、LII’、LIII' each independently is H or C1～4An alkyl group.
According to the invention, in formula (II '), when m is 2, there are 2 structural units as shown in formula (III'), L among the different structural unitsI’、LII’、LIII' (when they are all L in different structural unitsI’、 LII’、LIIIBy R0' when the bonding end of the group bonds) can be bonded to each other, preferably, only one L is present between each of the 2 structural unitsI’、LII' or LIII' mutually through R0' radical bonding, i.e. the bonding between 2 different structural units via only one R0' 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 in different structural unitsI’、LII’、LIII' (when they are all L in different structural unitsI’、LII’、LIIIBy 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 unitI’、LII' or LIII' and L in the intermediate structural unit adjacent theretoI’、LII' or LIIIBy R0' group bonding, 2L in each structural unit in the middleI’、LII' or LIII' L in the respective structural units adjacent theretoI’、LII' or LIII' byR0' radical bonding, i.e. by only one R between two different structural units which are connected0' group bonding.
According to the present invention, examples of the compounds represented by the formula (II') include:
Figure RE-GDA0003504642600000091
according to the present invention, preferably, the mass ratio between the ester compound of any one of the preceding aspects and the compound represented by formula (II') is 1: 0.1 to 5, more preferably 1: 0.3 to 3.
The antioxidant composition can well improve the oxidation stability, high-temperature corrosion resistance, low-temperature viscosity and low-temperature fluidity of lubricating oil (especially synthetic lubricating oil), is especially suitable for aviation synthetic lubricating oil (especially for four centistokes aviation lubricating oil), can effectively protect base oil, reduce the generation of oxidation products, reduce sediments and effectively relieve the problems of high-temperature oil deterioration and sedimentation of aviation engine oil.
In a third aspect, the present invention provides the use of the ester compound and the antioxidant composition of any one of the preceding aspects.
The ester compound in any aspect can be used as a high-temperature antioxidant, can obviously improve the high-temperature corrosion-resistant and oxidation-resistant stability of lubricating oil, particularly ester-based lubricating oil, and can obviously improve the solubility and stability of an additive in ester base oil, obviously improve the solubility and dispersibility of consumed additive residues in the base oil, obviously reduce the generation of deposits in a high-temperature environment of ester oil products, and simultaneously enable the ester lubricating oil to keep better low-temperature fluidity and low-temperature viscosity.
The antioxidant composition in any aspect can be used as a high-temperature antioxidant and a free radical scavenger, can remarkably improve the high-temperature oxidation resistance and the thermal degradation resistance of lubricating oil, particularly ester base oil, remarkably reduces the viscosity change rate of the lubricating oil before and after oxidation, the change of the total acid value, the generation of sediments and the quality change of metal test pieces before and after oxidation, prolongs the service time of the ester oil and reduces the oil change frequency.
In a fourth aspect, the present invention provides a lubricating oil composition.
The lubricating oil composition of the invention comprises lubricating base oil, the ester compound or the antioxidant composition of any one of the preceding aspects. The ester compound or the antioxidant composition in any aspect accounts for 0.5-10% of the total mass of the lubricating oil composition, and preferably accounts for 1.5-8% 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 oxidation stability and high temperature corrosion resistance. The optimized lubricating oil composition disclosed by the invention keeps excellent low-temperature viscosity and low-temperature fluidity at-51 ℃, and can ensure that an aeroengine can safely and stably work at high temperature and can be safely and quickly started at low temperature.
In a fifth aspect, the invention provides a preparation method of an ester compound.
The method for producing an ester compound of the present invention comprises a step of reacting a compound represented by the formula (X), a compound represented by the formula (Y), a compound represented by the formula (Z) and/or a polymer thereof;
Figure RE-GDA0003504642600000101
in the formula (X), n is an integer between 1 and 10, preferably an integer between 1 and 5, and more preferably an integer between 1 and 3; r0Selected from the group consisting of n-valent C1～30Straight or branched alkyl, C2～30Straight-chain or branched heteroalkyl, preferably selected from the group consisting of n-valent C1～20Straight or branched alkyl, C2～20A linear or branched heteroalkyl radical, more preferably selected from the group consisting of n-valent C1～10Straight or branched alkyl, C2～10A linear or branched heteroalkyl group; each R' group is independently selected from C1～10Straight or branched chainAlkylene, preferably selected from C1～5Straight or branched alkylene, more preferably selected from C1～3A linear or branched alkylene group; each R' group is independently selected from C1～30Straight or branched alkyl, preferably selected from C1～20Straight or branched alkyl, more preferably selected from C1～10A linear or branched alkyl group; each R' "group is independently selected from C1～30Straight or branched alkyl, preferably selected from C1～20Straight or branched alkyl, more preferably selected from C1～10A linear or branched alkyl group;
in the formula (Y), each RIEach independently selected from H, C1～10Straight or branched chain alkyl, preferably selected from H, C1～5Straight or branched chain alkyl, more preferably selected from H, C1～3A 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 isIIEach independently selected from H, C1～10Straight or branched chain alkyl, preferably selected from H, C1～5Straight or branched chain alkyl, more preferably selected from H, C1～3A linear or branched alkyl group; each y is independently selected from an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1; each R isIIIEach independently selected from H, C1～10Straight or branched chain alkyl, preferably selected from H, C1～5Straight or branched chain alkyl, more preferably selected from H, C1～3A linear or branched alkyl group; each z is independently selected from an integer between 0 and 4, preferably an integer between 0 and 2, more preferably 0 or 1;
in the formula (Z), R0Each "group is independently selected from H, C1～5Linear or branched alkylene, preferably selected from H, C1～3Straight or branched alkylene, more preferably selected from H, C1～2An alkylene group.
According to the preparation process of the present invention, the compound represented by the formula (X) is preferably selected from C1～18With C3～20Esterification products of fatty acids, said C1～18The polyhydric alcohol of (1) includes ethylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritolOne or more of pentaerythritol, C3～20The 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, palmitic acid, and oleic acid. The compound represented by the formula (X) is more preferably one or more of trimethylolpropane, pentaerythritol and dipentaerythritol and C3～20Further preferably an esterification product of a saturated fatty acid having a kinematic viscosity of (3.6-4.2) mm at 100 ℃2One or more of trimethylolpropane ester, pentaerythritol ester and dipentaerythritol ester per second.
According to the preparation method of the present invention, examples of the compound represented by the formula (X) include one or more of the following structural compounds:
Figure RE-GDA0003504642600000111
Figure RE-GDA0003504642600000121
according to the production method of the present invention, the mass ratio between the compound represented by the formula (X) and the compound represented by the formula (Y) is preferably 1: 0.1 to 5, more preferably 1: 0.3 to 3;
according to the production method of the present invention, the molar ratio between the compound represented by the formula (Y), the compound represented by the formula (Z), and/or the polymer thereof is preferably 1: 0.3 to 2.0, more preferably 1: 0.75 to 1.5; the temperature for the reaction of the compound represented by the formula (X), the compound represented by the formula (Y), the compound represented by the formula (Z) and/or the polymer thereof is preferably 60-120 ℃, and more preferably 70-110 ℃; the absolute pressure at which the compound represented by the formula (X), the compound represented by the formula (Y), the compound represented by the formula (Z) and/or the polymer thereof are reacted is not particularly limited, but is preferably 0.01MPa to 0.12MPa, more preferably 0.01MPa to 0.10 MPa.
According to the production method of the present invention, the time for the reaction of the compound represented by the formula (X), the compound represented by the formula (Y), the compound represented by the formula (Z) and/or the polymer thereof is preferably as long as the reaction proceeds smoothly, and is usually preferably 1 to 10 hours, more preferably 2 to 6 hours.
According to the production method of the present invention, preferably, in the compound represented by the formula (Y), the 4,6 positions of the naphthalene ring to which the amine group is attached are hydrogen atoms.
According to the preparation method of the present invention, preferably, the compound represented by the 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 isooctyl alcohol di-n-decanoate.
According to the preparation method of the present invention, preferably, the compound represented by formula (Y) may be selected from one or more of the following compounds: n- (p-tert-butylphenyl) -1-naphthylamine, N- (p-tert-octylphenyl) -1-naphthylamine, N- (p-phenylethylphenyl) -1-naphthylamine, N-phenyl-1-naphthylamine.
According to the preparation method of the present invention, preferably, the compound represented by formula (Z) may be selected from one or more of the following compounds: one or more of formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and paraformaldehyde.
According to the production method of the present invention, a catalyst may or may not be added, preferably a catalyst is added in the reaction of the compound represented by the formula (X), the compound represented by the formula (Y), the compound represented by the formula (Z) and/or the polymer thereof. The catalyst is preferably an acidic catalyst. 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 amount of the catalyst added is preferably 3 to 20% of the amount of the compound represented by the formula (X). The catalyst can be removed by vacuum distillation and alkali washing and water washing.
According to the preparation method of the present invention, the reaction of the compound represented by the formula (X), the compound represented by the formula (Y), the compound represented by the formula (Z) and/or the polymer thereof is preferably carried out under protection of an inert gas, preferably nitrogen.
According to the production method of the present invention, a solvent may or may not be added to the reaction of the compound represented by the formula (X), the compound represented by the formula (Y), the compound represented by the formula (Z) and/or the polymer thereof. The solvent is preferably C6～C20Alkanes, most preferably C6～C10Alkanes, such as n-decane, n-heptane, cyclohexane. The solvent may 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, the reaction product of the compound represented by the formula (X), the compound represented by the formula (Y), the compound represented by the formula (Z) and/or the polymer thereof may be a single ester compound, or a mixture of a plurality of ester compounds, or a mixture of one or more ester compounds and the compound represented by the formula (II') in the second aspect, or the compound represented by the formula (X).
According to the preparation method of the present invention, the reaction product of the compound represented by the formula (X), the compound represented by the formula (Y), the compound represented by the formula (Z) and/or the polymer thereof may be a single ester compound or a mixture of a plurality of ester compounds, which are all contemplated by the present invention, and the difference in the form does not affect the achievement of the effect of the present invention. Therefore, the reaction products are referred to collectively as the ester compounds 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 ester 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. Nevertheless, as the purification or separation method, for example, the reaction product may be purified and separated by a column chromatography method, a preparative chromatography method or the like.
According to the production method of the present invention, the reaction product of the compound represented by the formula (X), the compound represented by the formula (Y), the compound represented by the formula (Z) and/or the polymer thereof may be a mixture of one or more ester compounds and the compound represented by the formula (II') described in the second aspect, which is the antioxidant composition described in the second aspect of the present invention. In the reaction process, the compound shown in the formula (Y) can react with the compound shown in the formula (X) and also can perform 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'). The compound of formula (II ') thus includes the coupling product between unreacted compound of formula (Y) (i.e. the compound of formula (II ') wherein m is equal to 1) and the compound of formula (Y) itself (i.e. the compound of formula (II ') wherein m is greater than 1).
According to the production method of the present invention, when the reaction product of the compound represented by the formula (X), the compound represented by the formula (Y), the compound represented by the formula (Z) and/or the polymer thereof is a mixture of one or more ester compounds and the compound represented by the formula (II ') in the second aspect, the compound represented by the formula (II') in the second aspect may be isolated; it is also possible to use the compound represented by the formula (II') in the second aspect as the antioxidant composition of the present invention without isolating it.
According to the production method of the present invention, the reaction product of the compound represented by the formula (X), the compound represented by the formula (Y), the compound represented by the formula (Z) and/or the polymer thereof may be a mixture of one or more ester compounds with the compound represented by the formula (II') described in the second aspect, the compound represented by the formula (X). The reaction product may contain a compound represented by the formula (X), that is, an unreacted compound represented by the formula (X).
According to the production method of the present invention, when the reaction product of the compound represented by the formula (X), the compound represented by the formula (Y), the compound represented by the formula (Z) and/or the polymer thereof is a mixture of one or more ester compounds with the compound represented by the formula (II') described in the second aspect, the compound represented by the formula (X); it is also possible to use the compound of the formula (X) as an additional component without isolating the compound of the formula (X). Since the compound represented by the formula (X) is an ester compound, it can be used as a lubricating base oil, an antiwear agent, a friction modifier, and an additional component.
According to the production method of the present invention, there may be unreacted compound of formula (Z) and/or polymer thereof in the reaction product of compound of formula (X), compound of formula (Y), compound of formula (Z) and/or polymer thereof, and the unreacted compound of formula (Z) and/or polymer thereof may be removed by a conventional method such as distillation or extraction, and is not particularly limited.
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 operation include washing, recrystallization, and the like, and are not particularly limited.
According to the production method of the present invention, in the reaction of the compound represented by the formula (X), the compound represented by the formula (Y), the compound represented by the formula (Z) and/or a polymer thereof, the reaction product may be subjected to a purification operation to increase the purity of the reaction product. Examples of the purification method include washing, recrystallization, and the like, and are not particularly limited.
In a sixth aspect, the present invention further provides a method for improving oxidation and corrosion resistance of a lubricating oil composition, which comprises adding the ester antioxidant compound composition according to any one of the preceding aspects to a lubricating oil.
Drawings
FIG. 1 is a high performance liquid chromatography mass spectrum of a physical mixed system of reaction raw material N- (P-tert-octylphenyl) -1-naphthylamine (L06) and ester.
FIG. 2 is a high performance liquid chromatography mass spectrum of a synthesized product A1 (i.e., N- (P-tert-octylphenyl) -1-naphthylamine-ester formaldehyde polycondensate).
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).
In the context of the present specification, the heteroalkyl group refers to a group obtained by interrupting the carbon chain structure of an alkyl group with one or more (e.g., 1 to 5, 1 to 4, 1 to 3, 1 to 2, or 1) hetero groups selected from the group consisting of-Sx-, -O-, and-NR "", wherein 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, when a plurality of hetero groups are present, any two of the hetero groups are not directly bonded to each other. It is apparent that the hetero group is not at the end of the carbon chain of the hydrocarbyl group. For convenience of description, the number of carbon atoms of the alkyl group prior to the interruption is still used to refer to the number of carbon atoms of the heteroalkyl group after the interruption. For example, C4Straight chain alkyl (CH)3-CH2-CH2-CH2-) interrupted by a hetero-group-O-to obtain CH3-O-CH2-CH2-CH2-、 CH3-CH2-O-CH2-CH2-or CH3-CH2-CH2-O-CH2-equal C4The straight-chain heteroalkyl, interrupted by two hetero groups-S-, giving CH3-S-CH2-S-CH2-CH2-、CH3-CH2-S-CH2-S-CH2-or CH3-S-CH2-CH2-S-CH2-equal C4The straight-chain heteroalkyl, interrupted by three hetero groups-S-, giving CH3-S-CH2-S-CH2-S-CH2-equal C4A linear heteroalkyl group.
The percentages and ratios mentioned below are percentages by mass or ratios by mass unless otherwise stated.
The main raw materials used are as follows:
antioxidant L-06, p-tert-octylphenyl-1-naphthylamine, basf-Ciba Fine Ltd, chemically pure antioxidant PNA, n-phenyl-1-naphthylamine, institute of petrochemical technology, Xinpu, Chemicals pure
Antioxidant AO-150, chemical Limited of King chemical, Mixed alkyl Diphenylamine
Antirust agent 5-methyl benzotriazole, Shanghai chemical plant, chemical purity
VANLUBE9317, p-tert-octylphenyl-1-naphthylamine, a mixture of 4, 4' -diisooctyl diphenylamine and pentaerythritol ester, Van der Bilt, USA
VANLUBEV81, 4, 4' -diisooctyl diphenylamine, Van der Bill Ltd
VANLUBENA, a mixture of 4, 4' -diisooctyl diphenylamine and pentaerythritol ester, Van der Bill
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％
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 72.2g of 3.8mm kinematic viscosity at 100 ℃2Adding 7.2g of paraformaldehyde into the mixed system in/s trimethylolpropane saturated fatty acid ester;heating, stirring and dissolving the mixed reaction system in a nitrogen environment, maintaining the mixed system within the range of 80 ℃, and adding 18g of reaction catalyst 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, and 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 to obtain 142g of a reaction product A1; the reaction product A1 mainly contains the compounds of the structural formula P-1, the structural formula P-2 and the structural formula P-3, and also contains a small amount of the compounds of the structural formula II ' -1, the structural formula II ' -2 and the structural formula II ' -3, and a small amount of trimethylolpropane saturated fatty acid ester in the example. Respectively carrying out high performance liquid chromatography mass spectrometry on a physical mixed system of a reaction raw material N- (P-tert-octylphenyl) -1-naphthylamine (L06) and trimethylolpropane saturated fatty acid ester and a reaction product A1.
FIG. 1 is a high performance liquid chromatography mass spectrum of a physical mixed system of reaction raw material N- (P-tert-octylphenyl) -1-naphthylamine (L06) and ester.
FIG. 2 is a high performance liquid chromatography mass spectrum of a synthesized product A1 (i.e., N- (P-tert-octylphenyl) -1-naphthylamine-ester formaldehyde polycondensate).
As can be seen from comparative analysis, 330.9 can be seen in the mass-to-charge ratio peak of the reaction raw material N- (P-tert-octylphenyl) -1-naphthylamine in the mass spectrum of the high performance liquid chromatography of the physical mixed system of the reaction raw materials in FIG. 1; 523.8 and 551.3 are mass-to-charge ratio peaks of partial polyol ester in the polyol ester solvent oil; in the HPLC mass spectrum of reaction product A1 in FIG. 2, 895 and 916 are mass-to-charge ratio peaks of the ester-aromatic amine oligomer, and 675/1019/1225 is a aromatic amine bimolecular polycondensate, an aromatic amine trimolecular polycondensate, and a polycondensate of the aromatic amine bimolecular polycondensate and the ester, respectively. In addition, there are many other mass-to-charge ratio peaks of the polycondensate molecules in FIG. 2, which well illustrates the formaldehyde polycondensation reaction between the reaction raw materials to form the novel polycondensate composition of the present invention.
The mass to charge ratios for some of the synthesized aromatic amine formaldehyde polycondensate molecules are exemplified as follows:
(331.4+550.5+14-2+1)/1＝895.6；(331.4+572.2+14-2+1)/1＝916.2；
(331.4*2+14-2+1)/1＝675.8；(331.4*3+28-4+1)/1＝1019.2；
(331.4*2+523+28-4+1)/1＝1225.2……
example 2
Adding 99g of N- (p-tert-octylphenyl) -1-naphthylamine into 108g of mixed polyol saturated fatty acid ester (wherein, the weight of trimethylolpropane ester is 81g, and the weight of dipentaerythritol ester is 27g), and adding 12g of paraformaldehyde into the mixed system; heating, stirring and dissolving the mixed reaction system in a nitrogen environment, maintaining the mixed system at about 90 ℃, and adding 22g of reaction catalyst glacial acetic acid into the reaction system; carrying out reaction at 90 ℃ for 4h, carrying out reduced pressure distillation on the mixed reaction system at 110 ℃ and the vacuum degree of less than 500Pa for 60mins, and continuously carrying out full reduced pressure distillation at the temperature of not more than 160 ℃ and the vacuum degree of less than 500Pa for 30 mins-180 mins to obtain 210g of a reaction product A2; the reaction product A2 mainly contains compounds with similar structures of structural formula P-1, structural formula P-2 and structural formula P-3 (except that the ester group is the ester group of the mixed polyol saturated fatty acid ester used in the present example). While containing lesser amounts of the compounds of formula II ' -1, formula II ' -2, formula II ' -3, and minor amounts of the mixed polyol saturated fatty acid esters of this example.
Example 3
Adding 132g of N- (p-tert-octylphenyl) -1-naphthylamine into 156g of tetra centistokes polyol saturated fatty acid ester (wherein the mass ratio of the trimethylolpropane ester to the pentaerythritol ester to the fatty acid ester is 1:1), and adding 30g of paraformaldehyde into the mixed system; heating, stirring and dissolving the mixed reaction system in a nitrogen environment, maintaining the mixed system at about 100 ℃, and adding 30g of reaction catalyst 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, and 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 to obtain 153.5g of a reaction product A3; the reaction product A3 contained a compound mainly comprising a structure similar to the structure of formula P-1, formula P-2, and formula P-3 (except that the ester group was the ester group of the polyol saturated fatty acid ester used in this example). While containing lesser amounts of the compounds of formula II ' -1, formula II ' -2, formula II ' -3, and a minor amount of the polyol saturated fatty acid ester of this example.
Example 4
132g of N- (p-tert-octylphenyl) -1-naphthylamine is added to 156g of heptacentis dipentaerythritol saturated fatty acid ester, and 30g of paraformaldehyde is added to the mixed system; heating, stirring and dissolving the mixed reaction system in a nitrogen environment, maintaining the mixed system at about 100 ℃, and adding 30g of reaction catalyst 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, and 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 to obtain 153.5g of a reaction product A4; the reaction product A4 mainly contains the compounds of structural formula II ' -1, structural formula II ' -2 and structural formula II ' -3, and a small amount of dipentaerythritol saturated fatty acid ester in the example, and also contains compounds with structures similar to structural formula P-1, structural formula P-2 and structural formula P-3 (the difference is that the ester group in the compound is the ester group of dipentaerythritol saturated fatty acid ester). While containing lesser amounts of the compounds of formula II ' -1, formula II ' -2, formula II ' -3, and a minor amount of the dipentaerythritol saturated fatty acid ester of the present example.
Example 5
Adding 132g of N- (p-tert-octylphenyl) -1-naphthylamine into 156g of heptacentis trimethylolpropane oleate, and adding 30g of paraformaldehyde into the mixed system; heating, stirring and dissolving the mixed reaction system in a nitrogen environment, maintaining the mixed system at about 100 ℃, and adding 30g of reaction catalyst glacial acetic acid into the reaction system; the reaction is carried out for 3 hours at 100 ℃, the mixed reaction system is subjected to reduced pressure distillation for 60mins at the temperature of 110 ℃ and the vacuum degree of less than 500Pa, and is continuously subjected to sufficient reduced pressure distillation for 30 mins-180 mins at the temperature of no more than 160 ℃ and the vacuum degree of less than 500Pa, so as to obtain 150g of reaction product A5, wherein the reaction product A5 mainly comprises compounds of structural formula II ' -1, structural formula II ' -2 and structural formula II ' -3, a small amount of trimethylolpropane oleate used in the embodiment, and compounds with structures similar to structural formula P-1, structural formula P-2 and structural formula P-3 (the difference is that an ester group in the compound is an ester group of the trimethylolpropane oleate). While containing lesser amounts of the compounds of formula II ' -1, formula II ' -2, formula II ' -3, and a minor amount of trimethylolpropane oleate in this example.
Comparative antioxidant
Common antioxidants V81, L-06, phenyl-1-naphthylamine T531, thianthraquinone, Vanlube9317, Vanlube NA were used as comparative antioxidants.
Evaluation of high temperature Corrosion resistance and Oxidation stability
The reaction product of the present invention, the comparative antioxidant, and tricresyl phosphate (TCP) were added to the saturated fatty acid ester of tetrakiss polyol, respectively, and added and stirred at 80 ℃ to prepare examples 6 to 10 and comparative examples 1 to 6 of the lubricating oil composition, in which the mass percentage of tricresyl phosphate was 1%. The formulation ratios of the antioxidants in examples 6 to 10 and comparative examples 1 to 6 of the lubricating oil compositions are shown in Table 1.
TABLE 1 examples 6-10 and comparative examples 1-6 of lubricating oil compositions
Figure RE-GDA0003504642600000201
The kinematic viscosity at the low temperature of-51 ℃ of all the lubricating oil compositions corresponding to examples 6-10 and comparative examples 1-6 in the table 1 is measured, and the high-temperature corrosion and oxidation stability tests of all the lubricating oil compositions in the table 1 are carried out to evaluate the high-temperature oxidation resistance and the anti-deposition performance, the adopted evaluation method is an ASTM D4636 corrosion and oxidation stability test method specified by the evaluation of the high-temperature corrosion and oxidation stability of the four centistokes aviation lubricating oil in the MIL-PRF-7808L specification, the test conditions are as follows: 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 Gold such as copper, steel, silver, aluminum, titanium and the likeBelongs to the mass change of the unit area of the test piece. The invention uses the copper sheet quality change data to illustrate the test result.
The test results are shown in tables 2 and 3.
TABLE 2 evaluation test results of high temperature corrosion and oxidation stability
Figure RE-GDA0003504642600000211
Comparing the MIL-PRF-7808L specification index requirements with the results of the corrosion and oxidation stability evaluation data in tables 2 and 3, it can be seen that the 4 centi lubricating oil compositions of examples 6-9 to which the reaction product of the present invention was added have significant advantages over the lubricating oil compositions of comparative examples 1-4 in terms of sheet metal mass change, total acid value change, viscosity change rate, and deposit formation before and after oxidation, and their high temperature oxidation resistance is significantly superior to the monomeric arylamine antioxidant of comparative examples 1-4. The ester compound can better control the change of the total acid value of the oil product, the viscosity change rate and the sediment generation amount before and after the oxidation of the lubricating oil, and well meets the index requirements of MIL-PRF-7808L index corrosion and oxidation stability. The low-temperature viscosity at-51 ℃ of example 10 of the lubricating oil composition was larger than the standard value. The data of example 9 show that the ester compound synthesized by using the base oil of the saturated acid ester of the heptacentis dipentaerythritol also has good high-temperature oxidation resistance and deposit formation resistance, but the kinematic viscosity of the lubricating oil composition compounded with the base oil of the saturated organic acid ester of the 4 centis polyhydric alcohol at the temperature of-51 ℃ is more than or equal to 25000 (mm)2S) is not more than 20000 (mm) at-51 deg.C, and is also not suitable for MIL-PRF-7808L2S) requirements.
The kinematic viscosity at-51 ℃ of the compositions of examples 6 to 8 is not more than 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 to 6 correspond to 4 centistokes lubricating oil compositions having a kinematic viscosity at-51 ℃ of 21000 (mm) or more2(s) the kinematic viscosity at-51 ℃ is less than or equal to 20000 (mm) which does not meet the requirement of MIL-PRF-7808L2/s)。
TABLE 3 evaluation test results of high temperature corrosion and oxidation stability
Figure RE-GDA0003504642600000221
The lubricating oil composition blended by the ester compound of the invention has better high-temperature oxidation resistance and sediment formation resistance, and the high-temperature oxidation resistance of the lubricating oil composition is obviously superior to that of a monomer arylamine antioxidant. Meanwhile, the 4 centistokes lubricating oil composition has lower kinematic viscosity at low temperature and better low-temperature fluidity, and conforms to the MIL-PRF-7808L specification, and the kinematic viscosity at the temperature of-51 ℃ is less than or equal to 20000 (mm)2The index requirement of/s) is more beneficial to the low-temperature lubrication service of lubricating oil and the low-temperature quick start of the engine.

Claims (20)

1. The structure of the ester compound is shown as the formula (I):
Figure FDA0003307755880000011
in the formula (I), n is an integer between 1 and 10, preferably an integer between 1 and 5, and more preferably an integer between 1 and 3; r0Selected from the group consisting of n-valent C1～30Straight or branched alkyl, C2～30Straight-chain or branched heteroalkyl, preferably selected from the group consisting of n-valent C1～20Straight or branched alkyl, C2～20A linear or branched heteroalkyl radical, more preferably selected from the group consisting of n-valent C1～10Straight or branched alkyl, C2～10A linear or branched heteroalkyl group; each R' group is independently selected from C1～10Straight-chain or branched alkylene, preferably selected from C1～5Straight or branched alkylene, more preferably selected from C1～3A linear or branched alkylene group; each R' group is independently selected from C1～30Straight or branched alkyl, preferably selected from C1～20Straight or branched alkyl, more preferably selected from C1～10A linear or branched alkyl group; each R' "group is independently selected from C1～30Straight or branched alkyl, preferably selected from C1～20Straight or branched alkyl, more preferably selected from C1～10Straight or branched chainAn alkyl group; each A group is selected from the group represented by formula (II), H, C1～20A linear or branched alkyl group, preferably selected from the group represented by formula (II), H, C1～10A linear or branched alkyl group, more preferably selected from the group represented by the formula (II), H, C1～5A linear or branched alkyl group, and at least one A group in formula (I) is selected from the group consisting of 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 C1～6A linear or branched alkylene group;
Figure FDA0003307755880000012
the formula (II) is that m structural units shown as the formula (III) mutually pass through R0' group bonding to form a 1-valent radical, wherein R is present0' the groups are each independently selected from C1～6Straight-chain or branched alkylene, preferably selected from C1～4Straight or branched alkylene, more preferably selected from C1～3A linear or branched alkylene group;
Figure FDA0003307755880000013
in the formula (II), m is an integer between 1 and 10, preferably an integer between 1 and 5, and more preferably an integer between 1 and 3; each R isIEach independently selected from H, C1～10Straight or branched chain alkyl, preferably selected from H, C1～5Straight or branched chain alkyl, more preferably selected from H, C1～3A 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 isIIEach independently selected from H, C1～10Straight or branched chain alkyl, preferably selected from H, C1～5Straight or branched chain alkyl, more preferably selected from H, C1～3A linear or branched alkyl group; each y is independently selected from an integer between 0 and 4, preferably an integer between 0 and 2, more preferably 0 or 1; each R isIIIEach of the radicals beingIndependently selected from H, C1～10Straight or branched chain alkyl, preferably selected from H, C1～5Straight or branched chain alkyl, more preferably selected from H, C1～3A linear or branched alkyl group; each z 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、LII、LIIIEach independently is H, C1～10Alkyl, and L in different structural unitsI、LIIOr LIIIBy R0' bonding end of group bonding, through R0' bonding end of group to formula (I), 1-valent group represented by formula (IV) (preferably H, C)1～4Alkyl, and L in different structural unitsI、LIIOr LIIIBy R0' bonding end of group bonding, through R0' the bonding end of the group bonded to formula (I), a 1-valent group represented by formula (IV); in which each R present0' the groups are each independently selected from C1～6Straight-chain or branched alkylene, preferably selected from C1～4Straight or branched alkylene, more preferably selected from C1～3A linear or branched alkylene group;
in formula (II) there is only one LI、LIIOr LIIIThrough with R0' A group is bonded to formula (I), R0One end of the group is bonded to the naphthalene ring in the structural unit in which it is located, and the other end is bonded to formula (I);
Figure FDA0003307755880000021
in the 1-valent group represented by the formula (IV), represents and LI、LIIOr LIIIA bonded bonding end;
in the formula (IV), n is an integer between 1 and 10, preferably an integer between 1 and 5, and more preferably an integer between 1 and 3; r0Selected from the group consisting of n-valent C1～30Straight or branched alkyl, C2～30Straight-chain or branched heteroalkyl, preferably selected from the group consisting of n-valent C1～20Straight or branched alkyl, C2～20A linear or branched heteroalkyl radical, more preferably selected from the group consisting of n-valent C1～10Straight or branched alkyl, C2～10A linear or branched heteroalkyl group; each R is0' the groups are each independently selected from C1～6Straight-chain or branched alkylene, preferably selected from C1～4Straight or branched alkylene, more preferably selected from C1～3A linear or branched alkylene group; each R' group is independently selected from C1～10Straight or branched alkylene, preferably selected from C1～5Straight or branched alkylene, more preferably selected from C1～3A linear or branched alkylene group; each R' group is independently selected from C1～30Straight or branched alkyl, preferably selected from C1～20Straight or branched alkyl, more preferably selected from C1～10A linear or branched alkyl group; each R' "group is independently selected from C1～30Straight or branched alkyl, preferably selected from C1～20Straight or branched alkyl, more preferably selected from C1～10Straight or branched chain alkyl.
2. An ester compound according to claim 1,
in formula (II), when m is 1, LI、LII、LIIIIs through R0' the bonding end of the group to which the formula (I) is bonded, the other two being each independently H, C1～4Alkyl or a 1-valent group of the formula (IV)0One end of the group is bonded to the naphthalene ring in the structural unit in which it is located, and the other end is bonded to formula (I);
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 unitsI、LIIOr LIIIThrough each other by R0' group bonding;
in the formula (II), when m is more than 2, m structural units shown as the formula (III) 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 unitI、LIIOr LIIIAnd L in the intermediate structural unit adjacent theretoI、LIIOr LIIIBy R0' group bonding, 2L in each structural unit in the middleI、LIIOr LIIIL in the structural units adjacent to each otherI、LIIOr LIIIBy R0' group bonding.
3. An ester compound according to claim 1, wherein the group represented by the formula (II) comprises:
Figure FDA0003307755880000031
Figure FDA0003307755880000041
wherein represents by R0' the bonding end of the group to which formula (I) is bonded.
4. An ester compound according to claim 1, wherein the ester compound comprises:
Figure FDA0003307755880000042
wherein the group AN represents a group of formula (II).
5. An antioxidant composition comprising the ester compound of any one of claims 1 to 4 and a compound of formula (II');
Figure FDA0003307755880000051
the formula (II ') is that m structural units shown as the formula (III') mutually pass throughR0' the compound formed by bonding the groups,
Figure FDA0003307755880000052
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 isIEach independently selected from H, C1～10Straight or branched chain alkyl, preferably selected from H, C1～5Straight or branched chain alkyl, more preferably selected from H, C1～3A 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 isIIEach independently selected from H, C1～10Straight or branched chain alkyl, preferably selected from H, C1～5Straight or branched chain alkyl, more preferably selected from H, C1～3A linear or branched alkyl group; each y is independently selected from an integer between 0 and 4, preferably an integer between 0 and 2, more preferably 0 or 1; each R isIIIEach independently selected from H, C1～10Straight or branched chain alkyl, preferably selected from H, C1～5Straight or branched chain alkyl, more preferably selected from H, C1～3A linear or branched alkyl group; each z 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’、LII’、LIII' independently of each other is H, C1～4Alkyl, and L in different structural unitsI’、LII’、LIIIBy R0' bonding end of group linkage.
According to the invention, preferably, in formula (II'), L in said same structural unitI’、LII’、LIII' do not pass through R each other0' group bonding.
6. An antioxidant composition as claimed in claim 5,
in formula (II'), when m ═1 is, LI’、LII’、LIII' each independently is H or C1～4An alkyl group;
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 unitsI’、LII' or LIII' mutually through 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 unitI’、LII' or LIII' and L in the intermediate structural unit adjacent theretoI’、LII' or LIIIBy R0' group bonding, 2L in each structural unit in the middleI’、LII' or LIII' L in the respective structural units adjacent theretoI’、LII' or LIIIBy R0' group bonding.
7. Antioxidant composition according to claim 5, characterized in that the compound of formula (II') comprises:
Figure FDA0003307755880000061
8. antioxidant composition according to claim 5, characterized in that the mass ratio between the ester compound and the compound of formula (II') is 1: 0.1 to 5.
9. Use of the ester compound according to any one of claims 1 to 4 as a high-temperature antioxidant.
10. Use of the antioxidant composition of any of claims 5 to 8 as a high temperature antioxidant or a radical scavenger.
11. A lubricating oil composition comprising a lubricating base oil, the ester compound according to any one of claims 1 to 4 or the antioxidant composition according to any one of claims 5 to 8.
12. A method for producing an ester compound, comprising the step of reacting a compound represented by the formula (X), a compound represented by the formula (Y), a compound represented by the formula (Z) and/or a polymer thereof;
Figure FDA0003307755880000071
in the formula (X), n is an integer between 1 and 10, preferably an integer between 1 and 5, and more preferably an integer between 1 and 3; r0Selected from the group consisting of n-valent C1～30Straight or branched alkyl, C2～30Straight-chain or branched heteroalkyl, preferably selected from the group consisting of n-valent C1～20Straight or branched alkyl, C2～20A linear or branched heteroalkyl radical, more preferably selected from the group consisting of n-valent C1～10Straight or branched alkyl, C2～10A linear or branched heteroalkyl group; each R' group is independently selected from C1～10Straight-chain or branched alkylene, preferably selected from C1～5Straight or branched alkylene, more preferably selected from C1～3A linear or branched alkylene group; each R' group is independently selected from C1～30Straight or branched alkyl, preferably selected from C1～20Straight or branched alkyl, more preferably selected from C1～10A linear or branched alkyl group; each R' "group is independently selected from C1～30Straight or branched alkyl, preferably selected from C1～20Straight or branched alkyl, more preferably selected from C1～10A linear or branched alkyl group;
in the formula (Y), each RIEach independently selected from H, C1～10Straight or branched chain alkyl, preferably selected from H, C1～5Straight or branched chain alkyl, more preferably selected from H, C1～3A linear or branched alkyl group; each x is independentlyIndependently selected from integers between 0 and 4, preferably integers between 0 and 2, more preferably 0 or 1; each R isIIEach independently selected from H, C1～10Straight or branched chain alkyl, preferably selected from H, C1～5Straight or branched chain alkyl, more preferably selected from H, C1～3A linear or branched alkyl group; each y is independently selected from an integer between 0 and 4, preferably an integer between 0 and 2, more preferably 0 or 1; each R isIIIEach independently selected from H, C1～10Straight or branched chain alkyl, preferably selected from H, C1～5Straight or branched chain alkyl, more preferably selected from H, C1～3A linear or branched alkyl group; each z is independently selected from an integer between 0 and 4, preferably an integer between 0 and 2, more preferably 0 or 1;
in the formula (Z), R0Each "group is independently selected from H, C1～5Linear or branched alkylene, preferably selected from H, C1～3Straight or branched alkylene, more preferably selected from H, C1～2An alkylene group.
13. The method according to claim 12, wherein the compound of formula (X) is selected from C1～18With C3～20Esterification products of fatty acids, said C1～18The polyhydric alcohol of (A) comprises one or more of ethylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol, and the C is3～20The 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, palmitic acid, and oleic acid.
14. The method according to claim 12, wherein the compound of formula (X) is one or more of trimethylolpropane, pentaerythritol and dipentaerythritol and C3～20Preferably having a kinematic viscosity of (3.6-4.2) mm at 100 ℃ of an esterification product of a saturated fatty acid of (b)2One or more of trimethylolpropane ester, pentaerythritol ester and dipentaerythritol ester per second).
15. The method according to claim 12, wherein the mass ratio between the compound represented by the formula (X) and the compound represented by the formula (Y) is 1: 0.1 to 5; the molar ratio between the compound of formula (Y), the compound of formula (Z) and/or the polymers thereof is 1: 0.3 to 2.0; the temperature for the reaction of the compound represented by the formula (X), the compound represented by the formula (Y), the compound represented by the formula (Z) and/or the polymer thereof is 60-120 ℃.
16. The method according to claim 12, wherein in the compound represented by the formula (Y), hydrogen atoms are present at the 4-and 6-positions of the naphthalene ring to which the amine group is bonded.
17. The method according to claim 12, wherein the compound represented by formula (X) is selected from one or more of the following compounds: trimethylolpropane saturated acid ester, pentaerythritol saturated acid ester, dipentaerythritol saturated acid ester and isooctyl alcohol di-n-decanoate; and/or the presence of a gas in the gas,
the compound shown in the formula (Y) is selected from one or more of the following compounds: n- (p-tert-butylphenyl) -1-naphthylamine, N- (p-tert-octylphenyl) -1-naphthylamine, N- (p-phenylethylphenyl) -1-naphthylamine, N-phenyl-1-naphthylamine; and/or, the compound shown in the formula (Z) is selected from one or more of the following compounds: one or more of formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and paraformaldehyde.
18. The process according to claim 12, wherein a catalyst (preferably an acidic catalyst, more preferably glacial acetic acid, sulfuric acid, hydrochloric acid, phosphoric acid, SO) is added to the reaction of the compound of formula (X), the compound of formula (Y), the compound of formula (Z) and/or the polymer thereof3And P2O5Or an aqueous solution of one or more of these substances and mixtures thereof).
19. The method according to claim 12, wherein the reaction of the compound represented by the formula (X), the compound represented by the formula (Y), the compound represented by the formula (Z) and/or the polymer thereof is carried out under an inert gas atmosphere.
20. A method for improving the oxidation and corrosion resistance of a lubricating oil composition, which comprises adding the ester compound of any one of claims 1 to 4, the ester compound prepared by the method of any one of claims 12 to 19, or the antioxidant composition of any one of claims 5 to 8 into a lubricating base oil.
CN202111208336.3A 2020-10-26 2021-10-18 Ester compound, preparation method and application thereof, and antioxidant composition Pending CN114478289A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB767455A (en) * 1954-02-03 1957-02-06 Eastman Kodak Co Synthetic esters useful as lubricants
GB915161A (en) * 1958-02-07 1963-01-09 Heyden Newport Chemical Corp Improvements in or relating to synthetic lubricants
GB1469987A (en) * 1973-11-05 1977-04-14 Exxon Research Engineering Co Synthetic ester lubricant composition
US20040157753A1 (en) * 2000-07-26 2004-08-12 Toshinori Tazaki Lubricating oil for refrigerators and hydraulic fluid composition for refrigerator using the same
CN110382456A (en) * 2017-03-29 2019-10-25 慕尼黑克吕伯尔润滑器股份两合公司 New Ester compound, Its Preparation Method And Use
CN111057110A (en) * 2018-10-16 2020-04-24 中国石油化工股份有限公司 Phosphoramidate compound and preparation method and application thereof
CN111792993A (en) * 2019-04-08 2020-10-20 中国石油化工股份有限公司 Ester compound and preparation method and application thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB767455A (en) * 1954-02-03 1957-02-06 Eastman Kodak Co Synthetic esters useful as lubricants
GB915161A (en) * 1958-02-07 1963-01-09 Heyden Newport Chemical Corp Improvements in or relating to synthetic lubricants
GB1469987A (en) * 1973-11-05 1977-04-14 Exxon Research Engineering Co Synthetic ester lubricant composition
US20040157753A1 (en) * 2000-07-26 2004-08-12 Toshinori Tazaki Lubricating oil for refrigerators and hydraulic fluid composition for refrigerator using the same
CN110382456A (en) * 2017-03-29 2019-10-25 慕尼黑克吕伯尔润滑器股份两合公司 New Ester compound, Its Preparation Method And Use
CN111057110A (en) * 2018-10-16 2020-04-24 中国石油化工股份有限公司 Phosphoramidate compound and preparation method and application thereof
CN111792993A (en) * 2019-04-08 2020-10-20 中国石油化工股份有限公司 Ester compound and preparation method and application thereof

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