Phosphate ester salts and their preparation and use

Abstract

The present invention relates to a phosphate ester salt, which has a bicyclic organic base structure as a cation and a phosphate ester structure as an anion. The phosphate ester salt of the present invention can effectively improve the anti-wear performance and load-bearing capacity of a lubricating oil with a relatively small amount, and the lubricating oil exhibits excellent copper corrosion resistance. The present invention also provides a process for preparing the phosphate ester salt, a lubricating oil and a lubricating grease containing the phosphate ester salt, and uses of the phosphate ester salt.

Description

[Technical Field]

[0001] The present invention relates to phosphate ester salts, methods for preparing the same, complexes containing the same, and lubricating oils or greases containing the same. More particularly, the present invention relates to phosphate ester salts containing specific anionic groups and specific cationic groups, methods for preparing the same, blends thereof, and their use in lubricating oils or greases. [Background technology]

[0002] Phosphorus-nitrogen anti-wear additives, such as amine phosphate salts, have excellent anti-wear and load-bearing properties and are widely used in many fields, including high-end hydraulic oils, gear oils, and transmission system lubricants. In the paper "Tribofilm Formation, Friction, and Wear-Reducing Properties of Some Phosphorus-Containing Antiwear Additives" (Tribology Letters (2020) 68:75), it was observed that amine phosphate salts quickly form a tribofilm after friction occurs. Compared to other phosphorus-containing anti-wear additives, the tribofilm is relatively thin, exhibits a ridge-like morphology along the friction direction, and exhibits strong orientation. The tribofilm significantly reduces wear and the friction coefficient, effectively protecting the friction components.

[0003] Phosphate amine salts with simple structures are widely used in the field of lubricating oils as a known technology. Several new structures of phosphate ester amine salts have also been disclosed. CN Patent Application Publication No. 110573599 discloses an additive composition containing a mixture of orthophosphate monoester amine salt, orthophosphate diester amine salt, and pyrophosphate ester amine salt as the main anti-wear additive, and the amines used to form the salt include hydrocarbon-based primary amines, hydrocarbon-based secondary amines (including cyclic amines), hydrocarbon-based tertiary amines, ester-based amines, etc. CN Patent Application Publication No. 109715766 discloses a phosphate ester amine salt formed by an N-hydrocarbyl aromatic amine and an alkyl amide, and a pyrophosphate ester amine salt anti-wear additive.

[0004] Although the corrosion of copper metal caused by nitrogen-phosphorus anti-wear additives is relatively mild compared to other structural anti-wear additives, it cannot be ignored. CN Patent Application Publication No. 102260572 and CN Patent Application Publication No. 115010751 each disclose a nitrogen-phosphorus anti-wear additive with a benzotriazole structure, which utilizes molecular grafted benzotriazole groups to adsorb on the surface of friction pairs and achieve metal corrosion inhibition. This technical approach does not offer significant advantages over adding benzotriazole-based metal deactivators.

[0005] The development of new energy vehicles, high-end hydraulic equipment, and other industries has led to increased demands on the performance of phosphorus-nitrogen additives. To effectively protect friction pairs under medium to high loads, it is necessary to improve the maximum non-seizure load of phosphorus-nitrogen additives. Furthermore, copper corrosion caused by phosphorus-nitrogen additives at high temperatures remains significant. Therefore, to protect copper components in equipment that come into direct contact with lubricating oils, it is necessary to reduce copper corrosion caused by anti-wear additives. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Chinese Patent Application Publication No. 110573599 [Patent Document 2] Chinese Patent Application Publication No. 109715766 [Patent Document 3] Chinese Patent Application Publication No. 102260572 [Patent Document 4] Chinese Patent Application Publication No. 115010751 [Non-patent literature]

[0007] [Non-Patent Document 1] Tribofilm Formation, Friction and Wear-Reducing Properties of Some Phosphorus-Containing Antiwear Additives” (Tribology Letters (2020) 68:75) Summary of the Invention

[0008] Through thorough research, the inventors of the present invention have developed a novel phosphate ester salt. This phosphate ester salt has a bicyclic organic base structure as the cation and a phosphate ester structure as the anion. This phosphate ester salt exhibits excellent anti-wear properties at a relatively small amount and can effectively improve the load-bearing capacity of lubricating oils. This phosphate ester salt does not contain metal elements and minimizes ash formation. While exhibiting excellent anti-wear performance, it also reduces copper corrosion.

[0009] Specifically, the present invention provides the following solutions: The following formula (I): j(A) m+ ·k(P) n- (I) A phosphate ester salt having a structure represented by P is of formula (II): [ka] is a group represented by wherein two R1 are each independently selected from hydrogen and optionally substituted hydrocarbyl or heterohydrocarbyl, or R1 is absent and OR1 is O - group, wherein at least one of the two R1 is selected from optionally substituted hydrocarbyl or heterohydrocarbyl; A is a group represented by formula (III): [ka] is a group represented by During the ceremony, R3 is -(CH2) a -wherein a is an integer from 2 to 8; R4 is -(CH2) b - and b is an integer from 0 to 4; R5 is -(CH2) c where c is an integer from 1 to 5; X1 and X2 are each independently selected from CR6R6 and NR7; [ka] represents a single or double bond, and when X1 and / or X2 are NR7, they are protonated to form (NH) + capable of forming an R7 group, each R6 is present or absent, and each independently represents hydrogen or an optionally substituted C1-C6 straight or branched alkyl; R7 is present or absent and represents hydrogen or optionally substituted C1-C6 linear or branched alkyl; m is an integer of 1 to 3, n is an integer of 1 to 2, j is an integer of 1 to 2, k is an integer of 1 to 3, and k×n=j×m; When b is 0 and a double bond is formed between X1 and X2, the double bond can be rearranged so that a single bond is formed between X1 and X2 and a double bond is formed between X2 and the bridgehead N.

[0010] 1. A process for preparing a phosphate ester salt, comprising reacting an acidic phosphate ester having a structure represented by formula (VII) with an organic base: [ka] wherein two R8 are each independently selected from hydrogen and optionally substituted hydrocarbyl or heterohydrocarbyl, and two R8 are not simultaneously hydrogen; The organic base includes a bicyclic organic base having a structure represented by formula (VIII): [ka] In the formula, R3 is -(CH2) a -wherein a is an integer from 2 to 8; R4 is -(CH2) b - and b is an integer from 0 to 4; R5 is -(CH2) c where c is an integer from 1 to 5; X1 and X2 are each independently selected from CR6R6 and NR7; [ka] represents a single bond or a double bond, each R6 is present or absent, and each independently represents hydrogen or an optionally substituted C1-C6 straight or branched alkyl; R7 is present or absent and represents hydrogen or optionally substituted C1-C6 straight or branched alkyl.

[0011] A phosphate ester salt complex comprising at least one phosphate ester salt of the present invention or at least one phosphate ester salt prepared by the preparation process of the present invention.

[0012] A lubricating oil composition comprising a lubricating oil base oil and an additive, wherein the additive comprises the phosphate ester salt of the present invention, the phosphate ester salt prepared by the preparation process of the present invention, or the complex of the present invention.

[0013] A lubricating grease composition comprising a lubricating grease base oil and an additive, wherein the additive comprises a phosphate ester salt of the present invention, a phosphate ester salt prepared by the preparation process of the present invention, or a complex of the present invention.

[0014] Use of the phosphate ester salt of the present invention, the phosphate ester salt prepared by the preparation process of the present invention, or the complex of the present invention in lubricating oils and lubricating greases. The phosphate ester salt of the present invention, which has a bicyclic organic base cation structure and a phosphate ester anion structure, can exhibit significant anti-wear properties even in a relatively small amount and can effectively improve the load-bearing capacity of lubricating oils. In addition, the phosphate ester salt does not contain metal elements and is not prone to ash formation. Furthermore, the phosphate ester salt of the present invention exhibits excellent anti-wear performance while exhibiting low copper corrosion, making it a significant improvement over prior art phosphate ester amine salt compounds. [Brief explanation of the drawings]

[0015] [Figure 1] Infrared spectrum of the phosphate ester salt prepared in Example 3. [Figure 2] Infrared spectrum of the phosphate ester salt prepared in Example 5. DETAILED DESCRIPTION OF THE INVENTION

[0016] Although specific embodiments of the present invention will be described in detail below, it is pointed out that the scope of protection of the present invention is not limited by these specific embodiments, but is determined by the appended claims.

[0017] In the context of this specification, unless explicitly stated, any unmentioned items or matters can be directly applied to those known in the art without modification. Furthermore, any embodiment described in this specification can be freely combined with one or more other embodiments described in this specification, and the technical solutions or technical ideas obtained in this way shall be considered as part of the original disclosure or content of the present invention, and shall not be considered as new matters not disclosed or anticipated in this specification, unless a person skilled in the art considers the combination to be obviously unreasonable.

[0018] Unless expressly indicated, all percentages, parts, ratios, etc. referred to herein are by weight unless such weight basis is inconsistent with the common understanding of those skilled in the art.

[0019] Hereinafter, specific embodiments of the present invention will be described in detail, but it should be noted that the scope of protection of the present invention is not limited to these specific embodiments, but is determined by the appended claims.

[0020] In the context of the invention, unless otherwise specified, all physical properties of substances (such as boiling point) are measured at room temperature (25°C) and atmospheric pressure (101325 Pa).

[0021] In the present invention, when a spacer group may optionally be present between two groups, the absence of a spacer group indicates that the two groups are directly bonded. For example, the structural formula -CH2-(A) p Assuming -CH2-, A is a spacer group, and when p is 0, it means that the A group is absent, in which case two -CH2- groups are directly bonded to form a -CH2-CH2- structure.

[0022] As used herein, "hydrocarbyl" has the conventional meaning known in the art, including, but not limited to, straight or branched alkyl, straight or branched alkenyl, straight or branched alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, or combinations thereof.

[0023] In one embodiment of the present invention, the hydrocarbyl is C1-C 50 Linear or branched alkyl, or C1-C 20 Linear or branched alkyl, or C1-C 10 It may be a straight-chain or branched alkyl, or a C1 to C6 straight-chain or branched alkyl. The lower limit of the number of carbon atoms in each alkyl may be 2, 3, 4, or 5. In the present invention, specific examples of "alkyl" include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and its isomers, and hexyl and its isomers.

[0024] In one embodiment of the present invention, the hydrocarbyl is C2-C 50 Linear or branched alkenyl, or C2-C 20 Linear or branched alkenyl, or C2-C 10 It may be a straight-chain or branched alkenyl, or a C2-C6 straight-chain or branched alkenyl. The lower limit of the number of carbon atoms in each alkenyl may be 3, 4, or 5. In addition, the alkenyl has at least one double bond, and may have 2, 3, 4, or 5 double bonds, preferably one double bond, more preferably the double bond is located at the α-position. In the present invention, specific examples of "alkenyl" include vinyl, 1-propenyl, 2-propenyl, 1-butenyl and its isomers, 1-pentenyl and its isomers, and 1-hexenyl and its isomers.

[0025] In one embodiment of the present invention, the hydrocarbyl is C2-C 50 Straight-chain or branched alkynyl, or C2-C 20 Straight-chain or branched alkynyl, or C2-C10 It may be a straight-chain or branched alkynyl, or a C2-C6 straight-chain or branched alkynyl. The lower limit of the number of carbon atoms in each alkynyl may be 3, 4, or 5. In addition, the alkynyl has at least one carbon-carbon triple bond, and may have 2, 3, 4, or 5 carbon-carbon triple bonds, preferably one carbon-carbon triple bond, more preferably the carbon-carbon triple bond is located at the α-position. In the present invention, specific examples of "alkynyl" include ethynyl, 1-propynyl and its isomers, 1-butynyl and its isomers, 1-pentynyl and its isomers, and 1-hexynyl and its isomers.

[0026] In one embodiment of the present invention, the hydrocarbyl is C4-C 50 Cycloalkyl or C4-C 20 Cycloalkyl or C4-C 10 It may be cycloalkyl or C4-C8 cycloalkyl. Specific examples of "cycloalkyl" include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

[0027] In one embodiment of the present invention, the hydrocarbyl is C4-C 50 Cycloalkenyl, or C4-C 20 Cycloalkenyl, or C4-C 10 It may be a cycloalkenyl or a C4-C8 cycloalkenyl. The cycloalkenyl may have at least one double bond, or may have 2, 3, 4, or 5 double bonds, and preferably has one double bond. Specific examples of "cycloalkenyl" include groups formed by further adding one double bond to the above-mentioned cycloalkyl groups.

[0028] In one embodiment of the present invention, the hydrocarbyl is C-C 50 Cycloalkynyl, or C8-C 20 Cycloalkynyl, or C8-C 10It can be a cycloalkynyl. The cycloalkynyl has at least one carbon-carbon triple bond, and can also have 2, 3, 4, or 5 carbon-carbon triple bonds, and preferably has one carbon-carbon triple bond. Specific examples of "cycloalkynyl" include cyclooctynyl, cyclononynyl, and cyclodecynyl.

[0029] In one embodiment of the present invention, the hydrocarbyl is C-C 20 Aryl or C6-C 14 Aryl or C6-C 10 It can be aryl. Specific examples of "aryl" include phenyl, naphthyl, anthracenyl, and phenanthryl.

[0030] In one embodiment of the present invention, the substituent referred to in the phrase "optionally substituted" refers to at least one group selected from halogen, C1-C6 alkyl, C1-C6 haloalkyl, and phenyl. More specifically, it can be selected from fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and its isomers, hexyl and its isomers, halomethyl (e.g., trifluoromethyl), haloethyl (e.g., trifluoroethyl, pentafluoroethyl), halopropyl, haloisopropyl, halobutyl, haloisobutyl, halo-sec-butyl, halo-tert-butyl, halopentyl, halohexyl, phenyl, and halophenyl (e.g., chlorophenyl, dichlorophenyl, pentafluorophenyl). The upper limit on the number of substituents is the upper limit on the positions at which the substituted group can be substituted, and the number of substituents can be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. For example, the number of substituents may be 1 to 8, 1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 to 2. When multiple substituents are present, the substituents may be the same or different from each other.

[0031] In one embodiment of the present invention, [ka] represents a single or double bond, provided that this does not contradict the valence of the element.

[0032] In one embodiment of the present invention, examples of "linear or branched alkyl" include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, neopentyl, tert-pentyl, hexyl, sec-hexyl, heptyl, sec-heptyl, octyl, 2-ethylhexyl, 1-methylheptyl, 3,5,5-trimethylhexyl, n-nonyl, sec-nonyl, n-decyl, sec-decyl, n-undecyl, sec-undecyl, n-dodecyl, and sec-dodecyl. Examples of the alkyl esters include 2-octyl, n-tridecyl, isotridecyl, sec-tridecyl, n-tetradecyl, sec-tetradecyl, n-hexadecyl, sec-hexadecyl, n-octadecyl, eicosyl, didodecyl, ditetradecyl, triacontyl, 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldodecyl, 2-octyldodecyl, 2-decyltetradecyl, 2-dodecylhexadecyl, 2-hexadecyloctadecyl, and 2-tetradecyloctadecyl.

[0033] In one embodiment of the present invention, examples of the "straight-chain or branched alkenyl" include vinyl, allyl, propenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, oleyl, 9-octadecenyl, 9,12-octadecadienyl, and 12-hydroxy-9-octadecenyl.

[0034] In one embodiment of the present invention, examples of "aryl" include phenyl, naphthyl, anthracenyl, and phenanthryl.

[0035] In one embodiment of the present invention, examples of "cycloalkyl" include cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

[0036] [Phosphate ester salts] The present invention relates to a compound represented by the following formula (I): j(A) m+ ·k(P) n- (I) providing a phosphate ester salt having the structure P is a compound of formula (II) [ka] is a group represented by wherein two R1 are each independently selected from hydrogen and optionally substituted hydrocarbyl or heterohydrocarbyl, or R1 is absent and OR1 is O - group, wherein at least one of the two R1 is selected from optionally substituted hydrocarbyl or heterohydrocarbyl; A is a group represented by formula (III): [ka] is a group represented by During the ceremony, R3 is -(CH2) a -wherein a is an integer from 2 to 8; R4 is -(CH2) b - and b is an integer from 0 to 4; R5 is -(CH2) c where c is an integer from 1 to 5; X1 and X2 are each independently selected from CR6R6 and NR7; [ka] represents a single or double bond, and when X1 and / or X2 are NR7, they are protonated to form (NH) + can form an R7 group, each R6 is present or absent, and each independently represents hydrogen or an optionally substituted C1-C6 straight or branched alkyl; R7 is present or absent and represents hydrogen or optionally substituted C1-C6 linear or branched alkyl; m is an integer of 1 to 3, n is an integer of 1 to 2, j is an integer of 1 to 2, k is an integer of 1 to 3, and k×n=j×m; If b is 0 and a double bond is formed between X1 and X2, the double bond can be rearranged so that a single bond is formed between X1 and X2 and a double bond is formed between X2 and the bridgehead N.

[0037] The present invention provides a phosphate ester salt having a structure represented by formula (I): j(A) m+ ·k(P) n- (I) From this structure, A is a cationic group with a positive charge of m, and P is an anionic group with a negative charge of n, where k×n=j×m, and it can be clearly confirmed that the compound as a whole is electrically neutral.

[0038] More specifically, in the present invention, m can be an integer from 1 to 3, i.e., the A group can be a +1, +2, or +3 valent cationic group; n can be an integer from 1 to 2, i.e., the P group can be a -1 or -2 valent anionic group.

[0039] moreover, If m is 1 and n is 1, then j is 1 and k is 1; if m is 2 and n is 1, then j is 1 and k is 2; if m is 3 and n is 1, then j is 1 and k is 3; If m is 1 and n is 2, then j is 2 and k is 1; If m is 2 and n is 2, then j is 1 and k is 1; If m is 3 and n is 2, then j is 2 and k is 3.

[0040] It should be noted that j and k do not represent the absolute contents of anionic and cationic groups in the phosphate ester salt, but only the stoichiometric ratio of cationic groups to anionic groups in the phosphate ester salt.

[0041] In the present invention, P is a phosphate ester group represented by formula (II), which is a monovalent or divalent anionic group (ie, n is an integer of 1 or 2). [ka] wherein two R1 are each independently selected from hydrogen and optionally substituted hydrocarbyl or heterohydrocarbyl, or R1 is absent and OR1 is O - group, wherein at least one of the two R1 is selected from optionally substituted hydrocarbyl or heterohydrocarbyl.

[0042] In one embodiment of the present invention, in formula (II), at least one of the two R1 is selected from optionally substituted hydrocarbyl or heterohydrocarbyl.

[0043] In one embodiment of the present invention, in formula (II), one of the two R is absent and OR is O - It forms a group, namely the following group: [ka] In one embodiment of the present invention, in formula (II), R1 may be the same or different and each independently represents an optionally substituted C1 to C 18 Linear or branched alkyl, optionally substituted C2-C 18 Linear or branched alkenyl, optionally substituted C4-C 18 Cycloalkyl, optionally substituted C-C 18 Aryl, optionally substituted C3-C20 heterohydrocarbyl.

[0044] In one embodiment of the present invention, in formula (II), R1 may be the same or different and are each independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, n-hexyl, 2-ethylhexyl, n-octyl, 1-methylheptyl, 3,5,5-trimethylhexyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, 9-octadecenyl, 9,12-octadecadienyl, 12-hydroxy-9-octadecenyl, cyclohexyl, phenyl, benzyl, methylphenyl, or dimethylphenyl, all of which may be optionally substituted.

[0045] In the present invention, the heteroatom in the heterohydrocarbyl is at least one of O, N, and S, preferably O and / or S, and more preferably S.

[0046] In one embodiment of the present invention, in formula (II), R1 may be a heterohydrocarbyl, preferably a heterohydrocarbyl formed by replacing one or more -(CH2)- structural units in the specific groups listed above for R1 with -(NH)-, -O-, or -S-.

[0047] In one embodiment of the present invention, the phosphate ester group represented by formula (II) is derived from an acidic phosphate ester having a structure represented by formula (VII) below, i.e., a group formed by the loss of one or two protons from an acidic phosphate ester having a structure represented by formula (VII). [ka]

[0048] In one embodiment of the present invention, A is a group represented by formula (III). [ka]

[0049] In the present invention, the group represented by formula (III) is a +1-valent cationic group, a +2-valent cationic group, or a +3-valent cationic group.

[0050] In one embodiment of the present invention, R3 is -(CH2) a -, and a is an integer of 2 to 8, preferably an integer of 2 to 6, and more preferably an integer of 2 to 5.

[0051] In one embodiment of the present invention, R4 is -(CH2) b -, and b is an integer of 0 to 4; preferably b is an integer of 0 to 3, and more preferably b is an integer of 0 to 2.

[0052] In one embodiment of the present invention, R5 is -(CH2) c -, and c is an integer of 1 to 5, preferably c is an integer of 1 to 4, and more preferably c is an integer of 1 to 3.

[0053] In one embodiment of the present invention, X1 and X2 are each independently selected from CR6R6 and NR7.

[0054] In one embodiment of the present invention, X1 is NR7 and X2 is NR7.

[0055] In one embodiment of the present invention, X1 is CR6R6 and X2 is NR7.

[0056] In one embodiment of the present invention, X1 is NR7 and X2 is CR6R6.

[0057] In one embodiment of the present invention, X1 is CR6R6 and X2 is CR6R6.

[0058] In one embodiment of the present invention, [ka] represents a single bond or a double bond.

[0059] In one embodiment of the present invention, when one or both of X1 and X2 is NR7, it is protonated to (NH) + The R7 group can be formed.

[0060] In one embodiment of the present invention, X1 is NR7, [ka] When represents a single bond, it is protonated to (NH) + The R7 group can be formed.

[0061] In one embodiment of the present invention, X1 is NR7, [ka] represents a double bond, R7 is absent and is protonated to (NH) + It can form a group.

[0062] In one embodiment of the present invention, X2 is NR7; [ka] represents a single bond, in this case R7 is absent and is protonated to (NH) + It can form a group.

[0063] In one embodiment of the present invention, each R6 is present or absent and each independently represents hydrogen or an optionally substituted C1-C6 straight or branched alkyl.

[0064] In one embodiment of the present invention, R7 is present or absent and represents hydrogen or optionally substituted C1-C6 straight or branched alkyl.

[0065] In one embodiment of the present invention, X1 and X2 are not simultaneously NR7.

[0066] In one embodiment of the present invention, m is an integer of 1 or 2, n is an integer of 1 or 2, j is an integer of 1 or 2, k is an integer of 1 or 2, and k×n=j×m.

[0067] In one embodiment of the present invention, A is a group represented by formula (III-1) or formula (III-2). [ka] [ka]

[0068] In the group represented by formula (III-1), [ka] When represents a double bond, R6 is absent. In this case, the following groups can be formed: [ka]

[0069] In the group represented by formula (III-1), [ka] When represents a single bond, the following groups can be formed: [ka]

[0070] The group represented by formula (III-2) can be selected from the following groups: [ka]

[0071] In one embodiment of the present invention, b is 0.

[0072] In one embodiment of the present invention, b is 0; [ka] represents a single bond, and A is a group represented by formula (IV). [ka]

[0073] In one embodiment of the present invention, when A is a group of formula (IV), X1 and X2 are preferably not simultaneously NR7.

[0074] In one embodiment of the present invention, when A is a group of formula (IV), X2 is preferably not NR7.

[0075] In one embodiment of the present invention, when A is a group represented by formula (IV), X2 is CR6, and X1 is NR7, a group represented by the following formula (IV-1) is formed. [ka]

[0076] In one embodiment of the present invention, when b is 0 and a double bond is formed between X1 and X2, the double bond is such that a single bond is formed between X1 and X2, a double bond is formed between X2 and the bridgehead N, and simultaneously the previous bridgehead (NH) + The H above can be rearranged to move to X1.

[0077] In one embodiment of the present invention, b is 0; [ka] represents a double bond, and A is a group represented by formula (V) or formula (VI). [ka] [ka] In the formula, the group represented by formula (V) and the group represented by formula (VI) are tautomeric structures. [ka]

[0078] In one embodiment of the present invention, when b is 0 and X1 is NR7, a double bond is formed between X1 and X2, in which case R7 is absent, the bond between X1 and X2 changes to a single bond, the bond between X2 and the bridgehead N changes to a double bond, and simultaneously the previous bridgehead (NH) + The double bond can be rearranged so that the H on the top moves to X1. As a result, the N on X1 bonds to the H (H is the bridgehead (NH) + (The H from above is the one from the X1.) In this case, X1 is further protonated to form (NH)H + It can form a group.

[0079] In one embodiment of the present invention, when A is selected from the groups represented by formula (V) and formula (VI), X1 is NR7, in which case R7 is absent, thereby forming a group represented by formula (V-1) or formula (VI-1) below. [ka] [ka]

[0080] As described above, the group represented by formula (V-1) and the group represented by formula (VI-1) are tautomeric structures. [ka]

[0081] In all of the above cases, when one or both of X1 and X2 is NR7, it is protonated to (NH) + R7 groups can be formed. In this case, if R7 is absent, the N represented by X1 and X2 is protonated to form (NH) +Thus, a group in which one or both of X1 and X2 are NR7 will be protonated to form the following group: [ka]

[0082] In the present invention, the group represented by formula (III) can be derived from a bicyclic organic base having a structure represented by the following formula (VIII). [ka]

[0083] That is, in the present invention, a bicyclic organic base having a structure represented by formula (VIII) can be protonated with one proton, two protons, or three protons to derive a group represented by formula (III). The number of protonated groups depends on the number of N atoms in formula (VIII) and the molar ratio of the acidic phosphate ester to the bicyclic organic base.

[0084] In the present invention, by adjusting a, b, and c, the size of the ring structure of the bicyclic organic base of the group represented by (III) can be controlled, and the wear resistance and corrosion resistance to metal copper can be further optimized.

[0085] Furthermore, in the present invention, the basicity of these compounds and their dispersibility in the base oil can be controlled by adjusting the number of rings and the steric structure of the bicyclic organic base, and a bicyclic organic base having sufficiently stable chemical properties can be selected depending on the usage environment.

[0086] [Preparation process of phosphate ester salt] The present invention provides a process for preparing a phosphate ester salt, comprising the steps of: A process is provided, comprising reacting an acidic phosphate ester (also referred to herein as a phosphate ester) having a structure represented by formula (VII) with an organic base; [ka] wherein two R8 may be the same or different and are each selected from hydrogen and optionally substituted hydrocarbyl or heterohydrocarbyl, and both R8 are not simultaneously hydrogen; The organic base includes a bicyclic organic base having a structure represented by formula (VIII): [ka] During the ceremony, R3 is -(CH2) a -wherein a is an integer from 2 to 8; R4 is -(CH2) b - and b is an integer from 0 to 4; R5 is -(CH2) c where c is an integer from 1 to 5; X1 and X2 are each independently selected from CR6R6 and NR7; [ka] represents a single bond or a double bond, each R6 is present or absent, and each independently represents hydrogen or an optionally substituted C1-C6 straight or branched alkyl; R7 is present or absent and represents hydrogen or optionally substituted C1-C6 straight or branched alkyl.

[0087] In one embodiment of the present invention, in formula (VII), two R8 are not hydrogen at the same time.

[0088] In one embodiment of the present invention, in formula (VII), R8 may be the same or different and each independently represents an optionally substituted C1 to C 18 Linear or branched alkyl, optionally substituted C2-C 18 Linear or branched alkenyl, optionally substituted C4-C 18 Cycloalkyl, optionally substituted C-C 18 Aryl and optionally substituted C3-C20 heterohydrocarbyl.

[0089] In one embodiment of the present invention, in formula (VII), R8 may be the same or different and are each independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, n-hexyl, 2-ethylhexyl, n-octyl, 1-methylheptyl, 3,5,5-trimethylhexyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, 9-octadecenyl, 9,12-octadecadienyl, 12-hydroxy-9-octadecenyl, cyclohexyl, phenyl, benzyl, methylphenyl, or dimethylphenyl, all of which may be optionally substituted.

[0090] In the present invention, the heteroatom in the heterohydrocarbyl is at least one of O, N and S, preferably O and / or S, and more preferably S.

[0091] In one embodiment of the present invention, in formula (VII), R1 may be a heterohydrocarbyl, preferably a heterohydrocarbyl formed by replacing one or more -(CH2)- structural units in the specific groups listed above for R8 with -(NH)-, -O-, or -S-.

[0092] In one embodiment of the present invention, the source of the acidic phosphate ester having the structure represented by formula (VII) is not particularly limited, and the acidic phosphate ester may be a commercially available product or may be synthesized by a conventional method.

[0093] In one embodiment of the present invention, examples of acidic phosphate esters having a structure represented by formula (VII) include mono-n-butyl phosphate (CAS: 1623-15-0), di-n-butyl phosphate (CAS: 107-66-4), monoisobutyl phosphate (CAS: 2466-73-1), diisobutyl phosphate (CAS: 6303-30-6), mono-tert-butyl phosphate (CAS: 2382-75-4), di-tert-butyl phosphate (CAS: 33494-81-4), mono-n-hexyl phosphate (CAS: 3900-04-7), and phosphate. Di-n-hexyl (CAS: 3900-13-8), monophenyl phosphate (CAS: 701-64-4), diphenyl phosphate (CAS: 838-85-7), benzyl phosphate (CAS: 1623-07-0), dibenzyl phosphate (CAS: 1623-08-1), mono(methylphenyl) phosphate, di(methylphenyl) phosphate, mono-n-octyl phosphate (CAS: 3991-73-9), di-n-octyl phosphate (CAS: 3115-39-7), mono(2-ethylhexyl) phosphate (CAS: 1070-03-7), di( 2-ethylhexyl) (CAS: 298-07-7), mono(1-methylheptyl) phosphate (CAS: 10353-73-8), di(1-methylheptyl) phosphate (CAS: 77076-28-9), mono(3,5,5-trimethylhexyl) phosphate (CAS: 85006-34-4), di(3,5,5-trimethylhexyl) phosphate (CAS: 7153-98-2), mono-n-decyl phosphate (CAS: 3921-30-0), di-n-decyl phosphate (CAS: 7795-87-1), monolauryl phosphate, dilauryl phosphate, Examples of the phosphate include monomyristyl phosphate, dimyristyl phosphate, mono(hexadecyl) phosphate, di(hexadecyl) phosphate, monostearyl phosphate, distearyl phosphate, mono(9-octadecenyl) phosphate, di(9-octadecenyl) phosphate, mono(9,12-octadecadienyl) phosphate, di(9,12-octadecadienyl) phosphate, mono(12-hydroxy-9-octadecenyl) phosphate, di(12-hydroxy-9-octadecenyl) phosphate, or isomers of the above compounds, or mixtures thereof.

[0094] In one embodiment of the present invention, the acidic phosphate ester having the structure represented by formula (VII) can be used alone or in combination of two or more in the preparation process of the present invention.

[0095] In the present invention, the compound represented by formula (VIII) [ka] In a bicyclic organic base having a structure represented by R3 is -(CH2) a -wherein a is an integer from 2 to 8; R4 is -(CH2) b - and b is an integer from 0 to 4; R5 is -(CH2) c where c is an integer from 1 to 5; X1 and X2 are each independently selected from CR6R6 and NR7; [ka] represents a single bond or a double bond, each R6 is present or absent, and each independently represents hydrogen or an optionally substituted C1-C6 straight or branched alkyl; R7 is present or absent and represents hydrogen or optionally substituted C1-C6 straight or branched alkyl.

[0096] In one embodiment of the present invention, in formula (VIII), R3 is -(CH2) a In the formula, a is an integer of 2 to 8, preferably an integer of 2 to 6, and more preferably an integer of 2 to 5.

[0097] In one embodiment of the present invention, in formula (VIII), R4 is -(CH2) b -, and b is an integer of 0 to 4, preferably b is an integer of 0 to 3, and more preferably b is an integer of 0 to 2.

[0098] In one embodiment of the present invention, in formula (VIII), R5 is -(CH2)c In the formula, c is an integer of 1 to 5, preferably c is an integer of 1 to 4, and more preferably c is an integer of 1 to 3.

[0099] In one embodiment of the present invention, in formula (VIII), X1 and X2 are each independently selected from CR6R6 and NR7.

[0100] In one embodiment of the present invention, in formula (VIII), X1 is NR7 and X2 is NR7.

[0101] In one embodiment of the present invention, in formula (VIII), X1 is CR6R6 and X2 is NR7.

[0102] In one embodiment of the present invention, in formula (VIII), X1 is NR7 and X2 is CR6R6.

[0103] In one embodiment of the present invention, in formula (VIII): [ka] represents a single bond or a double bond.

[0104] In one embodiment of the present invention, in formula (VIII), each R6 is present or absent and each independently represents hydrogen or an optionally substituted C1-C6 straight or branched alkyl.

[0105] In one embodiment of the present invention, in formula (VIII), R7 is present or absent and represents hydrogen or optionally substituted C1-C6 linear or branched alkyl.

[0106] In one embodiment of the present invention, in formula (VIII), X1 and X2 are not simultaneously NR7.

[0107] The bicyclic organic base has a structure represented by at least one of formula (VIII-1) and formula (VIII-2). [ka] [ka]

[0108] In the structure represented by formula (VIII-1), [ka] If represents a double bond, R6 is absent. In this case, the following structures may be formed: [ka]

[0109] In the structure represented by formula (VIII-1), [ka] When is a single bond, the following structures can be formed: [ka]

[0110] The structure represented by formula (VIII-2) can be selected from the following structures: [ka]

[0111] In one embodiment of the present invention, b is 0.

[0112] In one embodiment of the present invention, b is 0, [ka] When represents a single bond, A is a structure represented by formula (VIII-3). [ka]

[0113] In one embodiment of the present invention, when A is a group represented by formula (VIII-3), X1 and X2 are preferably not simultaneously NR7.

[0114] In one embodiment of the present invention, when A is a group represented by formula (VIII-3), X2 is preferably not NR7.

[0115] In one embodiment of the present invention, when A is a group represented by formula (VIII-3), X2 is CR6 and X1 is NR7, in which case a structure represented by the following formula (VIII-3-1) is formed. [ka]

[0116] In one embodiment of the present invention, b is 0, [ka] When represents a double bond, A is a structure represented by formula (VIII-4). [ka]

[0117] In one embodiment of the present invention, when A is a group represented by formula (VIII-4), X1 is NR7 and R7 is absent, thus forming a structure represented by the following formula (VIII-4-1): [ka]

[0118] In the present invention, the source of the bicyclic organic base is not particularly limited. Commercially available products can be used directly, or they can be prepared by conventional methods known in the art.

[0119] In one embodiment of the present invention, the source of the bicyclic organic base having a structure represented by formula (VIII) is not particularly limited, and it may be a commercially available product or one synthesized by a conventional method.

[0120] In one embodiment of the present invention, examples of the bicyclic organic base represented by formula (VIII) include 1,4-diazabicyclo[2.2.2]octane (CAS: 280-57-9), 1-azabicyclo[2.2.2]octane (quinuclidine, CAS: 100-76-5), 1,5-diazabicyclo[4.3.0]-5-nonene (CAS: 3001-72-7), 1,8-diazabicyclo[5.4.0]undec-7-ene (CAS: 6674-22-2), and mixtures thereof in any ratio.

[0121] In one embodiment of the present invention, in the preparation process of the present invention, the organic base comprises one bicyclic organic base represented by formula (VIII), and may comprise two or more bicyclic organic bases represented by formula (VIII).

[0122] In one embodiment of the present invention, in the preparation process of the present invention, the organic base can be one bicyclic organic base represented by formula (VIII) or a mixture of two or more bicyclic organic bases represented by formula (VIII) (i.e., the organic base only comprises bicyclic organic bases represented by formula (VIII)).

[0123] In one embodiment of the present invention, in the preparation process of the present invention, the molar ratio of acidic phosphate ester to organic base is 1:0.1-10, preferably 1:0.3-2, more preferably 1:0.3-1.5.

[0124] In one embodiment of the present invention, it is particularly preferred that the molar ratio of the acid phosphate ester to the organic base is 1.0 or greater, that is, the acid phosphate ester is in excess relative to the organic base.

[0125] In the preparation process of the present invention, the reaction time is not particularly limited. In one embodiment of the present invention, the reaction temperature is 0°C to 200°C, preferably 30°C to 150°C, and more preferably 60°C to 100°C.

[0126] In the preparation process of the present invention, the reaction time is not particularly limited. In one embodiment of the present invention, to ensure a sufficient reaction, the reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours, and even more preferably 1 to 5 hours.

[0127] The preparation process of the present invention can be carried out in the presence or absence of a solvent.

[0128] In one embodiment of the present invention, the reaction is carried out in the presence of a solvent, which is a C6-C 10 Alkanes, C6-C 20 Aromatic hydrocarbons, C4-C 10 Aliphatic ethers, C2-C 20 Halogenated hydrocarbons and C3-C 10 At least one of the amides.

[0129] In one embodiment of the present invention, C6 to C 10 Examples of alkanes may include at least one of n-hexane, cyclohexane, and petroleum ether.

[0130] In one embodiment of the present invention, C6 to C 20 Examples of aromatic hydrocarbons include at least one of benzene, toluene, xylene, and isopropylbenzene.

[0131] In one embodiment of the present invention, C4 to C 10 Examples of the aliphatic ether include at least one of methyl tert-butyl ether, 1,2-dimethoxyethane, ethylene glycol diethyl ether, and 1,4-dioxane.

[0132] In one embodiment of the present invention, C2 to C20 Examples of halogenated hydrocarbons include at least one of dichloromethane, carbon tetrachloride, chlorobenzene, and 1,2-dichlorobenzene.

[0133] In one embodiment of the present invention, C3 to C 10 Examples of the amide include at least one of dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

[0134] In one embodiment of the present invention, the mass ratio of the total weight of the acidic phosphate ester and the organic base to the solvent is 1:0.5-10, preferably 1:0.5-5, and more preferably 1:0.8-3.

[0135] In one embodiment of the present invention, the preparation process further comprises recovering the solvent after the reaction and recycling the recovered solvent. The recovery method can include vacuum distillation.

[0136] In the present invention, there are no special requirements for the order of adding the acidic phosphate ester, the organic base, and the optional solvent to the reactor and for the specific operating conditions. Conventional operating methods in the art can be used. Preferably, the organic base is added slowly or dropwise in several portions to a solution of the acidic phosphate ester in the reaction solvent, and the reaction is carried out under continuous stirring while controlling the temperature within the above reaction temperature range.

[0137] In the present invention, the reaction pressure and atmosphere of the preparation process are not particularly limited, and the preparation process can be carried out under normal pressure and atmospheric conditions.

[0138] The preparation process provided by the present invention is a simple process that does not produce exhaust gases or wastewater, and is safe and environmentally friendly.

[0139] Complex The present invention provides a complex comprising at least one phosphate ester salt of the present invention or at least one phosphate ester salt prepared by the preparation process of the present invention.

[0140] In the composite of the present invention, the content of the phosphate ester salt relative to the total weight of the composite is 2% by weight or more, preferably 10% by weight or more, more preferably 20% by weight or more, even more preferably 40% by weight or more, and particularly preferably 50% by weight or more.

[0141] The complex of the present invention may further comprise at least one of the above-mentioned acidic phosphate ester represented by formula (VII) of the present invention, the above-mentioned bicyclic organic base represented by formula (VIII) of the present invention, and the above-mentioned reaction solvent used in the process for preparing the phosphate ester salt of the present invention.

[0142] In one embodiment of the present invention, after the phosphate ester salt is produced by the above-mentioned preparation process of the present invention, the phosphate ester salt can be directly used in the form of a mixture without separation or purification. In this case, the mixture is a complex of the present invention, which may contain, in addition to the phosphate ester salt of the present invention, incompletely reacted starting acidic phosphate ester and / or bicyclic organic base, and may also contain residual solvent.

[0143] In one embodiment of the present invention, when two or more acidic phosphate esters and / or bicyclic organic bases are used in the above-mentioned preparation process of the present invention, after the phosphate ester salts are produced, the phosphate ester salts can be directly used in the form of a mixture without separation or purification. In this case, the mixture is the complex of the present invention, and in addition to the two or more phosphate ester salts of the present invention, it may contain incompletely reacted raw acidic phosphate esters and / or bicyclic organic bases, as well as residual solvents.

[0144] In the present invention, the degree of reaction and the residual amount of the acidic phosphate ester and / or bicyclic organic base are related to the reaction conditions, feed ratio, and the like.

[0145] In the process for preparing the phosphate ester salt of the present invention, the resulting reaction product may be a single phosphate ester salt or a mixture containing two or more phosphate ester salts. All of these reaction products are anticipated by the present invention. Therefore, in the context of this specification, all of these reaction products will be collectively referred to as the phosphate ester salt of the present invention without distinction.

[0146] The phosphate ester salt of the present invention can exist, be produced, or be used in the form of a single (pure) compound or in the form of a mixture of two or more (in any ratio), without affecting the achievement of the effects of the present invention. In this case, the mixture of two or more phosphate ester salts (in any ratio) is the complex of the present invention.

[0147] Therefore, in the present invention, the (phosphate ester salt) product obtained by the preparation process of the present invention can be purified to remove unreacted reactants or to separate phosphate ester salts with different specific structures, or can be used directly in the form of a complex without purification.

[0148] The purification can be carried out by any conventional purification or separation method in the art, but the present invention is not particularly limited thereto. For example, the reaction product can be purified by distillation, heavy metal salting out, column chromatography, etc.

[0149] lubricating oil composition The present invention provides a lubricating oil composition comprising a lubricating base oil and an additive; the additive comprises a phosphate ester salt of the present invention or a phosphate ester salt prepared by the preparation process of the present invention or a complex comprising at least one phosphate ester salt of the present invention.

[0150] The phosphate ester salts and mixtures thereof provided by the present invention are free of metal elements, are less likely to produce ash or other precipitates, and exhibit significant anti-wear properties in relatively small amounts, effectively improving the anti-wear performance and load-bearing capacity of lubricating oils. In addition, when used as anti-wear additives for lubricating oils, the phosphate ester salts exhibit excellent anti-wear performance and low copper corrosion. These excellent properties are superior to those of acidic phosphate ester amine salt compounds of the prior art.

[0151] According to the present invention, the content of the phosphate ester salt is preferably 0.001% to 30%, more preferably 0.1% to 5%, and even more preferably 0.1% to 1%, based on the total weight of the lubricating oil composition. Compared with existing phosphate ester amine salts, the phosphate ester salt provided as an anti-wear additive by the present invention can exhibit good anti-wear performance and relatively little copper corrosion even in a very small amount.

[0152] In the present invention, the type of lubricating base oil is not particularly limited, and the lubricating base oil may be any lubricating base oil conventionally used in the art, for example, at least one of mineral base oil, animal oil, vegetable oil, and synthetic base oil. The mineral base oil may be, for example, a mineral base oil having a viscosity index of more than 80, or a mineral base oil having a saturated hydrocarbon content of more than 90 wt% and a sulfur content of less than 0.03 wt%. The synthetic base oil may be, for example, a polyolefin, a synthetic ester, a silicone oil, a polyether, etc.

[0153] According to the present invention, the additives in the lubricating oil composition may include other lubricating oil additives in addition to the phosphate ester salt provided by the present invention, and those skilled in the art can select them according to the performance requirements of the actual lubricating oil composition. For example, the lubricating oil composition may also include sulfur-containing extreme pressure additives, friction reducers, metal deactivators, rust inhibitors, dispersants, viscosity modifiers, etc. Specific types of these other lubricating oil additives are well known to those skilled in the art.

[0154] Lubricating grease composition The present invention provides a lubricating grease composition comprising a lubricating grease base oil and an additive, the additive comprising a phosphate ester salt of the present invention or a phosphate ester salt prepared by the preparation process of the present invention or a complex comprising at least one phosphate ester salt of the present invention.

[0155] According to the present invention, the content of the phosphate ester salt is preferably 0.001% to 30%, preferably 0.1% to 5%, more preferably 0.1% to 1%, based on the total weight of the lubricating grease composition. Compared with existing phosphate ester amine salts, the phosphate ester salt provided as an anti-wear additive according to the present invention exhibits better anti-wear performance and relatively low copper corrosion even in very small amounts.

[0156] In the present invention, there is no particular limitation on the type of base oil used in the lubricating grease, and it may be any lubricating grease base oil conventionally used in the art, and it may be a Class III base oil or a PAO synthetic oil. There is no particular limitation on the thickener used in the grease, but it is preferably a non-metal soap type thickener.

[0157] The lubricating grease may also contain other lubricating grease additives including metal deactivators, antioxidants, etc. The specific types of these other lubricating grease additives are well known to those skilled in the art.

[0158] use The present invention provides the use of the phosphate ester salt of the present invention, the phosphate ester salt prepared by the preparation process of the present invention, or the complex of the present invention in lubricating oils and lubricating greases.

[0159] The phosphate ester salt anti-wear additive provided by the present invention exhibits excellent anti-wear performance, load-bearing capacity, and relatively little copper corrosion, and is therefore particularly suitable for use as a multifunctional additive in the production of lubricating oil compositions and lubricating grease compositions that are expected to have particularly excellent anti-wear performance. The present invention also provides uses of the phosphate ester salt of the present invention, the phosphate ester salt prepared by the preparation process of the present invention, and the composite of the present invention in other fields such as flame retardants, metal extractants, flotation agents, and antioxidants. [Example]

[0160] Example 1 A 250 mL three-neck flask equipped with a magnetic stirrer, thermometer, condenser, and dropping funnel was charged with 5.61 g (50.01 mmol) of 1,4-diazabicyclo[2.2.2]octane (99%, Macklin) and 45.52 g of 1,2-dimethoxyethane (99.5%, InnoChem). The mixture was stirred rapidly and dissolved at room temperature, and 21.04 g (100.01 mmol) of di-n-butyl phosphate (>97%, InnoChem) was slowly added dropwise to the three-neck flask. The reaction mixture was heated to 85 °C, and the temperature was controlled between 80 and 85 °C under reflux for 4 hours. After completion of the reaction, the solvent was removed by vacuum distillation to yield 26.06 g of a yellowish, colorless, transparent, oily liquid. The product was recorded as S1.

[0161] Example 2 A 250 mL three-neck flask equipped with a magnetic stirrer, thermometer, condenser, and dropping funnel was charged with 21.02 g (100.00 mmol) of di-n-butyl phosphate (>97%, InnoChem) and 39.23 g of 1,2-dimethoxyethane (99.5%, InnoChem). The mixture was stirred rapidly and dissolved at room temperature. 15.22 g (99.97 mmol) of 1,8-diazabicyclo[5.4.0]undec-7-ene (99%, InnoChem) was slowly added dropwise to the three-neck flask. The reaction mixture was heated to 85 °C, the temperature was controlled between 80 and 85 °C, and the reaction was carried out under reflux for 4.5 hours. After the reaction was complete, the solvent was removed by vacuum distillation to yield 36.14 g of a clear liquid product. The product was recorded as S2.

[0162] Example 3 To a 250 mL three-neck flask equipped with a magnetic stirrer, thermometer, condenser, and dropping funnel, 21.01 g (99.95 mmol) of di-n-butyl phosphate (>97%, InnoChem) and 33.00 g of 1,2-dimethoxyethane (99.5%, InnoChem) were added. The mixture was stirred rapidly and dissolved at room temperature, and 7.16 g (49.99 mmol) of 1,8-diazabicyclo[5.4.0]undec-7-ene (99%, InnoChem) was slowly added dropwise to the three-neck flask. The reaction mixture was heated to 85 °C, and the temperature was controlled between 80 and 85 °C under reflux for 4.5 hours. After completion of the reaction, the solvent was removed by vacuum distillation to yield 28.57 g of a clear, yellowish liquid product. The product was recorded as S3.

[0163] ESI FT-ICR analysis and identification of S3 gave the following ion peaks, where di-n-butyl phosphate was designated as P, 1,8-diazabicyclo[5.4.0]undec-7-ene was designated as A, and the salt formed by the two was designated as AP:

[0164] [Table 1] Infrared analysis and identification were carried out on S3, and the infrared spectrum is shown in FIG.

[0165] Example 4 A 250 mL three-neck flask equipped with a magnetic stirrer, thermometer, condenser, and dropping funnel was charged with 5.34 g (25.40 mmol) of di-n-butyl phosphate (>97%, InnoChem) and 17.08 g of 1,2-dimethoxyethane (99.5%, InnoChem). The mixture was stirred rapidly and dissolved at room temperature. 7.16 g (49.99 mmol) of 1,8-diazabicyclo[5.4.0]undec-7-ene (99%, InnoChem) was slowly added dropwise to the three-neck flask. The reaction mixture was heated to 85 °C, and the temperature was controlled between 80 and 85 °C under reflux for 4.5 hours. After completion of the reaction, the solvent was removed by vacuum distillation to yield 12.91 g of a clear liquid product. This product was recorded as S4.

[0166] Example 5 To a 250 mL three-neck flask equipped with a magnetic stirrer, thermometer, condenser, and dropping funnel, 13.31 g (49.98 mmol) of di-n-hexyl phosphate (96.5%, homemade) and 19.65 g of 60-90 °C petroleum ether (InnoChem) were added. The mixture was stirred rapidly and dissolved at room temperature, and 3.81 g (25.03 mmol) of 1,8-diazabicyclo[5.4.0]undec-7-ene (99%, InnoChem) was slowly added dropwise to the three-neck flask. The reaction mixture was warmed to 70 °C and refluxed for 4.5 hours. After completion of the reaction, the solvent was removed by vacuum distillation to yield 17.10 g of a light yellow, transparent liquid product. This product was recorded as S5. As a result of ESI FT-ICR analysis and identification of S5, the following ion peaks were obtained. Di-n-hexyl phosphate was designated as P, 1,8-diazabicyclo[5.4.0]undec-7-ene was designated as A, and the salt formed by the two was designated as AP:

[0167] [Table 2] Infrared analysis and identification were carried out on S5, and the infrared spectrum is shown in FIG.

[0168] Example 6 To a 250 mL three-neck flask equipped with a magnetic stirrer, thermometer, condenser, and dropping funnel, 16.17 g (50.15 mmol) of di(2-ethylhexyl)phosphate (99%, InnoChem) and 19.92 g of 60-90 °C petroleum ether (InnoChem) were added. The mixture was stirred rapidly and dissolved at room temperature, and 3.81 g (25.03 mmol) of 1,8-diazabicyclo[5.4.0]undec-7-ene (99%, InnoChem) was slowly added dropwise to the three-neck flask. The reaction mixture was warmed to 70 °C and maintained at this temperature, allowing the reaction to proceed under reflux for 4 hours. After completion of the reaction, the solvent was removed by vacuum distillation to yield 19.91 g of a yellow, clear, oily liquid. The product was recorded as S6.

[0169] Comparative Example 1 Dibutyldi-n-hexylamine phosphate salt Commercially available dibutyl phosphate and di-n-hexylamine were used as raw materials. Dibutyl phosphate was dissolved in 60-90°C petroleum ether, and the mass ratio of dibutyl phosphate to 60-90°C petroleum ether was 1:1. Di-n-hexylamine was slowly added dropwise to the dibutyl phosphate solution under stirring, and the molar ratio of dibutyl phosphate to di-n-hexylamine was 1:1. The reaction mixture was heated to 80°C, controlled at 75-80°C, and reacted under reflux for 4 hours. After the reaction was completed, the solvent was evaporated to obtain the product, which was recorded as DS1.

[0170] Comparative Example 2 Dibutyl laurylamine phosphate Commercially available dibutyl phosphate and laurylamine were used as raw materials. Dibutyl phosphate was dissolved in 60-90°C petroleum ether, with a mass ratio of dibutyl phosphate to 60-90°C petroleum ether of 1:1. Laurylamine was dissolved in 60-90°C petroleum ether, with a mass ratio of laurylamine to petroleum ether of 1:1. Laurylamine was slowly added dropwise to the dibutyl phosphate solution with stirring, with a molar ratio of dibutyl phosphate to laurylamine of 1:1. The reaction mixture was heated to 80°C, controlled at 75-80°C, and reacted under reflux for 4 hours. After the reaction was completed, the solvent was removed by evaporation to obtain the product, which was recorded as DS2.

[0171] Comparative Example 3 Dibutyltripropylamine phosphate salt Commercially available dibutyl phosphate and tripropylamine were used as raw materials. Dibutyl phosphate was dissolved in 60-90°C petroleum ether, with a mass ratio of dibutyl phosphate to 60-90°C petroleum ether of 1:1. Tripropylamine was slowly added dropwise to the dibutyl phosphate solution under stirring, with a molar ratio of dibutyl phosphate to tripropylamine of 1:1. The reaction mixture was heated to 80°C, controlled at 75-80°C, and reacted under reflux for 4 hours. After the reaction was completed, the solvent was evaporated to obtain the product, which was recorded as DS3.

[0172] Comparative Example 4 Di(2-ethylhexyl)di-n-hexylamine phosphate salt Di(2-ethylhexyl) phosphate was dissolved in 60-90°C petroleum ether at a mass ratio of 1:1. Di-n-hexylamine was slowly added dropwise to the di(2-ethylhexyl) phosphate solution with stirring at a molar ratio of 1:1. The reaction mixture was heated to 80°C, controlled at 75-80°C, and reacted under reflux for 4 hours. After completion of the reaction, the solvent was evaporated to obtain the product, which was recorded as DS4.

[0173] Comparative Example 5 A commercially available phosphate ester amine salt type anti-wear additive, isooctyl phosphate butyl dodecyl amine salt extreme pressure anti-wear additive T-308B, hereinafter referred to as DS5.

[0174] Comparative Example 6 Recorded as CIBA Irgalube T349, DS6, a commercially available phosphate ester amine salt antiwear additive.

[0175] Comparative Example 7 CIBA Irgalube T349, a commercially available phosphate ester amine salt antiwear additive, was mixed with S3 in a 1:1 mass ratio and the mixture was recorded as DS7.

[0176] Test Example The products prepared in the Examples and Comparative Examples were mixed with a lubricating base oil at 60°C for 2 hours according to the compositions and amounts added in Table 1 to obtain lubricating oil compositions, and performance evaluations were carried out. The results are shown in Table 1.

[0177] The lubricant base oil was a Class III base oil, Yubase 4 (viscosity at 40°C: 19.2 cSt; viscosity at 100°C: 4.24 cSt; viscosity index VI=128).

[0178] A base oil containing no antiwear additives was used as a control sample.

[0179] (1) Wear resistance evaluation According to the SH / T0189 standard method, the lubricating oil composition was used as a test sample for evaluating anti-wear performance. The test conditions for the anti-wear test were as follows: 392 N (40 kg) force, oil bath temperature 75°C, upper ball rotation speed 1200 r / min, and time 60 minutes. The anti-wear performance of the sample was evaluated based on the average wear scar diameter of the three lower balls.

[0180] (2) Evaluation of lubricant load-bearing capacity According to the GB / T3142-2019 standard method, the lubricant load-bearing capacity was evaluated using the lubricant composition as the test sample. The test items include the maximum non-seizure load (P B ) and welding load (P D ) was included.

[0181] (3) Evaluation of copper piece corrosion According to ASTM D130 standard method, copper strip corrosion evaluation was carried out using the lubricating oil composition as a test sample. A polished copper strip was immersed in 30 ml of the sample, heated to a test temperature of 150°C, and maintained for 72 hours. After the test was completed, the copper strip was removed and the amount of copper dissolved in the test oil was measured.

[0182] [Table 3]

[0183] Comparative Examples 1-4 were higher purity phosphate ester amine salts, and Comparative Examples 5-6 were phosphate ester amine salt anti-wear additives used in the prior art.

[0184] As can be seen from the results in Table 1, the phosphate ester salt prepared according to the present invention exhibits significant anti-wear properties and a higher non-seizure load even in a smaller amount, effectively improving the anti-wear properties and load-bearing capacity of the lubricating oil. Meanwhile, a comparison between the Examples and Comparative Examples shows that the phosphate ester salt provided by the present invention has better copper corrosion resistance than the phosphate amine salt.

[0185] In particular, when the acid phosphate ester was used in excess relative to the bicyclic organic base, the resulting phosphate ester salt exhibited better anti-wear performance and copper corrosion resistance. Although the preferred embodiments of the present invention have been described in detail above, the present invention is not limited thereto.

[0186] Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the disclosure content of the present invention, and all belong to the protection scope of the present invention.

Claims

1. The following formula (I): j(A) ｍ＋ ・k(P) ｎ－ (I) A phosphate ester salt having a structure represented by wherein P is a group of formula (II) 【Chemical 1】 is a group represented by Two R's １ are each independently selected from hydrogen and optionally substituted hydrocarbyl or heterohydrocarbyl, or R １ does not exist OR １ Is O － group, and two R １ at least one of which is selected from optionally substituted hydrocarbyl or heterohydrocarbyl; A is a group represented by formula (III) 【Chemistry 2】 is a group represented by During the ceremony, R ３ Ha-(CH ２ ) ａ -, where a is an integer from 2 to 8; R ４ Ha-(CH ２ ) ｂ - and b is an integer from 0 to 4; R ５ Ha-(CH ２ ) ｃ -, where c is an integer from 1 to 5; X １ and X ２ are each independently CR ６ R ６ and NR ７ is selected from 【Chemistry 3】 represents a single bond or a double bond, X １ and / or X ２ NR ７ is protonated to (NH) ＋ R ７ can form a group, Each R ６ are present or absent, each independently hydrogen or optionally substituted C １ ~C ６ represents a linear or branched alkyl; R ７ is present or absent and is hydrogen or optionally substituted C １ ~C ６ represents a linear or branched alkyl; m is an integer of 1 to 3, n is an integer of 1 to 2, j is an integer of 1 to 2, k is an integer of 1 to 3, and k×n=j×m; b is 0, and X １ and X ２ When a double bond is formed between X １ and X ２ A single bond is formed between X ２ and bridgehead N. A phosphate ester salt that can rearrange to form a double bond between the

2. In formula (II), the R １ may be the same or different and each independently represent an optionally substituted C １ ~C １８ Linear or branched alkyl, optionally substituted C ２ ~C １８ Linear or branched alkenyl, optionally substituted C ４ ~C １８ Cycloalkyl, optionally substituted C ６ ~C １８ aryl, optionally substituted C ３ ~C ２０ heterohydrocarbyl, Preferably, the R １ may be the same or different and each independently selected from methyl, ethyl, propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, n-hexyl, 2-ethylhexyl, n-octyl, 1-methylheptyl, 3,5,5-trimethylhexyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, 9-octadecenyl, 9,12-octadecadienyl, 12-hydroxy-9-octadecenyl, cyclohexyl, phenyl, benzyl, methylphenyl, or dimethylphenyl, all of which may be optionally substituted.

3. A is a group represented by formula (III-1) or formula (III-2) 【Chemistry 4】 【Chemistry 5】 The phosphate ester salt according to claim 1 or 2, wherein the phosphate ester salt is a group represented by the formula:

4. A is a group represented by formula (IV), formula (V), or formula (VI), 【Chemistry 6】 【Chemistry 7】 【Chemistry 8】 is a group represented by Preferably, when A is a group represented by formula (IV), X １ and X ２ is preferably simultaneously NR ７ Instead, Preferably, when A is a group represented by formula (V) or formula (VI), X １ is preferably N and is protonated to (NH) ＋ The phosphate ester salt according to any one of claims 1 to 3, which is capable of forming a group.

5. The phosphate ester salt according to any one of claims 1 to 4, wherein a is an integer of 2 to 6; and / or c is an integer of 1 to 5; and / or m is an integer of 1 or 2, n is an integer of 1 or 2, j is an integer of 1 or 2, k is an integer of 1 or 2, and k×n=j×m.

6. A process for preparing a phosphate ester salt, comprising reacting an acidic phosphate ester having a structure represented by formula (VII) with an organic base: 【Chemistry 9】 In the formula, two R ８ are each independently selected from hydrogen and optionally substituted hydrocarbyl or heterohydrocarbyl, and two R ８ is not hydrogen at the same time; The organic base is represented by formula (VIII): 【Chemistry 10】 The bicyclic organic base has a structure represented by During the ceremony, R ３ Ha-(CH ２ ) ａ -, where a is an integer from 2 to 8; R ４ Ha-(CH ２ ) ｂ - and b is an integer from 0 to 4; R ５ Ha-(CH ２ ) ｃ -, where c is an integer from 1 to 5; X １ and X ２ are each independently CR ６ R ６ and NR ７ is selected from 【Chemistry 11】 represents a single bond or a double bond, Each R ６ are present or absent, and each independently represents hydrogen or optionally substituted C １ ~C ６ represents a linear or branched alkyl; R ７ is present or absent and is hydrogen or optionally substituted C １ ~C ６ represents a straight-chain or branched alkyl).

7. In formula (VII), the R ８ may be the same or different and each independently represent an optionally substituted C １ ~C １８ Linear or branched alkyl, optionally substituted C ２ ~C １８ Linear or branched alkenyl, optionally substituted C ４ ~C １８ Cycloalkyl, optionally substituted C ６ ~C １８ aryl, optionally substituted C ３ ~C ２０ heterohydrocarbyl, More preferably, R ８ may be the same or different and are each independently selected from methyl, ethyl, propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, n-hexyl, 2-ethylhexyl, n-octyl, 1-methylheptyl, 3,5,5-trimethylhexyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, 9-octadecenyl, 9,12-octadecadienyl, 12-hydroxy-9-octadecenyl, cyclohexyl, phenyl, benzyl, methylphenyl, or dimethylphenyl, all of which may be optionally substituted.

8. The bicyclic organic base is represented by the formula (VIII-1) and the formula (VIII-2): 【Chemistry 12】 【Chemistry 13】 The process for preparing according to claim 6 or 7, wherein the compound has a structure represented by at least one of the following:

9. The bicyclic organic base is represented by the formula (VIII-3) and the formula (VIII-4): 【Chemistry 14】 【Chemistry 15】 and having a structure represented by at least one of Preferably, when the bicyclic organic base has a structure represented by formula (VIII-3), X １ and X ２ is preferably simultaneously NR ７ Preferably, when the bicyclic organic base has a structure represented by formula (VIII-4), X １ The process for preparing according to any one of claims 6 to 8, wherein is preferably N.

10. The preparation process according to any one of claims 6 to 8, wherein a is an integer from 2 to 6; and / or c is an integer from 1 to 5.

11. the molar ratio of the acidic phosphate ester to the organic base is 1:0.1-10, preferably 1:0.3-2, more preferably 1:0.3-1.5; Preferably, the reaction conditions include: a reaction temperature of 0°C to 200°C, preferably 30°C to 150°C, more preferably 60°C to 100°C; a reaction time of 0.1 hours to 24 hours, preferably 0.5 hours to 12 hours, more preferably 1 to 5 hours; Preferably, the reaction is carried out in the presence of a solvent, and the solvent is C ６ ~C １０ Alkanes, C ６ ~C ２０ Aromatic hydrocarbons, C ４ ~C １０ Aliphatic ethers, C ２ ~C ２０ Halogenated hydrocarbons and C ３ ~C １０ amides, The preparation process according to any one of claims 6 to 10, wherein the mass ratio of the total mass of the acidic phosphate ester and the organic base to the solvent is 1:0.5-10, preferably 1:0.5-5, more preferably 1:0.8-3.

12. 12. A phosphate ester salt complex comprising at least one phosphate ester salt according to any one of claims 1 to 5 or at least one phosphate ester salt prepared by the preparation process according to any one of claims 6 to 11, wherein preferably the at least one phosphate ester salt constitutes at least 2 wt. %, preferably at least 10 wt. %, more preferably at least 20 wt. %, even more preferably at least 40 wt. %, and particularly preferably at least 50 wt. % of the total amount of the complex.

13. 13. The phosphate ester salt complex according to claim 12, further comprising at least one of an acidic phosphate ester represented by formula (VII) according to claim 6, a bicyclic organic base represented by formula (VIII) according to claim 6, and a solvent according to claim 11.

14. Use of the phosphate ester salt according to any one of claims 1 to 5, the phosphate ester salt prepared by the preparation process according to any one of claims 6 to 11, or the complex according to any one of claims 12 to 13 in a lubricating oil.

15. A lubricating oil composition comprising a lubricating base oil and an additive; the additive comprises a phosphate ester salt according to any one of claims 1 to 5, a phosphate ester salt prepared by the preparation process according to any one of claims 6 to 11, or a complex according to any one of claims 12 to 13; Preferably, the content of the phosphate ester salt is 0.001 to 30 wt %, preferably 0.1 to 5 wt %, and more preferably 0.1 to 1 wt %, based on the total weight of the lubricating oil composition.

16. Use of the phosphate ester salt according to any one of claims 1 to 5, the phosphate ester salt prepared by the preparation process according to any one of claims 6 to 11, or the composite according to any one of claims 12 to 13 in a lubricating grease.

17. a lubricating grease composition comprising a lubricating grease base oil and additives; the additive comprises a phosphate ester salt according to any one of claims 1 to 5, a phosphate ester salt prepared by the preparation process according to any one of claims 6 to 11, or a complex according to any one of claims 12 to 13; Preferably, the content of the phosphate ester salt is 0.001 to 30 wt. %, preferably 0.1 to 5 wt. %, and more preferably 0.1 to 1 wt. %, based on the total weight of the lubricating grease composition; Preferably, the additive further comprises a thickener, and more preferably, the thickener is a non-metal soap type thickener.

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