Photoluminescent grease compositions, photoluminescent materials, and methods of making the same

Abstract

The present application provides a thiazole derivative having a general formula (I): wherein the definitions of the groups are described in the specification. The thiazole derivative having the general formula (I) has an aggregation-induced emission property, and is particularly suitable for use in a light-emitting component and device, a fluorescent probe, biological imaging, a lubricating oil, and a grease. The present application provides a photoluminescent grease composition containing a light-emitting material. The grease composition of the present application has a photoluminescent property and one or more of an antioxidation property, an antiwear property, an extreme pressure property, and a rust-preventive property. The grease composition of the present application can be used on related mechanical equipment in the electric industry, the metallurgical industry, the food industry, the papermaking industry, the automobile industry, and the aircraft industry.

Description

Technical Field

[0001] This invention relates to photoluminescent materials, and more particularly to photoluminescent materials having aggregation-induced emission properties and photoluminescent grease compositions containing photoluminescent materials having aggregation-induced emission properties. Background Technology

[0002] Traditional organic luminescent materials typically exhibit strong luminescence at low concentrations, but weak or no luminescence at high concentrations or in the solid state, exhibiting an aggregation-induced fluorescence quenching effect. This is because, in the aggregated state, strong intermolecular interactions enhance the nonradiative decay process of the excited state, significantly reducing the fluorescence quantum yield. In practical applications, the aggregation-induced fluorescence quenching effect largely limits the practical use of organic light-emitting materials. Recent studies have discovered that some compounds exhibit properties opposite to traditional organic light-emitting materials, not only lacking the aggregation-induced fluorescence quenching effect but also displaying aggregation-induced emission (AIE) properties. Over the past decade or so, researchers have applied these AIEs to various research fields, including light-emitting devices, fluorescent probes, and bioimaging.

[0003] Grease is a solid to semi-fluid product prepared by dispersing a thickener in a liquid lubricant. It has the functions of lubrication, protection and sealing, and plays a vital role in industrial machinery, agricultural machinery, transportation industry, aerospace industry, electronics and information industry and various military equipment.

[0004] In many cases, the amount of remaining grease is difficult to observe directly with the naked eye. Monitoring grease is even more challenging under dark operating conditions. There is a need in the art for a grease composition that is easy to monitor. Summary of the Invention

[0005] This invention provides a photoluminescent grease composition containing a luminescent material, thereby solving the aforementioned problems in the art. This invention develops a photoluminescent material with aggregation-induced emission properties and uses it in the photoluminescent grease composition of this invention.

[0006] In one aspect, the present invention provides a photoluminescent material having aggregation-induced emission properties, which is a thiophene derivative having general formula (I):

[0007]

[0008] In general formula (I), each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups, each x is independently selected from an integer between 0 and 5;

[0009] Each G is independently selected from hydrogen and C. 1-6Straight-chain or branched alkyl groups, alkynyl groups represented by formula (I-1), alkynyl groups represented by formula (I-2), alkynyl groups represented by formula (I-3), alkynyl groups represented by formula (I-4), and groups represented by formula (I-1').

[0010]

[0011] In equations (I-1), (I-2), (I-3), and (I-4), each R1 is independently selected from hydrogen and C. 1-6 Straight-chain or branched alkyl groups; each R2 is independently selected from C 1-6 Straight-chain or branched alkylene groups; each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl; each x is independently selected from an integer between 0 and 5; each y is independently selected from an integer between 0 and 4; each z is independently selected from an integer between 1 and 4; in formula (I-1), one of A and A' is NR and the other is S, wherein R is selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups;

[0012] In equations (I), (I-2), and (I-3), each G' is independently selected from hydrogen and C. 1-6 Straight-chain or branched alkyl groups, groups represented by formula (I-1'), alkynyl groups represented by formula (I-2'), and alkynyl groups represented by formula (I-3');

[0013]

[0014] In equations (I-1') and (I-2'), each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl; each x is independently selected from an integer between 0 and 5; each y' is independently selected from an integer between 0 and 3; each z' is independently selected from an integer between 0 and 3;

[0015] In equation (I-3'), R3, R4, and R5 are each independently selected from hydrogen, C, and C. 1-20 Straight-chain or branched alkyl groups (preferably C14) 1-10 The following groups may be used: straight-chain or branched alkyl groups; groups represented by formula (II-1); groups represented by formula (II-2); and groups represented by formula (II-3), provided that at least one of R3, R4, and R5 is a group represented by formula (II-1), a group represented by formula (II-2), or a group represented by formula (II-3) (preferably R4 is a group represented by formula (II-1), and R3 and R5 are hydrogen; or R3 and R5 are groups represented by formula (II-3), and R4 is hydrogen).

[0016]

[0017] In equations (II-1) and (II-2), R6 represents hydrogen and C. 1-6 Straight-chain or branched hydrocarbon groups (preferably hydrogen, C) 1-4 (straight-chain or branched alkyl), R7 is hydrogen, C 1-6 Straight-chain or branched hydrocarbon groups (preferably hydrogen, C) 1-4 (linear or branched alkyl groups);

[0018]

[0019] In equation (II-3), R a Selected from hydrogen, C 1-20 Straight-chain or branched alkyl groups (preferably selected from C) 1-10 (straight-chain or branched alkyl); R b Selected from hydrogen, C 1-20 Straight-chain or branched alkyl groups;

[0020] In general formula (I), at least one G is selected from the alkynyl group shown in formula (I-1), the alkynyl group shown in formula (I-2), the alkynyl group shown in formula (I-3), or the alkynyl group shown in formula (I-4), or at least one G' is selected from the group shown in formula (I-1'), the alkynyl group shown in formula (I-2'), or the alkynyl group shown in formula (I-3').

[0021] In another aspect, the present invention provides a first method for preparing the thiophene derivative having general formula (I), comprising the step of reacting a thiophene compound of general formula (III-1) with one or more alkyne compounds of general formulas (III-1'), (III-2'), (III-3'), (III-4'), (III-5'), and (III-6').

[0022]

[0023] In general formula (III-1), each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups, each x is independently selected from an integer between 0 and 5; each G is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups, groups represented by formula (I-1'), and X groups; each G' is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups, groups represented by formula (I-1'), and X groups;

[0024]

[0025] In equation (I-1'), each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups; each x is independently selected from an integer between 0 and 5;

[0026] The X group is selected from F, Cl, Br, I, and OH, with Cl or Br being preferred;

[0027] At least one G or G' is selected from the X group;

[0028]

[0029]

[0030] In equations (III-1'), (III-2'), (III-3'), (III-4'), and (III-5'), each R1 is independently selected from hydrogen, C, and C. 1-6 Straight-chain or branched alkyl groups; each R2 is independently selected from C 1-6 Straight-chain or branched alkylene groups; each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl; each x is independently selected from an integer between 0 and 5; each y is independently selected from an integer between 0 and 4; each z is independently selected from an integer between 1 and 4; each y' is independently selected from an integer between 0 and 3; each z' is independently selected from an integer between 0 and 3.

[0031] In equation (III-1'), one of A and A' is NR, and the other is S, where R is selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups;

[0032] In equation (III-6'), R3, R4, and R5 are each independently selected from hydrogen, C, and C. 1-20 Straight-chain or branched alkyl groups (preferably C14) 1-10 The following are possible combinations of groups: linear or branched alkyl groups, hydroxyl groups, groups represented by formula (II-1), groups represented by formula (II-2), and groups represented by formula (II-3), provided that at least one of R3, R4, and R5 is a group represented by formula (II-1), a group represented by formula (II-2), a group represented by formula (II-3), or a hydroxyl group (preferably R4 is a group represented by formula (II-1), and R3 and R5 are hydrogen; or R3 and R5 are groups represented by formula (II-3), and R4 is hydrogen; or R3 and R5 are hydrogen, and R4 is a hydroxyl group).

[0033]

[0034] In equations (II-1) and (II-2), R6 represents hydrogen and C. 1-6 Straight-chain or branched hydrocarbon groups (preferably hydrogen, C) 1-4 (straight-chain or branched alkyl), R7 is hydrogen, C 1-6 Straight-chain or branched hydrocarbon groups (preferably hydrogen, C) 1-4 (linear or branched alkyl groups);

[0035]

[0036] In equation (II-3), R a Selected from hydrogen, C 1-20 Straight-chain or branched alkyl groups (preferably selected from C) 1-10 (straight-chain or branched alkyl); R b Selected from hydrogen, C 1-20 Straight-chain or branched alkyl groups.

[0037] In another aspect, the present invention also provides a second method for preparing the thiophene derivative having general formula (I), comprising the step of reacting a thiophene compound of general formula (III-1-1) with one or more compounds of general formulas (III-1'-1), (III-2'-1), (III-3'-1), (III-4'-1), (III-5'-1), and (III-6'-1).

[0038]

[0039] In general formula (III-1-1), each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups, each x is independently selected from an integer between 0 and 5; each G is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups, groups represented by formula (I-1') and (Right now Each G' is independently selected from hydrogen and C. 1-6 Straight-chain or branched alkyl groups, groups represented by formula (I-1') and

[0040]

[0041] In equation (I-1'), each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups; each x is independently selected from an integer between 0 and 5;

[0042] At least one G or G' is selected from

[0043]

[0044]

[0045] The X group is selected from F, Cl, Br, I, and OH, with Cl or Br being preferred;

[0046] In equations (III-1'-1), (III-2'-1), (III-3'-1), (III-4'-1), and (III-5'-1), each R1 is independently selected from hydrogen and C. 1-6 Straight-chain or branched alkyl groups; each R2 is independently selected from C 1-6 Straight-chain or branched alkylene groups; each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl; each x is independently selected from an integer between 0 and 5; each y is independently selected from an integer between 0 and 4; each z is independently selected from an integer between 1 and 4; each y' is independently selected from an integer between 0 and 3; each z' is independently selected from an integer between 0 and 3.

[0047] In equation (III-1'-1), one of A and A' is NR, and the other is S, where R is selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups;

[0048] In equation (III-6'-1), R3, R4, and R5 are each independently selected from hydrogen, C, and C. 1-20 Straight-chain or branched alkyl groups (preferably C14) 1-10 The following are possible combinations of groups: linear or branched alkyl groups, hydroxyl groups, groups represented by formula (II-1), groups represented by formula (II-2), and groups represented by formula (II-3), provided that at least one of R3, R4, and R5 is a group represented by formula (II-1), a group represented by formula (II-2), a group represented by formula (II-3), or a hydroxyl group (preferably R4 is a group represented by formula (II-1), and R3 and R5 are hydrogen; or R3 and R5 are groups represented by formula (II-3), and R4 is hydrogen; or R3 and R5 are hydrogen, and R4 is a hydroxyl group).

[0049]

[0050] In equations (II-1) and (II-2), R6 represents hydrogen and C. 1-6 Straight-chain or branched hydrocarbon groups (preferably hydrogen, C) 1-4 (straight-chain or branched alkyl), R7 is hydrogen, C 1-6 Straight-chain or branched hydrocarbon groups (preferably hydrogen, C) 1-4 (linear or branched alkyl groups);

[0051]

[0052] In equation (II-3), R a Selected from hydrogen, C 1-20 Straight-chain or branched alkyl groups (preferably selected from C) 1-10 (straight-chain or branched alkyl); R b Selected from hydrogen, C 1-20 Straight-chain or branched alkyl groups.

[0053] In another aspect, the present invention provides a photoluminescent grease composition comprising a luminescent material, a thickener, and a lubricating base oil. Preferably, the luminescent material is a photoluminescent material with aggregation-induced emission properties; more preferably, the photoluminescent material with aggregation-induced emission properties comprises a tetraphenylethylene compound and a thiophene derivative. Preferably, the tetraphenylethylene compound comprises tetraphenylethylene or a derivative thereof; more preferably, the structure of the tetraphenylethylene compound is:

[0054]

[0055] Among them, each R 11 They are the same or different from each other, and each is independently selected from C. 1-6 Straight-chain or branched alkyl groups; each m may be the same or different from the others, and each is independently selected from an integer between 0 and 5. Preferably, the thiophene derivatives include thiophene derivatives having general formula (I) and phenylthiophene derivatives having general formula (XI):

[0056]

[0057] Among them, each R 20 They are the same or different from each other, and each is independently selected from C. 1-6 Straight-chain or branched alkyl groups; each p may be the same as or different from the others, and each is independently selected from an integer between 0 and 5; R 21 Selected from C 1-6 Straight-chain or branched alkyl groups and C 6-10 Aryl; R 22 Selected from C 1-6 Straight-chain or branched alkyl groups and C 6-10 Aryl.

[0058] In another aspect, the present invention provides a method for preparing a photoluminescent grease composition, comprising: mixing and refining a lubricating base oil, a thickener, and a photoluminescent material, and grinding them into a grease.

[0059] The thiophene derivatives of the present invention, having general formula (I), possess excellent photoluminescence properties and are capable of emitting light under ultraviolet light irradiation. They can be applied to light-emitting components and devices, fluorescent probes, bioimaging, lubricating oils, and greases. The greases of the present invention also exhibit photoluminescence properties. A preferred embodiment of the present invention's grease further possesses one or more of the following properties: antioxidant properties, anti-wear properties, extreme pressure properties, and rust prevention properties. The greases of the present invention can be used in related machinery and equipment in the electrical, metallurgical, food, paper, automotive, and aerospace industries. Detailed Implementation

[0060] The present disclosure will be further described in detail below through specific embodiments. It should be understood that the specific embodiments described herein are only for illustration and explanation of the present disclosure, and do not limit the present invention in any way.

[0061] Any specific numerical values ​​disclosed herein (including the endpoints of numerical ranges) are not limited to their exact values, but should be understood to also include values ​​close to the exact value, such as all possible values ​​within ±5% of the exact value. Furthermore, with respect to the disclosed numerical ranges, one or more new numerical ranges can be obtained by arbitrarily combining the endpoint values ​​of the range, the endpoint values ​​with specific point values ​​within the range, and the specific point values ​​themselves; these new numerical ranges should also be considered as specifically disclosed herein.

[0062] Unless otherwise stated, the terms used herein have the same meaning as commonly understood by those skilled in the art, and if a term is defined herein and its definition differs from the common understanding in the art, the definition herein shall prevail.

[0063] In this application, except where expressly stated, any matters or issues not mentioned are directly applicable to those known in the art without any modification. Furthermore, any implementation described herein can be freely combined with one or more other implementations described herein, and the resulting technical solutions or concepts are considered part of the original disclosure or original record of this invention, and should not be regarded as new content not disclosed or anticipated herein, unless those skilled in the art consider the combination to be clearly unreasonable.

[0064] This invention provides a photoluminescent material with aggregation-induced emission properties, which is a thiophene derivative having general formula (I):

[0065]

[0066] In general formula (I), each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups, each x is independently selected from an integer between 0 and 5;

[0067] Each G is independently selected from hydrogen and C. 1-6 Straight-chain or branched alkyl groups, alkynyl groups represented by formula (I-1), alkynyl groups represented by formula (I-2), alkynyl groups represented by formula (I-3), alkynyl groups represented by formula (I-4), and groups represented by formula (I-1').

[0068]

[0069]

[0070] In equations (I-1), (I-2), (I-3), and (I-4), each R1 is independently selected from hydrogen and C. 1-6 Straight-chain or branched alkyl groups; each R2 is independently selected from C 1-6 Straight-chain or branched alkylene groups; each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl; each x is independently selected from an integer between 0 and 5; each y is independently selected from an integer between 0 and 4; each z is independently selected from an integer between 1 and 4; in formula (I-1), one of A and A' is NR and the other is S, wherein R is selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups;

[0071] In equations (I), (I-2), and (I-3), each G' is independently selected from hydrogen and C. 1-6 Straight-chain or branched alkyl groups, groups represented by formula (I-1'), alkynyl groups represented by formula (I-2'), and alkynyl groups represented by formula (I-3');

[0072]

[0073]

[0074] In equations (I-1') and (I-2'), each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl; each x is independently selected from an integer between 0 and 5; each y' is independently selected from an integer between 0 and 3; each z' is independently selected from an integer between 0 and 3;

[0075] In equation (I-3'), R3, R4, and R5 are each independently selected from hydrogen, C, and C. 1-20 Straight-chain or branched alkyl groups (preferably C14) 1-10 The following groups may be used: straight-chain or branched alkyl groups; groups represented by formula (II-1); groups represented by formula (II-2); and groups represented by formula (II-3), provided that at least one of R3, R4, and R5 is a group represented by formula (II-1), a group represented by formula (II-2), or a group represented by formula (II-3) (preferably R4 is a group represented by formula (II-1), and R3 and R5 are hydrogen; or R3 and R5 are groups represented by formula (II-3), and R4 is hydrogen).

[0076]

[0077] In equations (II-1) and (II-2), R6 represents hydrogen and C. 1-6 Straight-chain or branched hydrocarbon groups (preferably hydrogen, C) 1-4 (straight-chain or branched alkyl), R7 is hydrogen, C 1-6Straight-chain or branched hydrocarbon groups (preferably hydrogen, C) 1-4 (linear or branched alkyl groups);

[0078]

[0079] In equation (II-3), R a Selected from hydrogen, C 1-20 Straight-chain or branched alkyl groups (preferably selected from C) 1-10 (straight-chain or branched alkyl); R b Selected from hydrogen, C 1-20 Straight-chain or branched alkyl groups;

[0080] In general formula (I), at least one G is selected from the alkynyl group shown in formula (I-1), the alkynyl group shown in formula (I-2), the alkynyl group shown in formula (I-3), or the alkynyl group shown in formula (I-4), or at least one G' is selected from the group shown in formula (I-1'), the alkynyl group shown in formula (I-2'), or the alkynyl group shown in formula (I-3').

[0081] Examples of thiol derivatives having the general formula (I) may include the following compounds:

[0082]

[0083]

[0084]

[0085] The present invention provides a first method for preparing the thiophene derivative having general formula (I), comprising the step of reacting a thiophene compound of general formula (III-1) with one or more alkyne compounds of general formulas (III-1'), (III-2'), (III-3'), (III-4'), (III-5'), and (III-6').

[0086]

[0087] In general formula (III-1), each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups, each x is independently selected from an integer between 0 and 5; each G is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups, groups represented by formula (I-1'), and X groups; each G' is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups, groups represented by formula (I-1'), and X groups;

[0088]

[0089] In equation (I-1'), each R is independently selected from hydrogen, C1-6 Straight-chain or branched alkyl groups; each x is independently selected from an integer between 0 and 5;

[0090] The X group is selected from F, Cl, Br, I, and OH, with Cl or Br being preferred;

[0091] At least one G or G' is selected from the X group;

[0092]

[0093]

[0094] In equations (III-1'), (III-2'), (III-3'), (III-4'), and (III-5'), each R1 is independently selected from hydrogen, C, and C. 1-6 Straight-chain or branched alkyl groups; each R2 is independently selected from C 1-6 Straight-chain or branched alkylene groups; each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl; each x is independently selected from an integer between 0 and 5; each y is independently selected from an integer between 0 and 4; each z is independently selected from an integer between 1 and 4; each y' is independently selected from an integer between 0 and 3; each z' is independently selected from an integer between 0 and 3.

[0095] In equation (III-1'), one of A and A' is NR, and the other is S, where R is selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups;

[0096] In equation (III-6'), R3, R4, and R5 are each independently selected from hydrogen, C, and C. 1-20 Straight-chain or branched alkyl groups (preferably C14) 1-10 The following are possible combinations of groups: linear or branched alkyl groups, hydroxyl groups, groups represented by formula (II-1), groups represented by formula (II-2), and groups represented by formula (II-3), provided that at least one of R3, R4, and R5 is a group represented by formula (II-1), a group represented by formula (II-2), a group represented by formula (II-3), or a hydroxyl group (preferably R4 is a group represented by formula (II-1), and R3 and R5 are hydrogen; or R3 and R5 are groups represented by formula (II-3), and R4 is hydrogen; or R3 and R5 are hydrogen, and R4 is a hydroxyl group).

[0097]

[0098] In equations (II-1) and (II-2), R6 represents hydrogen and C. 1-6 Straight-chain or branched hydrocarbon groups (preferably hydrogen, C) 1-4 (straight-chain or branched alkyl), R7 is hydrogen, C 1-6Straight-chain or branched hydrocarbon groups (preferably hydrogen, C) 1-4 (linear or branched alkyl groups);

[0099]

[0100] In equation (II-3), R a Selected from hydrogen, C 1-20 Straight-chain or branched alkyl groups (preferably selected from C) 1-10 (straight-chain or branched alkyl); R b Selected from hydrogen, C 1-20 Straight-chain or branched alkyl groups.

[0101] Preferably, in the reaction step of the first preparation method, the molar ratio between the thiophene compound represented by (III-1) and one or more alkyne compounds represented by general formulas (III-1'), (III-2'), (III-3'), (III-4'), (III-5'), or (III-6') is preferably 0.1-10:1, most preferably 0.2-5:1. The reaction temperature is 0-50°C, preferably 15-35°C. Generally, the longer the reaction time, the better; the reaction time is preferably 12-96 h, more preferably 24-72 h.

[0102] Preferably, in the first preparation method, a catalyst is added to the reaction of the thiophene compound shown in (III-1) with one or more alkyne compounds shown in general formulas (III-1'), (III-2'), (III-3'), (III-4'), (III-5'), and (III-6'). The catalyst is preferably one or more of a metal phosphine complex, a metal halide, a hydrocarbon phosphine compound, and an azo compound; more preferably, it is a mixture of a metal phosphine complex, a metal halide, and a hydrocarbon phosphine compound, wherein the molar ratio of the three is preferably 1:0.1-10:0.1-10, more preferably 1:0.2-5:0.2-5.

[0103] Preferably, in the first preparation method, the structure of the metal phosphine complex is as follows: Wherein M is Pd, Ru, or Rh, and L is selected from PPh3, Ph, F, Cl, Br, and I. The metal phosphine complex may be one or more of tetrakis(triphenylphosphine)palladium, trikis(triphenylphosphine)chloride, dikis(triphenylphosphine)dichloride, (triphenylphosphine)trichloride, tetrakis(triphenylphosphine)ruthenium, trikis(triphenylphosphine)ruthenium, dikis(triphenylphosphine)dichloride, (triphenylphosphine)ruthenium, tetrakis(triphenylphosphine)rhodium, trikis(triphenylphosphine)rhodium, dikis(triphenylphosphine)dichloride, and (triphenylphosphine)rhodium, preferably one or more of tetrakis(triphenylphosphine)palladium, trikis(triphenylphosphine)chloride, dikis(triphenylphosphine)dichloride, and (triphenylphosphine)trichloride.

[0104] Preferably, in the first preparation method, the metal halide can be one or more of copper halides, iron halides, and zinc halides. For example, it can be one or more of copper chloride, cuprous chloride, copper bromide, cuprous bromide, copper iodide, cuprous iodide, ferric chloride, ferrous chloride, ferrous bromide, ferrous bromide, ferrous iodide, zinc chloride, zinc chloride, zinc bromide, zinc bromide, zinc iodide, and zinc iodide. More preferably, it can be one or more of copper chloride, cuprous chloride, copper bromide, cuprous bromide, copper iodide, and cuprous iodide.

[0105] Preferably, in the first preparation method, the structure of the hydrocarbon-based phosphine compound is as follows: Each R is independently selected from C6-C 10 The aryl group and the C1-C6 straight-chain or branched alkyl group, wherein at least one R is C6-C 10 The aryl group. The C6-C 10 The aryl group can be selected from phenyl or naphthyl; the C1-C6 straight-chain or branched alkyl group can be selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, or isohexyl. The alkylphosphine compound can be triphenylphosphine or diphenylbutylphosphine.

[0106] Preferably, in the first preparation method, the azo compound has the following structure: In the formula, each R' may be the same or different from the others, and each is independently selected from hydrogen, C, etc. 1-6 Straight-chain or branched alkyl groups, C 3-10 cycloalkyl, C 6-10 Aryl and C 1-6 Alkoxy group. The azo compound is preferably one or more selected from dimethyl azodiacetic acid, diethyl azodiacetic acid, dipropyl azodiacetic acid, and dibutyl azodiacetic acid.

[0107] Preferably, in the first preparation method, the amount of catalyst added is preferably 0.1%-100% of the mass of the thiophene compound shown in formula (III-1).

[0108] The present invention also provides a second method for preparing the thiophene derivative having general formula (I), comprising: reacting a thiophene compound of general formula (III-1-1) with one or more compounds of general formulas (III-1'-1), (III-2'-1), (III-3'-1), (III-4'-1), (III-5'-1), and (III-6'-1),

[0109]

[0110] In general formula (III-1-1), each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups, each x is independently selected from an integer between 0 and 5; each G is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups, groups represented by formula (I-1') and (Right now Each G' is independently selected from hydrogen and C. 1-6 Straight-chain or branched alkyl groups, groups represented by formula (I-1') and

[0111]

[0112] In equation (I-1'), each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups; each x is independently selected from an integer between 0 and 5;

[0113] At least one G or G' is selected from

[0114]

[0115] The X group is selected from F, Cl, Br, I, and OH, with Cl or Br being preferred;

[0116] In equations (III-1'-1), (III-2'-1), (III-3'-1), (III-4'-1), and (III-5'-1), each R1 is independently selected from hydrogen and C. 1-6 Straight-chain or branched alkyl groups; each R2 is independently selected from C 1-6 Straight-chain or branched alkylene groups; each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl; each x is independently selected from an integer between 0 and 5; each y is independently selected from an integer between 0 and 4; each z is independently selected from an integer between 1 and 4; each y' is independently selected from an integer between 0 and 3; each z' is independently selected from an integer between 0 and 3.

[0117] In equation (III-1'-1), one of A and A' is NR, and the other is S, where R is selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups;

[0118] In equation (III-6'-1), R3, R4, and R5 are each independently selected from hydrogen, C, and C. 1-20 Straight-chain or branched alkyl groups (preferably C14) 1-10The following are possible combinations of groups: linear or branched alkyl groups, hydroxyl groups, groups represented by formula (II-1), groups represented by formula (II-2), and groups represented by formula (II-3), provided that at least one of R3, R4, and R5 is a group represented by formula (II-1), a group represented by formula (II-2), a group represented by formula (II-3), or a hydroxyl group (preferably R4 is a group represented by formula (II-1), and R3 and R5 are hydrogen; or R3 and R5 are groups represented by formula (II-3), and R4 is hydrogen; or R3 and R5 are hydrogen, and R4 is a hydroxyl group).

[0119]

[0120] In equations (II-1) and (II-2), R6 represents hydrogen and C. 1-6 Straight-chain or branched hydrocarbon groups (preferably hydrogen, C) 1-4 (straight-chain or branched alkyl), R7 is hydrogen, C 1-6 Straight-chain or branched hydrocarbon groups (preferably hydrogen, C) 1-4 (linear or branched alkyl groups);

[0121]

[0122] In equation (II-3), R a Selected from hydrogen, C 1-20 Straight-chain or branched alkyl groups (preferably selected from C) 1-10 (straight-chain or branched alkyl); R b Selected from hydrogen, C 1-20 Straight-chain or branched alkyl groups.

[0123] In the second preparation method, preferably, the molar ratio between the thiophene compound represented by (III-1-1) and one or more compounds represented by general formulas (III-1'-1), (III-2'-1), (III-3'-1), (III-4'-1), (III-5'-1), or (III-6'-1) is 0.1-10:1, most preferably 0.2-5:1. The reaction temperature is 0-50°C, preferably 15-35°C. Generally, the longer the reaction time, the better; the reaction time is preferably 12-96 h, more preferably 24-72 h.

[0124] In the second preparation method, preferably, a catalyst is added to the reaction of the thiophene compound shown in (III-1-1) with one or more compounds shown in general formulas (III-1'-1), (III-2'-1), (III-3'-1), (III-4'-1), (III-5'-1), and (III-6'-1). The catalyst is preferably one or more of a metal phosphine complex, a metal halide, a hydrocarbon phosphine compound, and an azo compound; more preferably, a mixture of a metal phosphine complex, a metal halide, and a hydrocarbon phosphine compound; the molar ratio of the three is preferably 1:0.1-10:0.1-10, more preferably 1:0.2-5:0.2-5.

[0125] In the second preparation method, preferably, the structure of the metal phosphine complex is as follows: Wherein M is Pd, Ru, or Rh, and L is selected from PPh3, Ph, F, Cl, Br, and I. The metal phosphine complex may be one or more of tetrakis(triphenylphosphine)palladium, trikis(triphenylphosphine)chloride, dikis(triphenylphosphine)dichloride, (triphenylphosphine)trichloride, tetrakis(triphenylphosphine)ruthenium, trikis(triphenylphosphine)ruthenium, dikis(triphenylphosphine)dichloride, (triphenylphosphine)ruthenium, tetrakis(triphenylphosphine)rhodium, trikis(triphenylphosphine)rhodium, dikis(triphenylphosphine)dichloride, and (triphenylphosphine)rhodium, preferably one or more of tetrakis(triphenylphosphine)palladium, trikis(triphenylphosphine)chloride, dikis(triphenylphosphine)dichloride, and (triphenylphosphine)trichloride.

[0126] In the second preparation method, preferably, the metal halide can be one or more of copper halides, iron halides, and zinc halides. For example, it can be one or more of copper chloride, cuprous chloride, copper bromide, cuprous bromide, copper iodide, cuprous iodide, ferric chloride, ferrous chloride, ferrous bromide, ferrous bromide, ferrous iodide, zinc chloride, zinc chloride, zinc bromide, zinc bromide, zinc iodide, and zinc iodide. More preferably, it can be one or more of copper chloride, cuprous chloride, copper bromide, copper bromide, copper iodide, and cuprous iodide.

[0127] In the second preparation method, preferably, the structure of the hydrocarbon phosphine compound is as follows: Each R is independently selected from C6-C 10 The aryl group and the C1-C6 straight-chain or branched alkyl group, wherein at least one R is C6-C 10 The aryl group. The C6-C 10 The aryl group can be selected from phenyl or naphthyl; the C1-C6 straight-chain or branched alkyl group can be selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, or isohexyl. The alkylphosphine compound can be triphenylphosphine or diphenylbutylphosphine.

[0128] In the second preparation method, preferably, the azo compound has the following structure: In the formula, each R' may be the same or different from the others, and each is independently selected from hydrogen, C, etc. 1-6 Straight-chain or branched alkyl groups, C 3-10 cycloalkyl, C 6-10 Aryl and C 1-6 Alkoxy group. The azo compound is preferably one or more selected from dimethyl azodiacetic acid, diethyl azodiacetic acid, dipropyl azodiacetic acid, and dibutyl azodiacetic acid.

[0129] In the second preparation method, preferably, the amount of catalyst added is 0.1%-100% of the mass of the thiophene compound shown in formula (III-1-1).

[0130] This invention provides a photoluminescent grease composition comprising a luminescent material (particularly a photoluminescent material with aggregation-induced emission properties), a thickener, and a base lubricating oil. The luminescent material comprises 0.0005%-5% of the total mass of the grease composition, preferably 0.001%-2%; the thickener comprises 5%-30% of the total mass of the grease composition, preferably 10%-20%; and the base lubricating oil constitutes the main component of the grease composition.

[0131] Preferably, the photoluminescent material with aggregation-induced emission properties includes tetraphenylethylene compounds and thiophene derivatives.

[0132] Preferably, the tetraphenylethylene compound includes tetraphenylethylene or its derivatives, and more preferably, the structure of the tetraphenylethylene compound is as follows:

[0133]

[0134] Among them, each R 11 They are the same or different from each other, and each is independently selected from C. 1-6 Straight-chain or branched alkyl groups (preferably selected from C) 1-4 (straight-chain or branched alkyl); each m may be the same as or different from each other, and each is independently selected from an integer between 0 and 5 (preferably selected from 0, 1, 2 or 3).

[0135] Preferably, the tetraphenylethylene compound comprises the following compounds or mixtures thereof:

[0136]

[0137] Preferably, the thiophene derivative comprises the thiophene derivative having general formula (I) and a phenylthiophene derivative having general formula (XI):

[0138]

[0139] Among them, each R 20 They are the same or different from each other, and each is independently selected from C. 1-6 Straight-chain or branched alkyl groups (preferably selected from C) 1-4 (Straight-chain or branched alkyl); each p may be the same or different from each other, and each is independently selected from an integer between 0 and 5 (preferably selected from 0, 1, 2 or 3); R 21 Selected from C 1-6 Straight-chain or branched alkyl groups and C 6-10 Aryl (preferably selected from C) 1-4 (Straight-chain or branched alkyl, phenyl, and naphthyl); R2 is selected from C 1-6 Straight-chain or branched alkyl groups and C 6-10 Aryl (preferably selected from C) 1-4 Straight-chain or branched alkyl, phenyl, and naphthyl groups.

[0140] Preferably, the thiophene derivative having the general formula (XI) comprises the following compounds or mixtures thereof:

[0141]

[0142] The thickener includes one or more of polyurea thickener, calcium-based thickener, and composite aluminum-based thickener, preferably polyurea thickener or composite aluminum-based thickener.

[0143] The thickener can be a soap-based thickener or a non-soap-based thickener. The soap-based thickener is preferably a metal soap, which can be a single metal soap or a composite metal soap. The metal can be one or more of lithium, sodium, calcium, aluminum, zinc, potassium, barium, lead, and manganese. The non-soap-based thickener is preferably one or more of graphite, carbon black, asbestos, polyurea, bentonite, and organoclay.

[0144] The lubricating base oil may be one or more of mineral oil, vegetable oil and synthetic oil, preferably mineral oil or synthetic oil.

[0145] This invention provides a method for preparing a photoluminescent grease composition, comprising: mixing and refining a lubricating base oil, a thickener, and a luminescent material (particularly a photoluminescent material with aggregation-induced emission properties), and grinding it into a grease. The refining temperature is 160-240℃, preferably 180-220℃; the refining time is 10-240 min, preferably 20-60 min. Alternatively, all the lubricating base oil, the photoluminescent material with aggregation-induced emission properties, and the thickener can be mixed and refined together. Or, a portion of the lubricating base oil, a portion of the photoluminescent material with aggregation-induced emission properties, and the thickener can be mixed and refined, and then mixed with the remaining lubricating base oil and the remaining photoluminescent material with aggregation-induced emission properties.

[0146] The grease composition is preferably a polyurea grease composition, a lithium-based grease composition, or a composite aluminum-based grease composition.

[0147] The preparation method of the polyurea grease composition of the present invention includes: mixing a portion of lubricating base oil, the photoluminescent material having aggregation-induced light-emitting properties, an amine, and an isocyanate; reacting at 65-95°C for 10-60 minutes; after the reaction is complete, continuing to heat to 190-220°C for high-temperature refining; then adding the remaining base oil; cooling to 60-120°C; and grinding into a grease. The amine is C2-C... 20 Alkylamines and / or C6-C 20 Aromatic amines, such as octadecylamine, cyclohexylamine, and aniline, may be one or more of these; the isocyanate is C2-C. 20 The isocyanate can be one or more of toluene diisocyanate (TDI) and 4,4'-diphenylmethane diisocyanate (MDI).

[0148] The preparation method of the lithium-based lubricating grease composition of the present invention includes: mixing a portion of lubricating base oil and fatty acid in a reaction vessel and heating the mixture to 40-90°C; adding the photoluminescent material with aggregation-induced luminescence properties and an aqueous solution of lithium hydroxide; heating to remove water; continuing to heat to 190-220°C for high-temperature refining; adding the remaining lubricating base oil; cooling to 60-120°C; and grinding into a grease. The fatty acid is C... 12 -C 20 Fatty acids and / or C 12 -C 20 Hydroxy fatty acids can be one or more of lauric acid, palmitic acid, stearic acid, and 12-hydroxystearic acid.

[0149] The preparation method of the composite aluminum-based lubricating grease composition of the present invention includes: mixing and heating a portion of base oil, fatty acid, and small molecule acid in a reaction vessel to 40-90°C; adding the photoluminescent material with aggregation-induced luminescence properties; mixing another portion of lubricating base oil with an aluminum alkoxide compound and heating to 40-100°C; adding the aluminum alkoxide compound to the reaction vessel after it has completely dissolved; continuing to heat to 190-220°C for high-temperature refining; adding the remaining lubricating base oil; cooling to 60-120°C; and grinding into a grease. The fatty acid is C... 12 -C 20 Fatty acids and / or C 12 -C 20 The hydroxy fatty acid may be one or more of lauric acid, palmitic acid, stearic acid, and 12-hydroxystearic acid; the small molecule acid is C2-C. 11The organic acid can be one or more of acetic acid, propionic acid, oxalic acid, adipic acid, azelaic acid, sebacic acid, and terephthalic acid; the aluminum alkoxide compound is preferably selected from aluminum isopropoxide, aluminum isopropoxide dimer, and aluminum isopropoxide trimer.

[0150] In the method for preparing the lubricating grease composition of the present invention, preferably, a photoluminescent material having aggregation-induced emission properties is dissolved in a solvent beforehand. The solvent is preferably an aromatic solvent, such as benzene, toluene, or xylene, and the weight of the solvent is 0.5-1000 times, preferably 1-100 times, and more preferably 5-50 times, the weight of the photoluminescent material having aggregation-induced emission properties.

[0151] Example

[0152] The following embodiments will further illustrate this disclosure, but are not intended to limit it.

[0153] First Implementation Method

[0154] According to a first embodiment of the present invention, the structure of the thiophene derivative having general formula (I) is as follows:

[0155]

[0156] In general formula (II), each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups, each n independently selected from an integer between 0 and 5; R1 and R2 may be the same or different from each other, and are independently selected from hydrogen and C. 1-6 Straight-chain or branched alkyl groups; R3, R4, R5, R3', R4', and R5' may be the same as or different from each other, and each is independently selected from hydrogen, C 1-300 Straight-chain or branched alkyl groups (preferably C14) 1-10 The following are groups of general formula (II-I): straight-chain or branched alkyl groups or polyolefin groups with a number average molecular weight Mn of 300-3000; provided that at least one of R3, R4, and R5 is a group of general formula (II-I) and at least one of R3', R4', and R5' is a group of general formula (II-I).

[0157]

[0158] Each group R a They may be the same as or different from each other, and each is independently selected from hydrogen and C. 1-20 Straight-chain or branched alkyl groups (preferably selected from C) 1-10 Straight-chain or branched alkyl groups and groups represented by general formulas (II-I); each group R b They may be the same as or different from each other, and each is independently selected from hydrogen and C. 1-20 Straight-chain or branched alkyl groups and groups represented by general formulas (II-I).

[0159] According to a first embodiment of the present invention, R3 and R5 are preferably groups represented by general formula (II-I); R3' and R5' are preferably groups represented by general formula (II-I); R4 and R4' are preferably hydrogen or groups represented by general formula (II-I). According to the present invention, the thiophene derivative having general formula (II) includes the following compounds:

[0160]

[0161] The preparation of the thiophene derivative having general formula (II) according to the second preparation method of the present invention includes the step of reacting a thiophene compound represented by general formula (III-I) and an alkyne compound represented by general formula (IV-I).

[0162]

[0163] In the general formula (III-I), each R is independently selected from hydrogen, C, and so on. 1-6 Straight-chain or branched alkyl groups, each n independently selected from integers between 0 and 5; each group X may be the same or different from each other, and is independently selected from F, Cl, Br, I, OH, preferably Cl or Br; R1 and R2 may be the same or different from each other, and are independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups; R3, R4, and R5 may be the same or different from each other, and each is independently selected from hydrogen, C... 1-300 Straight-chain or branched alkyl groups (preferably C14) 1-10 The groups are straight-chain or branched alkyl groups or polyolefin groups with a number average molecular weight Mn of 300-3000, and are represented by the general formula (VI), provided that at least one of the groups R3, R4, and R5 is represented by the general formula (VI).

[0164]

[0165] Each group R a They may be the same as or different from each other, and each is independently selected from hydrogen and C. 1-20 Straight-chain or branched alkyl groups (preferably selected from C) 1-10 (Straight-chain or branched alkyl); each group R b They may be the same as or different from each other, and each is independently selected from hydrogen and C. 1-20 Straight-chain or branched alkyl groups.

[0166] Thiol compounds of general formula (III-I) that can be used include:

[0167]

[0168] Alkyne compounds of general formula (IV-I) that can be used include:

[0169]

[0170] A catalyst is preferably added to the reaction. The type and amount of the catalyst are as described above. According to a first embodiment of the invention, preferably, in the reaction, the molar ratio between the thiophene compound represented by general formula (III-I) and the alkyne compound represented by general formula (IV-I) is 1-6:1, most preferably 2-4:1. The reaction temperature is 0-50°C, preferably 15-35°C. The reaction time is 12-96 h, preferably 24-72 h.

[0171] The specific sources of the raw materials used in the examples are as follows:

[0172] The chemical reagents, including 1,1-dimethyl-2,5-dibromo-3,4-diphenylthiophene, 3,5-di(dimethylamino)phenylacetylene, 3,5-di(diethylamino)phenylacetylene, 3,5-di(dipropylamino)phenylacetylene, cuprous iodide, triphenylphosphine, tetra-triphenylphosphine palladium, octadecylamine, MDI, stearic acid, benzoic acid, aluminum isopropoxide trimer, tetrahydrofuran, triethylamine, dichloromethane, and methanol, were obtained from Bailingwei Reagent Company, Inokai Reagent Company, or Sigma Reagent Company, and were of analytical grade. The PAO10 base oil was obtained from ExxonMobil, and 500SN was obtained from SK Chemicals.

[0173] Example I-1

[0174] In a 100 mL Schlenk reaction flask, 420 mg (1 mmol) of 1,1-dimethyl-2,5-dibromo-3,4-diphenylthiophene, 733 mg (3 mmol) of 3,5-di(diethylamino)phenylacetylene, 19 mg (0.1 mmol) of cuprous iodide, and 26 mg (0.1 mmol) of triphenylphosphine were added. Under nitrogen protection, 23 mg (0.02 mmol) of tetratetraphenylphosphine palladium and 30 mL of tetrahydrofuran / triethylamine (2 / 1, v / v) were added, and the reaction was carried out at room temperature for 48 hours. After the reaction was completed, the mixture was filtered and the filtrate was evaporated to dryness. The product was separated and purified by column chromatography using a dichloromethane / methanol (20 / 1, v / v) mixture as the eluent, yielding 460 mg of a yellow solid product, with a yield of 62%. The NMR results of the product are as follows: 1 H NMR (400MHz, CDCl3), δ (TMS, ppm): 7.11–6.85 (m, 10H), 6.57 (m, 4H), 6.36 (m, 2H), 3.43 (m, 16H), 1.27 (m, 24H), 0.49 (s, 6H); MS (MALDI-TOF): m / z calcd:746.5[M]+,found:746.5.

[0175] Example equations are shown below:

[0176]

[0177] Example I-2

[0178] In a 100 mL Schlenk reaction flask, 420 mg (1 mmol) of 1,1-dimethyl-2,5-dibromo-3,4-diphenylthiophene, 901 mg (3 mmol) of 3,5-bis(dipropylamino)phenylacetylene, 19 mg (0.1 mmol) of cuprous iodide, and 26 mg (0.1 mmol) of triphenylphosphine were added. Under nitrogen protection, 23 mg (0.02 mmol) of tetratetraphenylphosphine palladium and 30 mL of tetrahydrofuran / triethylamine (2 / 1, v / v) were added, and the reaction was carried out at room temperature for 48 hours. After the reaction was completed, the mixture was filtered and the filtrate was evaporated to dryness. The product was separated and purified by column chromatography using a dichloromethane / methanol (20 / 1, v / v) mixture as the eluent, yielding 507 mg of a yellow solid product, with a yield of 59%. The NMR results of the product were as follows: 1 H NMR (400MHz, CDCl3), δ (TMS, ppm): 7.12–6.84 (m, 10H), 6.55 (m, 4H), 6.34 (m, 2H ),3.42(m,16H),1.62(m,16H),0.83(m,24H),0.49(s,6H); MS(MALDI-TOF):m / z calcd:858.6[M]+,found:858.6.

[0179] Example equations are shown below:

[0180]

[0181] Example I-3

[0182] In a 100 mL Schlenk reaction flask, 420 mg (1 mmol) of 1,1-dimethyl-2,5-dibromo-3,4-diphenylthiophene, 565 mg (3 mmol) of 3,5-di(dimethylamino)phenylacetylene, 19 mg (0.1 mmol) of cuprous iodide, and 26 mg (0.1 mmol) of triphenylphosphine were added. Under nitrogen protection, 23 mg (0.02 mmol) of tetratetraphenylphosphine palladium and 30 mL of tetrahydrofuran / triethylamine (2 / 1, v / v) were added, and the reaction was carried out at room temperature for 48 hours. After the reaction was completed, the mixture was filtered and the filtrate was evaporated to dryness. The product was separated and purified by column chromatography using a dichloromethane / methanol (20 / 1, v / v) mixture as the eluent, yielding 406 mg of a yellow solid product, with a yield of 64%. The NMR results of the product were as follows: 1¹H NMR (400MHz, CDCl₃), δ (TMS, ppm): 7.10–6.84 (m, 10H), 6.55 (m, 4H), 6.35 (m, 2H), 3.12 (m, 24H), 0.49 (s, 6H); MS (MALDI-TOF): m / z calcd: 634.4 [M]⁺, found: 634.4. Example equations are shown below.

[0183]

[0184] Example I-4

[0185] 60g of 500SN base oil and 7.84g of 12-hydroxystearic acid were mixed in a reaction vessel and heated to 85°C. 0.2g of 1,1-dimethyl-2,5-bis(3,5-diethylaminophenylethynyl)-3,4-diphenylthiophene was dissolved in 5g of toluene and added to the reaction vessel. 1.21g of lithium hydroxide monohydrate was mixed with 8g of distilled water and heated to 95°C. After the lithium hydroxide was completely dissolved, it was added to the reaction vessel for saponification reaction for 20min. The mixture was stirred and heated to 110-150°C for dehydration and detoxification. Then, the temperature was further increased to 210°C for high-temperature refining for 10min. 32g of 500SN base oil was added. After cooling to 110°C, 0.5g of barium petroleum sulfonate and 1g of dialkyl dithiocarbamate were added. After cooling to room temperature, the mixture was ground into a grease.

[0186] Example I-5

[0187] 60g of 500SN base oil and 7.84g of 12-hydroxystearic acid were mixed in a reaction vessel and heated to 85°C. 0.5g of 1,1-dimethyl-2,5-bis(3,5-diethylaminophenylethynyl)-3,4-diphenylthiophene was dissolved in 5g of toluene and added to the reaction vessel. 1.21g of lithium hydroxide monohydrate was mixed with 8g of distilled water and heated to 95°C. After the lithium hydroxide was completely dissolved, it was added to the reaction vessel for saponification reaction for 20min. The mixture was stirred and heated to 110-150°C for dehydration and detoxification. Then, the temperature was further increased to 210°C for high-temperature refining for 10min. 32g of 500SN base oil was added. After cooling to 110°C, 0.5g of barium petroleum sulfonate and 1g of dialkyl dithiocarbamate were added. After cooling to room temperature, the mixture was ground into a grease.

[0188] Example I-6

[0189] 60g of PAO10 base oil and 7.84g of 12-hydroxystearic acid were mixed in a reaction vessel and heated to 85°C. 0.2g of 1,1-dimethyl-2,5-bis(3,5-diethylaminophenylethynyl)-3,4-diphenylthiophene was dissolved in 5g of toluene and added to the reaction vessel. 1.21g of lithium hydroxide monohydrate was mixed with 8g of distilled water and heated to 95°C. After the lithium hydroxide was completely dissolved, it was added to the reaction vessel for saponification reaction for 20min. The mixture was stirred and heated to 110-150°C for dehydration and detoxification. Then, the temperature was further increased to 210°C for high-temperature refining for 10min. 32g of PAO10 base oil was added. After cooling to 110°C, 0.5g of barium dinonylnaphthalenesulfonate and 1g of dialkyl dithiocarbamate were added. After cooling to room temperature, the mixture was ground into a grease.

[0190] Example I-7

[0191] 60g of PAO10 base oil and 7.84g of 12-hydroxystearic acid were mixed in a reaction vessel and heated to 85°C. 0.5g of 1,1-dimethyl-2,5-bis(3,5-diethylaminophenylethynyl)-3,4-diphenylthiophene was dissolved in 5g of toluene and added to the reaction vessel. 1.21g of lithium hydroxide monohydrate was mixed with 8g of distilled water and heated to 95°C. After the lithium hydroxide was completely dissolved, it was added to the reaction vessel for saponification reaction for 20min. The mixture was stirred and heated to 110-150°C for dehydration and detoxification. Then, the temperature was further increased to 210°C for high-temperature refining for 10min. 32g of PAO10 base oil was added. After cooling to 110°C, 0.5g of barium dinonylnaphthalenesulfonate and 1g of dialkyl dithiocarbamate were added. After cooling to room temperature, the mixture was ground into a grease.

[0192] Example I-8

[0193] Mix 60g of PAO10 base oil with 7.84g of 12-hydroxystearic acid in a reaction vessel and heat to 85°C. Mix 1.21g of lithium hydroxide monohydrate with 8g of distilled water and heat to 95°C. After the lithium hydroxide is completely dissolved, add it to the reaction vessel for saponification reaction for 20min. Stir and heat to 110-150°C for dehydration, then continue to heat to 210°C for high-temperature refining for 10min. Add 32g of PAO10 base oil, cool to 110°C, and add 0.5g of 1,1-dimethyl-2,5-bis(3,5-diethylaminophenylethynyl)-3,4-diphenylthiophene, 0.5g of barium dinonylnaphthalenesulfonate, and 1g of dialkyl dithiocarbamate. After cooling to room temperature, grind into a grease.

[0194] Comparative Example I-1

[0195] Mix 60g of 500SN base oil and 7.84g of 12-hydroxystearic acid in a reaction vessel and heat to 85°C. Mix 1.21g of lithium hydroxide monohydrate and 8g of distilled water and heat to 95°C. After the lithium hydroxide is completely dissolved, add it to the reaction vessel for saponification reaction for 20min. Stir and heat to 110-150°C for dehydration, then continue to heat to 210°C for high-temperature refining for 10min. Add 160g of 500SN base oil, cool to 110°C, and add 0.5g of diphenylamine, 0.5g of barium petroleum sulfonate, and 1g of dialkyl dithiocarbamate. After cooling to room temperature, grind into grease.

[0196] Comparative Example I-2

[0197] Mix 60g of PAO10 base oil with 7.84g of 12-hydroxystearic acid in a reaction vessel and heat to 85°C. Mix 1.21g of lithium hydroxide monohydrate with 8g of distilled water and heat to 95°C. After the lithium hydroxide is completely dissolved, add it to the reaction vessel for saponification reaction for 20min. Stir and heat to 110-150°C for dehydration, then continue to heat to 210°C for high-temperature refining for 10min. Add 32g of PAO10 base oil, cool to 110°C and add 0.5g of diphenylamine, 0.5g of barium dinonylnaphthalenesulfonate and 1g of dialkyl dithiocarbamate. After cooling to room temperature, grind into a grease.

[0198] The performance of the greases in Examples I-4-I-8, Comparative Examples I-1, and I-2 was evaluated. The evaluation methods included the following: Grease wide temperature range dropping point test method GB / T 3498, Grease and petroleum grease cone penetration test method GB / T 269, Grease oxidation stability test method SH / T0325, Grease stencil oil separation test method SH / T 0324, Grease extreme pressure performance test method SH / T0202, Grease anti-wear performance test method SH / T 0204, and Grease copper strip corrosion test method GB / T 7326. The evaluation results are shown in Tables I-1 and I-2.

[0199] Table I-1 Performance Evaluation of Lubricating Greases

[0200]

[0201] Second Implementation Method

[0202] According to a second embodiment of the present invention, the structure of the thiophene derivative having general formula (I) is as follows:

[0203]

[0204] In equations (I-II), each R is independently selected from hydrogen, C 1-6Straight-chain or branched alkyl groups, each n independently selected from an integer between 0 and 5; R1 and R2 may be the same or different from each other, and are independently selected from hydrogen and C. 1-6 Straight-chain or branched alkyl groups; R3, R4, R5, R3', R4', and R5' may be the same as or different from each other, and each is independently selected from hydrogen, C 1-300 Straight-chain or branched hydrocarbon groups (preferably C) 1-10 The following are provided: straight-chain or branched hydrocarbon groups or polyolefin groups with a number average molecular weight Mn of 300-3000; groups represented by formula (II-II) and groups represented by formula (III-II), provided that at least one of R3, R4, and R5 is a group represented by formula (II-II), and at least one of R3', R4', and R5' is a group represented by formula (II-II) or (III-II);

[0205]

[0206] Where R6 is hydrogen, C 1-6 Straight-chain or branched hydrocarbon groups (preferably hydrogen, C) 1-4 (straight-chain or branched alkyl), R7 is hydrogen, C 1-6 Straight-chain or branched hydrocarbon groups (preferably hydrogen, C) 1-4 (linear or branched alkyl groups).

[0207] The preparation of the thiophene derivative having general formula (I-II) according to the second preparation method of the present invention includes the step of reacting the thiophene compound represented by formula (IV-II) and the alkyne compound represented by formula (V-II).

[0208]

[0209] In formula (IV-II), each group X may be the same or different from each other, and each is independently selected from F, Cl, Br, I, OH, preferably Cl or Br; R1, R2, R3, R4, and R5 in formula (IV-II) and formula (V-II) are the same as described above.

[0210] Thiol compounds of formula (IV-II) that can be used include:

[0211]

[0212] The alkyne compounds represented by formula (V-II) that can be used include:

[0213]

[0214] According to a second embodiment of the present invention, preferably, a catalyst is added to the reaction. The type and amount of the catalyst are the same as in the first embodiment.

[0215] According to a second embodiment of the present invention, preferably, a solvent is added to the reaction. The solvent is preferably C1-C2. 10 Organic amines and furans, such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, and tetrahydrofuran, can be selected, with C1-C being the most preferred. 10 The solvent is a mixture of an organic amine and furan, with a volume ratio preferably of 1:0.1-10. The amount of solvent added is preferably 10-500 times the mass of the thiophene compound shown in formula (IV-II).

[0216] According to a second embodiment of the present invention, preferably, the reaction is carried out under an inert gas protection, and most preferably under a nitrogen protection.

[0217] According to a second embodiment of the present invention, preferably, in the reaction, the molar ratio between the thiophene compound represented by formula (IV-II) and the alkyne compound represented by formula (V-II) is 1-6, most preferably 2-4. The reaction temperature is 0-50°C, preferably 15-35°C. The reaction time is 12-96 h, preferably 24-72 h.

[0218] According to a second embodiment of the present invention, preferably, the product of the reaction is purified. Purification can be performed by one or more of the following methods: filtration, washing with water, distillation, column chromatography, and recrystallization, without particular limitation. When column chromatography is used to purify the product of the reaction, dichloromethane and / or methanol are preferably used as eluents, more preferably a mixture of dichloromethane and methanol, with a preferred volume ratio of 5-50:1.

[0219] The specific sources of the raw materials used in the examples are as follows:

[0220] The chemical reagents, including 1,1-dimethyl-2,5-dibromo-3,4-diphenylthiophene, 1,1-diphenyl-2,5-dibromo-3,4-diphenylthiophene, 4-(dicyanovinyl)phenylacetylene, cuprous iodide, triphenylphosphine, tetratriphenylphosphine palladium, octadecylamine, MDI, tetrahydrofuran, triethylamine, dichloromethane, and methanol, were obtained from Bailingwei Reagent Company, Inokai Reagent Company, or Sigma Reagent Company, and were of analytical grade; the PAO10 base oil was obtained from ExxonMobil.

[0221] The testing methods used are as follows:

[0222] Test methods for wide temperature range dropping point of grease (GB / T 3498), test method for cone penetration of grease and petroleum grease (GB / T269), test method for oil separation of grease on steel mesh (SH / T 0324), test method for extreme pressure properties of grease (SH / T0202), test method for anti-wear properties of grease (SH / T 0204), test method for copper strip corrosion of grease (GB / T 7326).

[0223] Example II-1

[0224] In a 100 mL Schlenk reaction flask, 420 mg (1 mmol) of 1,1-dimethyl-2,5-dibromo-3,4-diphenylthiophene, 534 mg (3 mmol) of 4-(dicyanovinyl)phenylacetylene, 19 mg (0.1 mmol) of cuprous iodide, and 26 mg (0.1 mmol) of triphenylphosphine were added. Under nitrogen protection, 23 mg (0.02 mmol) of tetratetraphenylphosphine palladium and 30 mL of tetrahydrofuran / triethylamine (2 / 1, v / v) were added, and the reaction was carried out at 25 °C for 48 hours. After the reaction, the mixture was filtered, and the filtrate was evaporated to dryness. The product was purified by column chromatography using a dichloromethane / methanol (20 / 1, v / v) mixture as the eluent, yielding 360 mg of a red solid product, with a yield of 59%. NMR results were as follows: 1 H NMR (400MHz, CDCl3), δ (TMS, ppm): 7.79 (s, 2H), 7.51 (d, 4H), 7.35 (d, 4H), 7.12–6.85 (m, 10H), 0.49 (s, 6H) MS (MALDI-TOF): m / z calcd: 614.2[M] + ,found:614.1. An example reaction is shown below.

[0225]

[0226] Example II-2

[0227] Mix 145g of PAO10 base oil with 44.39g of octadecylamine in a reaction vessel and heat to 60°C. Dissolve 2.5g of 1,1-dimethyl-2,5-bis(dicyanovinylphenylethynyl)-3,4-diphenylthiophene in 25g of toluene and add to the reaction vessel. Mix 145g of PAO10 base oil with 20.61g of MDI and heat to 60°C. After the MDI is completely dissolved, add to the reaction vessel and heat to 80°C. React for 30 minutes, then continue heating to 210°C. Add another 145g of PAO10 base oil and cool to about 100°C before grinding.

[0228] Comparative Example II-1

[0229] Mix 145g of PAO10 base oil with 44.39g of octadecylamine in a reaction vessel and heat to 60°C. Mix 145g of PAO10 base oil with 20.61g of MDI and heat to 60°C. After the MDI is completely dissolved, add it to the reaction vessel, raise the temperature to 80°C and react for 30 minutes. Continue to raise the temperature to 210°C, then add another 145g of PAO10 base oil, cool to about 100°C, and grind.

[0230] Comparative Example II-2

[0231] Example II-1 was repeated by replacing 4-(dicyanovinyl)phenylacetylene with 475 mg (3 mmol) of 4-tert-butylphenylacetylene. After the reaction was complete, the mixture was filtered and the filtrate was evaporated to dryness. The product was then separated and purified by column chromatography using a dichloromethane / methanol (20 / 1, v / v) mixture as the eluent, yielding 290 mg of a yellow-green solid product in 50% yield. NMR results were as follows: 1 H NMR (400MHz, CDCl3), δ (TMS, ppm): 7.35 (d, 4H), 7.24 (d, 4H), 7.12–6.85 (m, 10H), 1.32 (s, 18H), 0.49 (s, 6H) MS (MALDI-TOF): m / z calcd: 574.3[M] + ,found:574.3.

[0232]

[0233] Mix 145g of PAO10 base oil with 44.39g of octadecylamine in a reaction vessel and heat to 60°C. Dissolve 2.5g of 1,1-dimethyl-2,5-bis(tert-butylphenylethynyl)-3,4-diphenylthiophene in 25g of toluene and add it to the reaction vessel. Mix 145g of PAO10 base oil with 20.61g of MDI and heat to 60°C. After the MDI is completely dissolved, add it to the reaction vessel. Heat to 80°C and react for 30 minutes. Continue to heat to 210°C, then add another 145g of PAO10 base oil. Cool to about 100°C and grind.

[0234] The physicochemical properties of the greases in Example II-2, Comparative Example II-1, and Comparative Example II-2 were tested respectively, and the test results are shown in Table II-1.

[0235] Table II-1

[0236]

[0237] Third Implementation Method

[0238] According to a third embodiment of the present invention, the structure of the thiophene derivative having general formula (I) is as shown in formulas (I-III):

[0239]

[0240] In general formulas (I-III), R1 and R2 may be the same or different from each other, and are each independently selected from hydrogen and C. 1-6 Straight-chain or branched alkyl, aryl; each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl; x is an integer between 0 and 4; y is an integer between 0 and 3; z is an integer between 0 and 2.

[0241] According to a third embodiment of the present invention, preferably, R1 and R2 are the same or different from each other, and are each independently selected from hydrogen and C. 1-4 Straight-chain or branched alkyl, phenyl; each R is independently selected from hydrogen, C 1-4 Straight-chain or branched alkyl; x is an integer between 0 and 3; y is an integer between 0 and 2; z is 0 or 1.

[0242] The preparation of the thiophene derivatives having general formulas (I-III) according to the second preparation method of the present invention includes the step of reacting thiophene compounds represented by general formulas (II-III) and alkyne compounds represented by general formulas (III-III).

[0243]

[0244] In general formulas (II-III), R1 and R2 may be the same or different from each other, and are independently selected from hydrogen and C. 1-6 Straight-chain or branched alkyl or aryl groups; each group X may be the same or different from the others, and each is independently selected from F, Cl, Br, I, OH; in general formulas (II-III) and (III-III), each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl; x is an integer between 0 and 5; y is an integer between 0 and 3; z is an integer between 0 and 2.

[0245] According to a third embodiment of the present invention, preferably, R1 and R2 are the same or different from each other, and are each independently selected from hydrogen and C. 1-4 Straight-chain or branched alkyl or aryl groups; each X group is independently selected from Cl or Br; each R group is independently selected from hydrogen or C. 1-4 Straight-chain or branched alkyl; x is an integer between 0 and 3; y is an integer between 0 and 2; z is 0 or 1.

[0246] Thiol compounds of general formulas (II-III) that can be used include:

[0247]

[0248] According to a third embodiment of the present invention, preferably, a catalyst is added to the reaction. The type and amount of the catalyst are the same as in the first embodiment.

[0249] According to a third embodiment of the present invention, preferably, a solvent is added to the reaction. The solvent is preferably C1-C. 10 Organic amines and furans, such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, and tetrahydrofuran, can be selected, with C1-C being the most preferred. 10 The solvent is a mixture of an organic amine and furan, with a preferred volume ratio of 1:0.1-10. The solvent can be removed after the reaction by methods known in the art, without particular limitation, including distillation, evaporation, and column chromatography. Preferably, when separating and purifying the thiophene derivatives of the present invention using column chromatography, a mixed solvent of dichloromethane and petroleum ether can be used as the eluent, with a preferred volume ratio of 1:0.5-5.

[0250] According to a third embodiment of the present invention, preferably, in the reaction, the molar ratio between the alkyne compound represented by general formula (III-III) and the thiophene compound represented by general formula (II-III) is 1-6, most preferably 2-4. The reaction temperature is 0-50°C, preferably 15-35°C. The reaction time is 12-96 h, preferably 24-72 h.

[0251] According to a third embodiment of the present invention, preferably, after the reaction is completed, the reaction product can be purified. The purification method includes one or more of the following methods: washing with water, distillation, filtration, drying and recrystallization, without any particular limitation.

[0252] The specific raw materials and their sources used in the examples are as follows:

[0253] The chemical reagents, including 1,1-dimethyl-2,5-dibromo-3,4-diphenylthiophene, 1,1-diphenyl-2,5-dibromo-3,4-diphenylthiophene, 2-hydroxy-6-ethynylnaphthol, cuprous iodide, triphenylphosphine, tetratriphenylphosphine palladium, octadecylamine, MDI, tetrahydrofuran, triethylamine, dichloromethane, and methanol, were obtained from Bailingwei Reagent Company, Inokai Reagent Company, or Sigma Reagent Company, and were of analytical grade; the PAO10 base oil was obtained from ExxonMobil.

[0254] Example III-1

[0255] In a 100 mL Schlenk flask, 420 mg (1 mmol) of 1,1-dimethyl-2,5-dibromo-3,4-diphenylthiophene, 505 mg (3 mmol) of 2-hydroxy-6-ethynylnaphthol, 19 mg (0.1 mmol) of cuprous iodide, and 26 mg (0.1 mmol) of triphenylphosphine were added. Under nitrogen protection, 23 mg (0.02 mmol) of tetratetraphenylphosphine palladium and 30 mL of tetrahydrofuran / triethylamine (2 / 1, v / v) were added, and the reaction was carried out at room temperature for 48 hours. After the reaction was completed, the mixture was filtered, and the filtrate was evaporated to dryness. The product was separated and purified by column chromatography using a dichloromethane / petroleum ether (2 / 1, v / v) mixed solvent as the eluent, yielding 410 mg of a yellow solid product, with a yield of 69%. The NMR results of the product are as follows: 1 H NMR (400MHz, CDCl3), δ (TMS, ppm): 7.83–7.75 (m, 6H), 7.45 (m, 2H), 7.18 (m, 2H), 7.11–6.85 (m, 10H), 0.48 (s, 6H); MS (MALDI-TOF): m / z calcd: 594.2[M] + ,found:594.2.

[0256] The chemical reaction formula of the product of Example III-1 is shown below.

[0257]

[0258] Example III-2

[0259] In a 100 mL Schlenk reaction flask, 544 mg (1 mmol) of 1,1-diphenyl-2,5-dibromo-3,4-diphenylthiophene, 505 mg (3 mmol) of 2-hydroxy-6-ethynylnaphthol, 19 mg (0.1 mmol) of cuprous iodide, and 26 mg (0.1 mmol) of triphenylphosphine were added. Under nitrogen protection, 23 mg (0.02 mmol) of tetratetraphenylphosphine palladium and 30 mL of tetrahydrofuran / triethylamine (2 / 1, v / v) were added, and the reaction was carried out at room temperature for 48 hours. After the reaction was completed, the mixture was filtered and the filtrate was evaporated to dryness. The product was separated and purified by column chromatography using a dichloromethane / petroleum ether (2 / 1, v / v) mixed solvent as the eluent, yielding 460 mg of a yellow solid product, with a yield of 64%. The NMR results of the product are as follows: 1 H NMR (400MHz, CDCl3), δ (TMS, ppm): 7.85–7.75 (m, 6H), 7.46 (m, 2H), 7.18 (m, 2H), 7.13–6.85 (m, 20H); MS (MALDI-TOF): m / z calcd: 718.2[M] + ,found:718.2.

[0260] The chemical reaction formula of the product of Example III-2 is shown below.

[0261]

[0262] Example III-3

[0263] 145 g of PAO10 base oil and 44.39 g of octadecylamine were mixed in a reaction vessel and heated to 60 °C. 2.5 g of 1,1-dimethyl-2,5-bis(2-hydroxy-6-ethynylnaphthol)-3,4-diphenylthiophene was dissolved in 25 g of toluene and added to the reaction vessel. 145 g of PAO10 base oil and 20.61 g of MDI were mixed and heated to 60 °C. After the MDI was completely dissolved, it was added to the reaction vessel. The temperature was raised to 80 °C and reacted for 30 min. The temperature was then raised to 210 °C. 145 g of PAO10 base oil was added, and the mixture was cooled to about 100 °C and ground into a grease.

[0264] Example III-4

[0265] 145 g of PAO10 base oil and 44.39 g of octadecylamine were mixed in a reaction vessel and heated to 60 °C. 2.5 g of 1,1-diphenyl-2,5-bis(2-hydroxy-6-ethynylnaphthol)-3,4-diphenylthiophene was dissolved in 25 g of toluene and added to the reaction vessel. 145 g of PAO10 base oil and 20.61 g of MDI were mixed and heated to 60 °C. After the MDI was completely dissolved, it was added to the reaction vessel. The temperature was raised to 80 °C and reacted for 30 min. The temperature was then raised to 210 °C. 145 g of PAO10 base oil was added, and the mixture was cooled to about 100 °C and ground into a grease.

[0266] Example III-5

[0267] Mix 145g of PAO10 base oil with 44.39g of octadecylamine in a reaction vessel and heat to 60°C. Mix 145g of PAO10 base oil with 20.61g of MDI and heat to 60°C. After the MDI is completely dissolved, add it to the reaction vessel and heat to 80°C for 30 minutes. Continue to heat to 210°C, add another 145g of PAO10 base oil, cool to about 100°C, add 2.5g of 1,1-diphenyl-2,5-bis(2-hydroxy-6-ethynylnaphthol)-3,4-diphenylthiophene and grind into a ester.

[0268] Comparative Example III-1

[0269] Mix 145g of PAO10 base oil with 44.39g of octadecylamine in a reaction vessel and heat to 60°C. Mix 145g of PAO10 base oil with 20.61g of MDI and heat to 60°C. After the MDI is completely dissolved, add it to the reaction vessel, raise the temperature to 80°C and react for 30 minutes. Continue to raise the temperature to 210°C, add another 145g of PAO10 base oil, cool to about 100°C and grind into a grease.

[0270] The performance of the greases in Examples III-3, III-4, III-5, and Comparative Example III-1 was evaluated using the following methods: wide temperature range dropping point test for greases (GB / T 3498), cone penetration test for greases and petroleum greases (GB / T 269), oxidation induction period test for lubricating oils (SH / T 0719), oxidation stability test for greases (SH / T 0325), and oil separation test for greases using a stencil (SH / T 0324). The evaluation results are shown in Table III-1.

[0271] Table III-1 Evaluation Results

[0272]

[0273] Fourth Implementation Method

[0274] According to a fourth embodiment of the present invention, the structure of the thiophene derivative having general formula (I) is as shown in general formulas (I-IV):

[0275]

[0276] In general formulas (I-IV), each R1 is independently selected from hydrogen, C, and so on. 1-6 Straight-chain or branched alkyl groups, C 6-10 Aryl; each R2 is independently selected from C 1-6 Straight-chain or branched alkylene groups; each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl; x is an integer between 0 and 5; y is an integer between 0 and 4; z is an integer between 1 and 4.

[0277] According to a fourth embodiment of the present invention, preferably, each R1 is independently selected from hydrogen, C 1-4 Straight-chain or branched alkyl or phenyl groups; each R2 is independently selected from C 1-4 Straight-chain or branched alkylene groups; each R is independently selected from hydrogen, C 1-4 Straight-chain or branched alkyl; x is an integer between 0 and 3; y is 0, 1 or 2.

[0278] The preparation of the thiophene derivatives having general formulas (I-IV) according to the first preparation method of the present invention includes the step of reacting the thiophene compounds represented by general formulas (II-IV) with the phenolic compounds represented by general formulas (III-IV) and the compounds represented by general formulas (IV-IV).

[0279]

[0280]

[0281] In general formulas (II-IV), R1 is selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups, C 6-10 aryl group; each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl; x is an integer between 0 and 5;

[0282] In general formulas (III-IV), R is selected from hydrogen, C 1-6 Straight-chain or branched alkyl; y is an integer between 0 and 4; X is selected from F, Cl, Br, I, and OH;

[0283] In the general formula (IV-IV), each R2 is independently selected from C. 1-6 Straight-chain or branched alkylene groups; X' is selected from F, Cl, Br, I, OH, and z is an integer between 1 and 4.

[0284] According to a fourth embodiment of the present invention, preferably, in general formulas (II-IV), R1 is selected from hydrogen, C 1-4 Straight-chain or branched alkyl, phenyl; each R is independently selected from hydrogen, C 1-4 Straight-chain or branched alkyl; x is an integer between 0 and 3; in general formulas (III-IV), R is selected from hydrogen, C 1-4 Straight-chain or branched alkyl; y is 0, 1, or 2; X is selected from Cl, Br, I, and OH; in general formulas (IV-IV), each R2 is independently selected from C 1-4 Straight-chain or branched alkylene groups; X' is selected from Cl, Br, I, and OH.

[0285] The thiophene compounds represented by general formulas (II-IV) that can be used include the specific compounds shown below:

[0286]

[0287] Phenolic compounds of general formulas (III-IV) that can be used include the specific compounds shown below:

[0288]

[0289] According to a fourth embodiment of the present invention, preferably, the compounds represented by general formulas (IV-IV) include the specific compounds shown below:

[0290]

[0291] According to a fourth embodiment of the present invention, preferably, a catalyst is added to the reaction. The type and amount of the catalyst are the same as in the first embodiment.

[0292] According to a fourth embodiment of the present invention, preferably, in the reaction, the molar ratio between the thiophene compound represented by general formula (II-IV) and the phenolic compound represented by general formula (III-IV) and the compound represented by general formula (IV-IV) is preferably 1:0.5-5:0.2-5, and most preferably 1:0.8-3:0.3-3. The reaction temperature is 0-50°C, preferably 15-35°C.

[0293] According to a fourth embodiment of the present invention, preferably, the reaction time is 6-96 hours, more preferably 12-72 hours.

[0294] According to a fourth embodiment of the present invention, preferably, a solvent is added to the reaction. The solvent is preferably C1-C. 10 Organic amines and furans, such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, and tetrahydrofuran, can be selected, with C1-C being the most preferred. 10 The solvent is a mixture of an organic amine and furan, with a preferred volume ratio of 1:0.1-10. The solvent can be removed after the reaction by methods known in the art, without particular limitation, including distillation, evaporation, and column chromatography. Preferably, when separating and purifying the thiophene derivatives of the present invention using column chromatography, a mixed solvent of dichloromethane and petroleum ether can be used as the eluent, with a preferred volume ratio of 1:0.5-5.

[0295] According to a fourth embodiment of the present invention, preferably, the thiophene compound represented by general formula (II-IV) can be reacted with the phenolic compound represented by general formula (III-IV) first, and then the reaction product can be reacted with the compound represented by general formula (IV-IV).

[0296] According to a fourth embodiment of the present invention, preferably, in the reaction of the thiophene compound of general formula (II-IV) and the phenolic compound of general formula (III-IV), the molar ratio between the thiophene compound of general formula (II-IV) and the phenolic compound of general formula (III-IV) is preferably 1:0.5-5, more preferably 1:0.8-3; the reaction temperature is preferably 0-50°C, more preferably 15-35°C; generally, the longer the reaction time, the higher the conversion rate, and the reaction time can be 6-96 h, preferably 12-72 h.

[0297] According to a fourth embodiment of the present invention, preferably, a catalyst is added to the reaction of the thiophene compound of general formula (II-IV) with the phenolic compound of general formula (III-IV). The type and amount of the catalyst are the same as in the first embodiment.

[0298] According to a fourth embodiment of the present invention, preferably, in the reaction product of the thiophene compound of general formula (II-IV) and the phenolic compound of general formula (III-IV) and the compound of general formula (IV-IV), the molar ratio between the thiophene compound of general formula (II-IV) and the compound of general formula (IV-IV) is preferably 1:0.2-5, more preferably 1:0.3-3; the reaction temperature is preferably 0-50°C, more preferably 15-35°C; generally, the longer the reaction time, the higher the conversion rate, and the reaction time can be 6-96 h, preferably 12-72 h.

[0299] According to a fourth embodiment of the present invention, preferably, a catalyst is added to the reaction product of the thiophene compound of general formula (II-IV) and the phenolic compound of general formula (III-IV) and the compound of general formula (IV-IV). The catalyst is preferably a alkylphosphine compound and / or an azo compound, more preferably a mixture of alkylphosphine compound and azo compound, wherein the molar ratio between the two is preferably 1:0.1-10, more preferably 1:0.2-5. The preferred structure of the alkylphosphine compound is as follows: Each R is independently selected from C6-C 10 The aryl group and the C1-C6 straight-chain or branched alkyl group, wherein at least one R is C6-C 10 The aryl group. The C6-C 10 The aryl group can be selected from phenyl or naphthyl; the C1-C6 straight-chain or branched alkyl group can be selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, or isohexyl. The alkylphosphine compound can be triphenylphosphine or diphenylbutylphosphine. The preferred structure of the azo compound is: In the formula, each R' may be the same or different from the others, and each is independently selected from hydrogen, C, etc. 1-6 Straight-chain or branched alkyl groups, C3-10 cycloalkyl, C 6-10 Aryl and C 1-6 Alkoxy group. The azo compound is preferably one or more selected from dimethyl azodiacetic acid, diethyl azodiacetic acid, dipropyl azodiacetic acid, and dibutyl azodiacetic acid.

[0300] According to a fourth embodiment of the present invention, in the reaction product of the thiorrole compound of formula (II-IV) and the phenolic compound of formula (III-IV) and the compound of formula (IV-IV), the amount of catalyst added is preferably 0.1%-100% of the mass of the thiorrole compound of formula (II-IV).

[0301] The specific sources of the raw materials used in the examples are as follows:

[0302] The chemical reagents, including 1-alkynyl-1,2,3,4,5-pentaphenylthiophene, 1-methyl-1-alkynyl-2,3,4,5-tetraphenylthiophene, p-iodophenol, cuprous iodide, triphenylphosphine, tetratriphenylphosphine palladium, diethyl azodicarboxylate, octadecylamine, MDI, tetrahydrofuran, triethylamine, dichloromethane, and petroleum ether, were obtained from Bailingwei Reagent Company, Inokai Reagent Company, or Sigma Reagent Company, and were of analytical grade; the PAO10 base oil was obtained from ExxonMobil.

[0303] Example IV-1

[0304] In a 100 mL Schlenk reaction flask, 487 mg (1 mmol) of 1-alkynyl-1,2,3,4,5-pentaphenylthiophene, 264 mg (1.2 mmol) of p-iodophenol, 19 mg (0.1 mmol) of cuprous iodide, and 26 mg (0.1 mmol) of triphenylphosphine were added. Under nitrogen protection, 23 mg (0.02 mmol) of tetratetraphenylphosphine palladium and 30 mL of tetrahydrofuran / triethylamine (2 / 1, v / v) were added, and the reaction was carried out at room temperature for 48 hours. After the reaction was completed, the mixture was filtered, and the filtrate was evaporated to dryness. The product was separated and purified by column chromatography using a dichloromethane / petroleum ether (1 / 1, v / v) mixed solvent as the eluent, yielding 430 mg of a yellow solid product, with a yield of 74%. The NMR results of the product are as follows: 1 HNMR (400MHz, CDCl3), δ (TMS, ppm): 7.74 (m, 2H), 7.36 (m, 3H), 7.15–6.85 (m, 24H); MS (MALDI-TOF): m / z calcd: 578.2[M] + ,found:578.2.

[0305] The reaction formula for Example IV-1 is shown below:

[0306]

[0307] Example IV-2

[0308] 1158 mg (2 mmol) of 1-(4-hydroxybenzyne)-1,2,3,4,5-pentaphenylthiophene, 178 mg (1 mmol) of thiodipropionic acid, 630 mg (2.4 mmol) of triphenylphosphine, and 30 mL of tetrahydrofuran were added to a 100 mL reaction flask. 418 mg (2.4 mmol) of diethyl azodicarboxylate was slowly added dropwise at 0 °C, and the reaction was carried out at room temperature for 18 hours. After the reaction was complete, the mixture was filtered, and the filtrate was evaporated to dryness. The product was purified by column chromatography using a dichloromethane / petroleum ether (1 / 2, v / v) mixture as the eluent, yielding 960 mg of a yellow solid product, with a yield of 78%. The NMR results of the product are as follows: 1 H NMR (400MHz, CDCl3), δ (TMS, ppm): 7.72 (m, 4H), 7.35 (m, 6H), 7.13–6.85 (m, 48H), 2.92 (m, 4H), 2.78 (m, 4H); MS (MALDI-TOF): m / z calcd: 1298.4[M] + ,found:1298.4.

[0309] The reaction formula for Example IV-2 is shown below:

[0310]

[0311] Example IV-3

[0312] In a 100 mL Schlenk reaction flask, 425 mg (1 mmol) of 1-methyl-1-ynyl-2,3,4,5-tetraphenylthiophene, 264 mg (1.2 mmol) of p-iodophenol, 19 mg (0.1 mmol) of cuprous iodide, and 26 mg (0.1 mmol) of triphenylphosphine were added. Under nitrogen protection, 23 mg (0.02 mmol) of tetratetraphenylphosphine palladium and 30 mL of tetrahydrofuran / triethylamine (2 / 1, v / v) were added, and the reaction was carried out at room temperature for 48 hours. After the reaction was completed, the mixture was filtered, and the filtrate was evaporated to dryness. The product was separated and purified by column chromatography using a dichloromethane / petroleum ether (1 / 1, v / v) mixed solvent as the eluent, yielding 400 mg of a yellow solid product, with a yield of 78%. The NMR results of the product are as follows: 1 H NMR (400MHz, CDCl3), δ (TMS, ppm): 7.15–6.85 (m, 24H), 0.22 (s, 3H); MS (MALDI-TOF): m / z calcd: 516.2[M] + ,found:516.2.

[0313] The reaction formula for Example IV-3 is shown below:

[0314]

[0315] Example IV-4

[0316] In a 100 mL reaction flask, 949 mg (2 mmol) of 1-(4-hydroxybenzyne)-1,2,3,4,5-pentaphenylthiophene, 178 mg (1 mmol) of thiodipropionic acid, 630 mg (2.4 mmol) of triphenylphosphine, and 30 mL of tetrahydrofuran were added. 418 mg (2.4 mmol) of diethyl azodicarboxylate was then slowly added dropwise at 0 °C, and the reaction was carried out at room temperature for 18 hours. After the reaction was complete, the mixture was filtered, and the filtrate was evaporated to dryness. The product was purified by column chromatography using a dichloromethane / petroleum ether (1 / 2, v / v) mixture as the eluent, yielding 870 mg of a yellow solid product, with a yield of 74%. The NMR results of the product were as follows: 1 H NMR (400MHz, CDCl3), δ (TMS, ppm): 7.13–6.85 (m, 48H), 2.92 (m, 4H), 2.78 (m, 4H), 0.22 (s, 6H); MS (MALDI-TOF): m / z calcd: 1174.4[M] + ,found:1174.4.

[0317] The reaction formula for Example IV-4 is shown below:

[0318]

[0319] Example IV-5

[0320] 145 g of PAO10 base oil and 44.39 g of octadecylamine were mixed in a reaction vessel and heated to 60 °C. 2.5 g of di(4-(1,2,3,4,5-pentaphenylthiopyrrolynyl))phenyl thiodipropionate was dissolved in 25 g of toluene and added to the reaction vessel. 145 g of PAO10 base oil and 20.61 g of MDI were mixed and heated to 60 °C. After the MDI was completely dissolved, it was added to the reaction vessel. The temperature was raised to 80 °C and reacted for 30 min. The temperature was then raised to 210 °C. 145 g of PAO10 base oil was added, and the mixture was cooled to about 100 °C and ground into a grease.

[0321] Example IV-6

[0322] 145 g of PAO10 base oil and 44.39 g of octadecylamine were mixed in a reaction vessel and heated to 60 °C. 2.5 g of di(4-(1-methyl-2,3,4,5-tetraphenylthiopyrynyl))phenyl thiodipropionate was dissolved in 25 g of toluene and added to the reaction vessel. 145 g of PAO10 base oil and 20.61 g of MDI were mixed and heated to 60 °C. After the MDI was completely dissolved, it was added to the reaction vessel. The temperature was raised to 80 °C and reacted for 30 min. The temperature was then raised to 210 °C. 145 g of PAO10 base oil was added, and the mixture was cooled to about 100 °C and ground into a grease.

[0323] Example IV-7

[0324] Mix 145g of PAO10 base oil with 44.39g of octadecylamine in a reaction vessel and heat to 60°C. Mix 145g of PAO10 base oil with 20.61g of MDI and heat to 60°C. After the MDI is completely dissolved, add it to the reaction vessel and heat to 80°C for 30 minutes. Continue to heat to 210°C, add another 145g of PAO10 base oil, cool to about 100°C, add 2.5g of di(4-(1,2,3,4,5-pentaphenylthiopyroxyynyl)) phenyl thiodipropionate and grind into a ester.

[0325] Comparative Example IV-1

[0326] Mix 145g of PAO10 base oil with 44.39g of octadecylamine in a reaction vessel and heat to 60°C. Mix 145g of PAO10 base oil with 20.61g of MDI and heat to 60°C. After the MDI is completely dissolved, add it to the reaction vessel, raise the temperature to 80°C and react for 30 minutes. Continue to raise the temperature to 210°C, add another 145g of PAO10 base oil, cool to about 100°C and grind into a grease.

[0327] The performance of the greases in Examples IV-5, IV-6, IV-7, and Comparative Example IV-1 was evaluated using the following methods: wide temperature range dropping point test for greases (GB / T 3498), cone penetration test for greases and petroleum greases (GB / T269), oxidation induction period test for lubricating oils (SH / T 0719), oxidation stability test for greases (SH / T 0325), and oil separation test for greases using a stencil (SH / T 0324). The evaluation results are shown in Table IV-1.

[0328] Table IV-1 Analysis Results

[0329]

[0330] Fifth Implementation Method

[0331] According to a fifth embodiment of the present invention, the structure of the thiophene derivative having general formula (I) is as shown in general formula (IV):

[0332]

[0333] In general formula (IV), each R is independently selected from hydrogen, C, and so on. 1-6 Straight-chain or branched alkyl; x is an integer between 0 and 5; y is an integer between 0 and 3; z is an integer between 0 and 4; R1 is selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups, C 6-10 Aryl.

[0334] According to a fifth embodiment of the present invention, preferably, in general formula (IV), each R is selected from hydrogen, C 1-4 Straight-chain or branched alkyl; x is an integer between 0 and 3; y is 0, 1, or 2; z is 0, 1, or 2; R1 is selected from hydrogen, C 1-4 Straight-chain or branched alkyl or phenyl groups.

[0335] The method for preparing the thiophene derivative having general formula (IV) according to the first preparation method of the present invention includes the step of reacting a thiophene compound represented by general formulas (II-V) and a phenothiazine compound represented by general formulas (III-V).

[0336]

[0337] In general formulas (II-V) and (III-V), each R is independently selected from hydrogen, C, and C. 1-6 Straight-chain or branched alkyl; x is an integer between 0 and 5; y is an integer between 0 and 3; z is an integer between 0 and 4; R1 is selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups, C 6-10 Aryl group; X is selected from F, Cl, Br, I, OH.

[0338] According to a fifth embodiment of the present invention, preferably, in general formula (IV), each R is selected from hydrogen, C 1-4 Straight-chain or branched alkyl; x is an integer between 0 and 3; y is 0, 1, or 2; z is 0, 1, or 2; R1 is selected from hydrogen, C 1-4 Straight-chain or branched alkyl or phenyl groups; X is selected from Cl, Br, I, and OH.

[0339] Thiol compounds of general formulas (II-V) that can be used include:

[0340]

[0341] The phenothiazine compounds represented by general formulas (III-V) that can be used include:

[0342]

[0343] According to a fifth embodiment of the present invention, preferably, a catalyst is added to the reaction. The type and amount of the catalyst are the same as in the first embodiment.

[0344] According to a fifth embodiment of the present invention, preferably, in the reaction, the molar ratio between the thiophene compound represented by general formula (II-V) and the phenothiazine compound represented by general formula (III-V) is 1:0.5-5, most preferably 1:0.8-1.2. The reaction temperature is 0-50°C, preferably 15-35°C. The reaction time is 6-96 h, preferably 12-72 h.

[0345] According to a fifth embodiment of the present invention, preferably, a solvent is added to the reaction. The solvent is preferably C1-C. 10 Organic amines and furans, such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, and tetrahydrofuran, can be selected, with C1-C being the most preferred. 10 The solvent is a mixture of an organic amine and furan, with a preferred volume ratio of 1:0.1-10. The solvent can be removed after the reaction by methods known in the art, without particular limitation, including distillation, evaporation, and column chromatography. Preferably, when separating and purifying the thiophene derivatives of the present invention using column chromatography, a mixed solvent of dichloromethane and petroleum ether can be used as the eluent, with a preferred volume ratio of 1:0.5-5.

[0346] The main raw materials used in the examples are as follows:

[0347] The chemical reagents, including 1-alkynyl-1,2,3,4,5-pentaphenylthiophene, 1-methyl-1-alkynyl-2,3,4,5-tetraphenylthiophene, 2-iodophenthiazine, cuprous iodide, triphenylphosphine, tetratriphenylphosphine palladium, octadecylamine, MDI, tetrahydrofuran, triethylamine, dichloromethane, and petroleum ether, were obtained from Bailingwei Reagent Company, Inokai Reagent Company, or Sigma Reagent Company, and were of analytical grade; the PAO10 base oil was obtained from ExxonMobil.

[0348] Example V-1

[0349] In a 100 mL Schlenk reaction flask, 487 mg (1 mmol) of 1-alkynyl-1,2,3,4,5-pentaphenylthiophene, 390 mg (1.2 mmol) of 2-iodophenothiazine, 19 mg (0.1 mmol) of cuprous iodide, and 26 mg (0.1 mmol) of triphenylphosphine were added. Under nitrogen protection, 23 mg (0.02 mmol) of tetratetraphenylphosphine palladium and 30 mL of tetrahydrofuran / triethylamine (2 / 1, v / v) were added, and the reaction was carried out at room temperature for 48 hours. After the reaction was completed, the mixture was filtered, and the filtrate was evaporated to dryness. The product was separated and purified by column chromatography using a dichloromethane / petroleum ether (1 / 2, v / v) mixed solvent as the eluent, yielding 490 mg of a yellow solid product, with a yield of 72%. The NMR results of the product are as follows: 1 H NMR (400MHz, CDCl3), δ (TMS, ppm): 7.74 (m, 2H), 7.36 (m, 3H), 7.20–6.82 (m, 27H); MS (MALDI-TOF): m / z calcd: 683.2[M] + ,found:683.2.

[0350] The reaction formula for Example V-1 is shown below:

[0351]

[0352] Example V-2

[0353] In a 100 mL Schlenk reaction flask, 425 mg (1 mmol) of 1-methyl-1-ynyl-2,3,4,5-tetraphenylthiophene, 390 mg (1.2 mmol) of 2-iodophenothiazine, 19 mg (0.1 mmol) of cuprous iodide, and 26 mg (0.1 mmol) of triphenylphosphine were added. Under nitrogen protection, 23 mg (0.02 mmol) of tetratetraphenylphosphine palladium and 30 mL of tetrahydrofuran / triethylamine (2 / 1, v / v) were added, and the reaction was carried out at room temperature for 48 hours. After the reaction was completed, the mixture was filtered, and the filtrate was evaporated to dryness. The product was separated and purified by column chromatography using a dichloromethane / petroleum ether (1 / 2, v / v) mixed solvent as the eluent, yielding 460 mg of a yellow solid product, with a yield of 74%. The NMR results of the product are as follows: 1 H NMR (400MHz, CDCl3), δ (TMS, ppm): 7.18–6.84 (m, 27H), 0.24 (s, 3H); MS (MALDI-TOF): m / z calcd: 621.2[M] + ,found:621.2.

[0354] The reaction formula for Example V-2 is shown below:

[0355]

[0356] Example V-3

[0357] Mix 145g of PAO10 base oil with 44.39g of octadecylamine in a reaction vessel and heat to 60°C. Dissolve 2.5g of 1-(2-ynylphenthiazine)-1,2,3,4,5-pentaphenylthiophene in 25g of toluene and add to the reaction vessel. Mix 145g of PAO10 base oil with 20.61g of MDI and heat to 60°C. After the MDI is completely dissolved, add to the reaction vessel and heat to 80°C. React for 30 minutes, then continue heating to 210°C. Add another 145g of PAO10 base oil, cool to about 100°C, and grind into a grease.

[0358] Example V-4

[0359] 145 g of PAO10 base oil and 44.39 g of octadecylamine were mixed in a reaction vessel and heated to 60 °C. 2.5 g of 1-methyl-1-(2-ynylphenthiazine)-2,3,4,5-tetraphenylthiophene was dissolved in 25 g of toluene and added to the reaction vessel. 145 g of PAO10 base oil and 20.61 g of MDI were mixed and heated to 60 °C. After the MDI was completely dissolved, it was added to the reaction vessel. The temperature was raised to 80 °C and reacted for 30 min. The temperature was then raised to 210 °C. 145 g of PAO10 base oil was added, and the mixture was cooled to about 100 °C and ground into a grease.

[0360] Example V-5

[0361] Mix 145g of PAO10 base oil with 44.39g of octadecylamine in a reaction vessel and heat to 60°C. Mix 145g of PAO10 base oil with 20.61g of MDI and heat to 60°C. After the MDI is completely dissolved, add it to the reaction vessel and heat to 80°C for 30 minutes. Continue heating to 210°C, then add another 145g of PAO10 base oil. Cool to about 100°C and add 2.5g of 1-(2-ynylphenthiazine)-1,2,3,4,5-pentaphenylthiophene. Grind into a grease.

[0362] Comparative Example V-1

[0363] Mix 145g of PAO10 base oil with 44.39g of octadecylamine in a reaction vessel and heat to 60°C. Mix 145g of PAO10 base oil with 20.61g of MDI and heat to 60°C. After the MDI is completely dissolved, add it to the reaction vessel, raise the temperature to 80°C and react for 30 minutes. Continue to raise the temperature to 210°C, add another 145g of PAO10 base oil, cool to about 100°C and grind into a grease.

[0364] The performance of the greases in Examples V-3, V-4, V-5, and Comparative Example V-1 was evaluated using the following methods: wide temperature range dropping point test for greases (GB / T 3498), cone penetration test for greases and petroleum greases (GB / T 269), oxidation induction period test for lubricating oils (SH / T 0719), oxidation stability test for greases (SH / T 0325), and oil separation test for greases using a stencil (SH / T 0324). The evaluation results are shown in Table V-1.

[0365] Table V-1 Evaluation Results

[0366]

[0367] Sixth Implementation Method

[0368] According to a sixth embodiment of the present invention, the structure of the thiophene derivative having general formula (I) is as shown in general formulas (I-VI):

[0369]

[0370] In general formulas (I-VI), each R is independently selected from hydrogen, C, and so on. 1-6 Straight-chain or branched alkyl groups; x is an integer between 0 and 5; y is an integer between 0 and 3; z is an integer between 1 and 4; R1 is selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups, C 6-10 aryl; R2 is selected from single bond, C 1-6 Straight-chain or branched alkylene groups.

[0371] According to a sixth embodiment of the present invention, preferably, in general formulas (I-VI), each R is selected from hydrogen, C 1-4 Straight-chain or branched alkyl; x is an integer between 0 and 3; y is 0, 1, or 2; z is 1, 2, or 3; R1 is selected from hydrogen, C 1-4 Straight-chain or branched alkyl or phenyl groups; R2 is selected from C 1-4 Straight-chain or branched alkylene groups.

[0372] The method for preparing the thiophene derivatives having general formulas (I-VI) according to the first preparation method of the present invention includes the step of reacting thiophene compounds represented by general formulas (II-VI) with phenolic compounds represented by general formulas (III-VI) and compounds represented by general formulas (IV-VI).

[0373]

[0374] In general formulas (II-VI), each R is independently selected from hydrogen, C, and so on. 1-6 Straight-chain or branched alkyl; x is an integer between 0 and 5; R1 is selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups, C6-10 Aryl; in general formula (III-VI), each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl; y is an integer between 0 and 3; X is selected from F, Cl, Br, I, OH; in general formulas (IV-VI), each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl; y is an integer between 0 and 3; z is an integer between 1 and 4; R2 is selected from single bonds, C 1-6 Straight-chain or branched alkylene groups; X is selected from F, Cl, Br, I, and OH.

[0375] According to a sixth embodiment of the present invention, preferably, in general formulas (II-VI), each R is independently selected from hydrogen, C 1-4 Straight-chain or branched alkyl; x is an integer between 0 and 3; R1 is selected from hydrogen, C 1-4 Straight-chain or branched alkyl or phenyl groups; in general formulas (III-VI), each R is independently selected from hydrogen, C... 1-4 Straight-chain or branched alkyl; y is 0, 1, or 2; X is selected from Cl, Br, I, and OH; in general formulas (IV-VI), each R is independently selected from hydrogen, C 1-4 Straight-chain or branched alkyl; y is 0, 1, or 2; z is 1, 2, or 3; R2 is selected from single bonds, C 1-4 Straight-chain or branched alkylene groups; X is selected from Cl, Br, I, and OH.

[0376] Thiol compounds of general formulas (II-VI) that can be used include:

[0377]

[0378] Phenolic compounds represented by general formulas (III-VI) that can be used include:

[0379]

[0380] According to a sixth embodiment of the present invention, preferably, a catalyst is added to the reaction. The type and amount of the catalyst are the same as in the first embodiment.

[0381] According to a sixth embodiment of the present invention, preferably, in the reaction, the molar ratio between the thiophene compound represented by general formula (II-VI) and the phenolic compound represented by general formula (III-VI) and the compound represented by general formula (IV-VI) is preferably 1:0.5-5:0.2-5, and most preferably 1:0.8-3:0.3-3.

[0382] According to a sixth embodiment of the present invention, preferably, the reaction temperature is 0-50°C, more preferably 15-35°C. The reaction time is 6-96 hours, more preferably 12-72 hours.

[0383] According to a sixth embodiment of the present invention, preferably, a solvent is added to the reaction. The solvent is preferably C1-C. 10 Organic amines and furans, such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, and tetrahydrofuran, can be selected, with C1-C being the most preferred. 10 The solvent is a mixture of an organic amine and furan, with a preferred volume ratio of 1:0.1-10. The solvent can be removed after the reaction by methods known in the art, without particular limitation, including distillation, evaporation, and column chromatography. Preferably, when separating and purifying the thiophene derivatives of the present invention using column chromatography, a mixed solvent of dichloromethane and petroleum ether can be used as the eluent, with a preferred volume ratio of 1:0.5-5.

[0384] According to a sixth embodiment of the present invention, preferably, the thiophene compound represented by general formula (II-VI) can be reacted with the phenolic compound represented by general formula (III-VI) first, and then the reaction product can be reacted with the compound represented by general formula (IV-VI).

[0385] According to a sixth embodiment of the present invention, preferably, in the reaction of the thiophene compound of general formula (II-VI) and the phenolic compound of general formula (III-VI), the molar ratio between the thiophene compound of general formula (II-VI) and the phenolic compound of general formula (III-VI) is 1:0.5-5, more preferably 1:0.8-3; the reaction temperature is preferably 0-50°C, more preferably 15-35°C; generally, the longer the reaction time, the higher the conversion rate, and the reaction time can be 6-96 h, preferably 12-72 h.

[0386] According to a sixth embodiment of the present invention, preferably, a catalyst is added to the reaction of the thiophene compound of general formula (II-VI) with the phenolic compound of general formula (III-VI). The type and amount of the catalyst are the same as in the first embodiment. Preferably, in the reaction of the reaction product of the thiophene compound of general formula (II-VI) and the phenolic compound of general formula (III-VI) with the compound of general formula (IV-VI), the molar ratio between the thiophene compound of general formula (II-VI) and the compound of general formula (IV-VI) is preferably 1:0.2-5, more preferably 1:0.3-3; the reaction temperature is preferably 0-50°C, more preferably 15-35°C; generally, the longer the reaction time, the higher the conversion rate, and the reaction time can be 6-96 h, preferably 12-72 h.

[0387] According to a sixth embodiment of the present invention, preferably, a catalyst is added to the reaction product of the thiophene compound of general formula (II-VI) and the phenolic compound of general formula (III-VI) and the compound of general formula (IV-VI). The catalyst is preferably a alkylphosphine compound and / or an azo compound, more preferably a mixture of alkylphosphine compound and azo compound, wherein the molar ratio between the two is preferably 1:0.1-10, more preferably 1:0.2-5. The preferred structure of the alkylphosphine compound is as follows: Each R is independently selected from C6-C 10 The aryl group and the C1-C6 straight-chain or branched alkyl group, wherein at least one R is C6-C 10 The aryl group. The C6-C 10 The aryl group can be selected from phenyl or naphthyl; the C1-C6 straight-chain or branched alkyl group can be selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, or isohexyl. The alkylphosphine compound can be triphenylphosphine or diphenylbutylphosphine. The preferred structure of the azo compound is: In the formula, each R' may be the same or different from the others, and each is independently selected from hydrogen, C, etc. 1-6 Straight-chain or branched alkyl groups, C 3-10 cycloalkyl, C 6-10 Aryl and C 1-6 Alkoxy group. The azo compound is preferably one or more selected from dimethyl azodiacetic acid, diethyl azodiacetic acid, dipropyl azodiacetic acid, and dibutyl azodiacetic acid.

[0388] According to a sixth embodiment of the present invention, in the reaction product of the thiorrole compound of general formula (II-VI) and the phenolic compound of general formula (III-VI) and the compound of general formula (IV-VI), the amount of catalyst added is preferably 0.1%-100% of the mass of the thiorrole compound of formula (II-VI).

[0389] The main raw materials used in the examples are as follows:

[0390] The chemical reagents, including 1-alkynyl-1,2,3,4,5-pentaphenylthiophene, 1-methyl-1-alkynyl-2,3,4,5-tetraphenylthiophene, p-iodophenol, cuprous iodide, triphenylphosphine, tetratriphenylphosphine palladium, di(4-carboxylic acid benzyl)disulfide, diethyl azodicarboxylate, octadecylamine, MDI, tetrahydrofuran, triethylamine, dichloromethane, and petroleum ether, were obtained from Bailingwei Reagent Company, Inokai Reagent Company, or Sigma Reagent Company, and were of analytical grade; the PAO10 base oil was obtained from ExxonMobil.

[0391] Example VI-1

[0392] In a 100 mL Schlenk reaction flask, 487 mg (1 mmol) of 1-alkynyl-1,2,3,4,5-pentaphenylthiophene, 264 mg (1.2 mmol) of p-iodophenol, 19 mg (0.1 mmol) of cuprous iodide, and 26 mg (0.1 mmol) of triphenylphosphine were added. Under nitrogen protection, 23 mg (0.02 mmol) of tetratetraphenylphosphine palladium and 30 mL of tetrahydrofuran / triethylamine (2 / 1, v / v) were added, and the reaction was carried out at room temperature for 48 hours. After the reaction was completed, the mixture was filtered, and the filtrate was evaporated to dryness. The product was separated and purified by column chromatography using a dichloromethane / petroleum ether (1 / 1, v / v) mixed solvent as the eluent, yielding 430 mg of a yellow solid product, with a yield of 74%. The NMR results of the product are as follows: 1 HNMR (400MHz, CDCl3), δ (TMS, ppm): 7.74 (m, 2H), 7.36 (m, 3H), 7.15–6.85 (m, 24H); MS (MALDI-TOF): m / z calcd: 578.2[M] + ,found:578.2.

[0393] The reaction formula for Example VI-1 is shown below:

[0394]

[0395] Example VI-2

[0396] 1158 mg (2 mmol) of 1-(4-hydroxybenzyne)-1,2,3,4,5-pentaphenylthiophene, 334 mg (1 mmol) of benzyl 4-carboxylate disulfide, 630 mg (2.4 mmol) of triphenylphosphine, and 30 mL of tetrahydrofuran were added to a 100 mL reaction flask. 418 mg (2.4 mmol) of diethyl azodicarboxylate was slowly added dropwise at 0 °C, and the reaction was carried out at room temperature for 18 hours. After the reaction was complete, the mixture was filtered, and the filtrate was evaporated to dryness. The product was purified by column chromatography using a dichloromethane / petroleum ether (1 / 2, v / v) mixture as the eluent, yielding 1080 mg of a yellow solid product, with a yield of 74%. The NMR results of the product are as follows: 1 H NMR (400MHz, CDCl3), δ (TMS, ppm): 7.92 (m, 4H), 7.72 (m, 4H), 7.43 (m, 4H), 7.35 (m, 6H), 7.15–6.87 (m, 48H), 3.38 (m, 4H); MS (MALDI-TOF): m / z calcd:1455.4[M] + ,found:1455.4.

[0397] The reaction formula for Example VI-2 is shown below:

[0398]

[0399] Example VI-3

[0400] In a 100 mL Schlenk reaction flask, 425 mg (1 mmol) of 1-methyl-1-ynyl-2,3,4,5-tetraphenylthiophene, 264 mg (1.2 mmol) of p-iodophenol, 19 mg (0.1 mmol) of cuprous iodide, and 26 mg (0.1 mmol) of triphenylphosphine were added. Under nitrogen protection, 23 mg (0.02 mmol) of tetratetraphenylphosphine palladium and 30 mL of tetrahydrofuran / triethylamine (2 / 1, v / v) were added, and the reaction was carried out at room temperature for 48 hours. After the reaction was completed, the mixture was filtered, and the filtrate was evaporated to dryness. The product was separated and purified by column chromatography using a dichloromethane / petroleum ether (1 / 1, v / v) mixed solvent as the eluent, yielding 400 mg of a yellow solid product, with a yield of 78%. The NMR results of the product are as follows: 1 H NMR (400MHz, CDCl3), δ (TMS, ppm): 7.15–6.85 (m, 24H), 0.22 (s, 3H); MS (MALDI-TOF): m / z calcd: 516.2[M] + ,found:516.2.

[0401] The reaction formula for Example VI-3 is shown below:

[0402]

[0403] Example VI-4

[0404] 949 mg (2 mmol) of 1-(4-hydroxybenzyne)-1,2,3,4,5-pentaphenylthiophene, 334 mg (1 mmol) of thiodipropionic acid, 630 mg (2.4 mmol) of triphenylphosphine, and 30 mL of tetrahydrofuran were added to a 100 mL reaction flask. 418 mg (2.4 mmol) of diethyl azodicarboxylate was slowly added dropwise at 0 °C, and the reaction was carried out at room temperature for 18 hours. After the reaction was complete, the mixture was filtered, and the filtrate was evaporated to dryness. The product was purified by column chromatography using a dichloromethane / petroleum ether (1 / 2, v / v) mixture as the eluent, yielding 870 mg of a yellow solid product, with a yield of 74%. The NMR results of the product are as follows: 1 H NMR (400MHz, CDCl3), δ (TMS, ppm): 7.92 (m, 4H), 7.43 (m, 4H), 7.15–6.87 (m, 48H), 3.42 (m, 4H), 0.22 (s, 6H); MS (MALDI-TOF): m / zcalcd: 1330.4[M] + ,found:1330.4.

[0405] The reaction formula for Example VI-4 is shown below:

[0406]

[0407] Example VI-5

[0408] 145 g of PAO10 base oil and 44.39 g of octadecylamine were mixed in a reaction vessel and heated to 60 °C. 2.5 g of di(4-(1,2,3,4,5-pentaphenylthiopyrrolynyl))phenyl ester of dithiodibenzylbenzoate was dissolved in 25 g of toluene and added to the reaction vessel. 145 g of PAO10 base oil and 20.61 g of MDI were mixed and heated to 60 °C. After the MDI was completely dissolved, it was added to the reaction vessel. The temperature was raised to 80 °C and reacted for 30 min. The temperature was then raised to 210 °C. 145 g of PAO10 base oil was added, and the mixture was cooled to about 100 °C and ground into a grease.

[0409] Example VI-6

[0410] 145 g of PAO10 base oil and 44.39 g of octadecylamine were mixed in a reaction vessel and heated to 60 °C. 2.5 g of di(4-(1-methyl-2,3,4,5-tetraphenylthiopyrynyl))phenyl dithiodibenzylbenzoate was dissolved in 25 g of toluene and added to the reaction vessel. 145 g of PAO10 base oil and 20.61 g of MDI were mixed and heated to 60 °C. After the MDI was completely dissolved, it was added to the reaction vessel. The temperature was raised to 80 °C and reacted for 30 min. The temperature was then raised to 210 °C. 145 g of PAO10 base oil was added, and the mixture was cooled to about 100 °C and ground into a grease.

[0411] Example VI-7

[0412] Mix 145g of PAO10 base oil with 44.39g of octadecylamine in a reaction vessel and heat to 60°C. Mix 145g of PAO10 base oil with 20.61g of MDI and heat to 60°C. After the MDI is completely dissolved, add it to the reaction vessel and heat to 80°C for 30 minutes. Continue to heat to 210°C, add another 145g of PAO10 base oil, cool to about 100°C, add 2.5g of di(4-(1,2,3,4,5-pentaphenylthiopyrrolylynyl)) phenyl ester of dithiodibenzylbenzoate and grind into a ester.

[0413] Comparative Example VI-1

[0414] Mix 145g of PAO10 base oil with 44.39g of octadecylamine in a reaction vessel and heat to 60°C. Mix 145g of PAO10 base oil with 20.61g of MDI and heat to 60°C. After the MDI is completely dissolved, add it to the reaction vessel, raise the temperature to 80°C and react for 30 minutes. Continue to raise the temperature to 210°C, add another 145g of PAO10 base oil, cool to about 100°C and grind into a grease.

[0415] The performance of the greases in Examples VI-5, VI-6, VI-7, and Comparative Example VI-1 was evaluated using the following methods: Grease wide temperature range dropping point test (GB / T 3498), Grease and petroleum grease cone penetration test (GB / T269), Lubricating oil oxidation induction period test (SH / T 0719), Grease extreme pressure performance test (SH / T 0202), Grease anti-wear performance test (SH / T 0204), and Grease stencil oil separation test (SH / TSH / T 0324). The evaluation results are shown in Table VI-1.

[0416] Table VI-1 Evaluation Results

[0417]

[0418] Seventh Implementation Method

[0419] According to a seventh embodiment of the present invention, the structure of the thiophene derivative having general formula (I) is as shown in general formulas (I-VII):

[0420]

[0421] In general formulas (I-VII), each R is independently selected from hydrogen, C, and so on. 1-6 Straight-chain or branched alkyl; each x is independently selected from an integer between 0 and 5; R1 is selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups, C 6-10 aryl; R2 is selected from single bond, C 1-20 Straight-chain or branched alkylene groups.

[0422] According to a seventh embodiment of the present invention, preferably, in general formulas (I-VII), each R is independently selected from hydrogen, C 1-4 Straight-chain or branched alkyl; each x is independently selected from an integer between 0 and 3; R1 is selected from hydrogen, C 1-4 Straight-chain or branched alkyl or phenyl groups; R2 is selected from single bonds and C 6-18 Straight-chain or branched alkylene groups.

[0423] According to a seventh embodiment of the present invention, preferably, the thiophene derivative having general formulas (I-VII) includes one or more of the following compounds:

[0424]

[0425] The preparation of the thiophene derivatives having general formulas (I-VII) according to the first preparation method of the present invention includes the step of reacting the thiophene compounds represented by general formulas (II-VII) and the compounds represented by general formulas (III-VII).

[0426]

[0427] In general formulas (II-VII), each R is independently selected from hydrogen, C, and so on. 1-6 Straight-chain or branched alkyl; each x is independently selected from an integer between 0 and 5; R1 is selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups, C 6-10 Aryl; in general formulas (III-VII), R2 is selected from single bonds, C 1-20 Straight-chain or branched alkylene groups; X is selected from F, Cl, Br, and I.

[0428] According to a seventh embodiment of the present invention, preferably, in general formulas (II-VII), each R is independently selected from hydrogen, C 1-4 Straight-chain or branched alkyl; each x is independently selected from an integer between 0 and 3; R1 is selected from hydrogen, C 1-4 Straight-chain or branched alkyl or phenyl; in general formulas (III-VII), R2 is selected from single bonds, C 6-18 Straight-chain or branched alkylene groups; X is selected from Cl, Br, and I.

[0429] The thiophene compounds represented by general formulas (II-VII) that can be used include one or more of the following compounds:

[0430]

[0431] The compounds represented by general formulas (III-VII) that can be used include one or more of the following compounds:

[0432]

[0433] According to a seventh embodiment of the present invention, preferably, a catalyst is added to the reaction. The type and amount of the catalyst are the same as in the first embodiment.

[0434] According to a seventh embodiment of the present invention, preferably, in the reaction, the molar ratio between the thiophene compound represented by general formula (II-VII) and the compound represented by general formula (III-VII) is preferably 1:0.5-5, and most preferably 1:0.8-1.2.

[0435] According to a seventh embodiment of the present invention, preferably, the reaction temperature is 0-50°C, more preferably 15-35°C. The reaction time is 6-96 hours, more preferably 12-72 hours.

[0436] According to a seventh embodiment of the present invention, preferably, a solvent is added to the reaction. The solvent is preferably C1-C. 10 Organic amines and furans, such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, and tetrahydrofuran, can be selected, with C1-C being the most preferred. 10 The solvent is a mixture of an organic amine and furan, with a preferred volume ratio of 1:0.1-10. The solvent can be removed after the reaction by methods known in the art, without particular limitation, including distillation, evaporation, and column chromatography. Preferably, the thiophene derivatives of the present invention are separated and purified by column chromatography, using a mixed solvent of a haloalkane and petroleum ether (preferably a mixture of dichloromethane and petroleum ether) as the eluent, with a preferred volume ratio of 1:0.5-5.

[0437] The main raw materials used in the examples are as follows:

[0438] The chemical reagents, including 1-alkynyl-1,2,3,4,5-pentaphenylthiophene, 1-methyl-1-alkynyl-2,3,4,5-tetraphenylthiophene, 8-bromooctanoic acid, cuprous iodide, triphenylphosphine, tetratriphenylphosphine palladium, octadecylamine, MDI, tetrahydrofuran, triethylamine, dichloromethane, and petroleum ether, were obtained from Bailingwei Reagent Company, Inokai Reagent Company, or Sigma Reagent Company, and were of analytical grade; the PAO10 base oil was obtained from ExxonMobil.

[0439] Example VII-1

[0440] In a 100 mL Schlenk reaction flask, 487 mg (1 mmol) of 1-alkynyl-1,2,3,4,5-pentaphenylthiophene, 268 mg (1.2 mmol) of 8-bromooctanoic acid, 19 mg (0.1 mmol) of cuprous iodide, and 26 mg (0.1 mmol) of triphenylphosphine were added. Under nitrogen protection, 23 mg (0.02 mmol) of tetratetraphenylphosphine palladium and 30 mL of tetrahydrofuran / triethylamine (2 / 1, v / v) were added, and the reaction was carried out at room temperature for 48 hours. After the reaction was completed, the mixture was filtered, and the filtrate was evaporated to dryness. The product was separated and purified by column chromatography using a dichloromethane / methanol (20 / 1, v / v) mixture as the eluent, yielding 450 mg of a yellow solid product, with a yield of 72%. The NMR results of the product are as follows: 1HNMR (400MHz, CDCl3), δ (TMS, ppm): 7.78 (m, 2H), 7.34 (m, 3H), 7.13–6.87 (m, 20H), 2.55 (m,2H),2.18(m,2H),1.54(m,2H),1.42(m,2H),1.32–1.26(m,6H); MS(MALDI-TOF):m / z calcd:628.3[M] + ,found:628.3.

[0441] The reaction formula for Example VII-1 is shown below:

[0442]

[0443] Example VII-2

[0444] In a 100 mL Schlenk reaction flask, 425 mg (1 mmol) of 1-methyl-1-ynyl-2,3,4,5-tetraphenylthiophene, 268 mg (1.2 mmol) of 8-bromooctanoic acid, 19 mg (0.1 mmol) of cuprous iodide, and 26 mg (0.1 mmol) of triphenylphosphine were added. Under nitrogen protection, 23 mg (0.02 mmol) of tetratetraphenylphosphine palladium and 30 mL of tetrahydrofuran / triethylamine (2 / 1, v / v) were added, and the reaction was carried out at room temperature for 48 hours. After the reaction was completed, the mixture was filtered, and the filtrate was evaporated to dryness. The product was separated and purified by column chromatography using a dichloromethane / methanol (20 / 1, v / v) mixture as the eluent, yielding 390 mg of a yellow solid product, with a yield of 69%. The NMR results of the product were as follows: 1 H NMR (400MHz, CDCl3), δ (TMS, ppm): 7.14–6.85 (m, 20H), 2.56 (m, 2H), 2.22 (m, 2H) ,1.55(m,2H),1.38(m,2H),1.33–1.26(m,6H),0.22(s,3H); MS(MALDI-TOF):m / z calcd:566.3[M] + ,found:566.3.

[0445] The reaction formula for Example VII-2 is shown below:

[0446]

[0447] Example VII-3

[0448] 145 g of PAO10 base oil and 44.39 g of octadecylamine were mixed in a reactor and heated to 60 °C. 2.5 g of 1-methyl-1-(9-carboxynonynyl)-2,3,4,5-tetraphenylthiophene was dissolved in 25 g of toluene and added to the reactor. 145 g of PAO10 base oil and 20.61 g of MDI were mixed and heated to 60 °C. After the MDI was completely dissolved, it was added to the reactor. The temperature was raised to 80 °C and reacted for 30 min. The temperature was then raised to 210 °C. Another 145 g of PAO10 base oil was added, and the mixture was cooled to about 100 °C. 10 g of molybdenum dibutyldithiocarbamate was added and ground into a grease.

[0449] Example VII-4

[0450] 145 g of PAO10 base oil and 44.39 g of octadecylamine were mixed in a reactor and heated to 60 °C. 2.5 g of 1-(9-carboxynonynyl)-1,2,3,4,5-pentaphenylthiophene was dissolved in 25 g of toluene and added to the reactor. 145 g of PAO10 base oil and 20.61 g of MDI were mixed and heated to 60 °C. After the MDI was completely dissolved, it was added to the reactor. The temperature was raised to 80 °C and reacted for 30 min. The temperature was then raised to 210 °C, and another 145 g of PAO10 base oil was added. The mixture was cooled to about 100 °C, and 10 g of molybdenum dibutyldithiocarbamate was added and ground into a grease.

[0451] Examples VII-5

[0452] Mix 145g of PAO10 base oil with 44.39g of octadecylamine in a reaction vessel and heat to 60°C. Mix 145g of PAO10 base oil with 20.61g of MDI and heat to 60°C. After the MDI is completely dissolved, add it to the reaction vessel and heat to 80°C for 30 minutes. Continue to heat to 210°C, add another 145g of PAO10 base oil, cool to about 100°C, add 2.5g of 1-(9-carboxynonynyl)-1,2,3,4,5-pentaphenylthiophene and 10g of molybdenum dibutyldithiocarbamate and grind into a grease.

[0453] Comparative Example VII-1

[0454] Mix 145g of PAO10 base oil with 44.39g of octadecylamine in a reaction vessel and heat to 60°C. Mix 145g of PAO10 base oil with 20.61g of MDI and heat to 60°C. After the MDI is completely dissolved, add it to the reaction vessel and heat to 80°C for 30 minutes. Continue to heat to 210°C, add another 145g of PAO10 base oil, cool to about 100°C, add 10g of molybdenum dibutyldithiocarbamate, and grind into a grease.

[0455] The performance of the greases in Examples VII-3, VII-4, VII-5, and Comparative Example VII-1 was evaluated using the following methods: wide temperature range dropping point test for greases (GB / T 3498), cone penetration test for greases and petroleum greases (GB / T 269), copper strip corrosion test for greases (GB / T 7326), and stencil oil separation test for greases (SH / T 0324). The evaluation results are shown in Table VII-1.

[0456] Table VII-1 Evaluation Results

[0457]

[0458] Eighth Implementation Method

[0459] An eighth embodiment of the present invention relates to a grease composition containing a thiophene derivative having general formula (XI). Specifically, the grease composition contains a thiophene derivative having general formula (XI), a thickener, and a lubricating base oil; the thiophene derivative having general formula (XI) accounts for 0.0005%-5% (preferably 0.001%-2%) of the total weight of the grease composition, the thickener accounts for 5%-30% (preferably 10%-20%) of the total weight of the grease composition, and the lubricating base oil constitutes the main component of the grease composition; the structure of the thiophene derivative having general formula (XI) is as follows:

[0460]

[0461] Among them, each R 20 They are the same or different from each other, and each is independently selected from C. 1-6 Straight-chain or branched alkyl groups (preferably selected from C) 1-4 (Straight-chain or branched alkyl); each p may be the same or different from each other, and each is independently selected from an integer between 0 and 5 (preferably selected from 0, 1, 2 or 3); R 21 Selected from C 1-6 Straight-chain or branched alkyl groups and C 6-10 Aryl (preferably selected from C) 1-4 (straight-chain or branched alkyl, phenyl, and naphthyl); R 22 Selected from C 1-6 Straight-chain or branched alkyl groups and C 6-10 Aryl (preferably selected from C) 1-4 Straight-chain or branched alkyl, phenyl, and naphthyl groups.

[0462] Preferably, the thiophene derivative having the general formula (XI) comprises:

[0463]

[0464] The main raw materials used in the examples are as follows:

[0465] The chemical reagents, such as hexaphenylthiophene, octadecylamine, MDI, 12-hydroxystearic acid, lithium hydroxide monohydrate, stearic acid, benzoic acid, aluminum isopropoxide trimer, tetrahydrofuran, triethylamine, dichloromethane, methanol, and toluene, are from Bailingwei Reagent Company, Inokai Reagent Company, or Sigma Reagent Company, while the PAO10 base oil is from ExxonMobil.

[0466] Example VIII-1

[0467] Mix 145g of PAO10 base oil with 44.39g of octadecylamine in a reaction vessel and heat to 60°C. Dissolve 2.5g of hexaphenylthiophene in 25g of toluene and add it to the reaction vessel. Mix 145g of PAO10 base oil with 20.61g of MDI and heat to 60°C. After the MDI is completely dissolved, add it to the reaction vessel. Heat to 80°C and react for 30 minutes. Continue to heat to 210°C, add another 145g of PAO10 base oil, cool to 100°C, and grind into a grease.

[0468] Example VIII-2

[0469] Mix 300g of PAO10 base oil with 39.21g of 12-hydroxystearic acid in a reaction vessel and heat to 85°C. Dissolve 2.5g of hexaphenylthiophene in 25g of toluene and add it to the reaction vessel. Mix 6.06g of lithium hydroxide monohydrate with 40g of distilled water and heat to 95°C. After the lithium hydroxide is completely dissolved, add it to the reaction vessel. Heat to remove water and continue to raise the temperature to 210°C. Then add 160g of PAO10 base oil. After cooling, grind into a grease.

[0470] Example VIII-3

[0471] Mix 200g of PAO10 base oil, 32.5g of stearic acid, and 14g of benzoic acid in a reaction vessel and heat to 90°C. Dissolve 2.5g of hexaphenylthiophene in 25g of toluene and add it to the reaction vessel. Mix 100g of PAO10 base oil with 32g of aluminum isopropoxide trimer and heat until the aluminum isopropoxide trimer is completely dissolved. Add the mixture to the reaction vessel and continue heating to 210°C for 30 minutes. Then add 150g of PAO10 base oil, cool, and grind into a grease.

[0472] Example VIII-4

[0473] Mix 300g of PAO10 base oil with 39.21g of 12-hydroxystearic acid in a reaction vessel and heat to 85°C. Mix 6.06g of lithium hydroxide monohydrate with 40g of distilled water and heat to 95°C. After the lithium hydroxide is completely dissolved, add it to the reaction vessel. Heat to remove water and continue heating to 210°C. Then add 160g of PAO10 base oil. After cooling, add 2.5g of hexaphenylthiophene and grind into a grease.

[0474] Comparative Example VIII-1

[0475] Mix 145g of PAO10 base oil with 44.39g of octadecylamine in a reaction vessel and heat to 60°C. Mix 145g of PAO10 base oil with 20.61g of MDI and heat to 60°C. After the MDI is completely dissolved, add it to the reaction vessel, raise the temperature to 80°C and react for 30 minutes. Continue to raise the temperature to 210°C, add another 145g of PAO10 base oil, cool to 100°C, and grind into a grease.

[0476] Comparative Example VIII-2

[0477] Mix 300g of PAO10 base oil with 39.21g of 12-hydroxystearic acid in a reaction vessel and heat to 85°C. Mix 6.06g of lithium hydroxide monohydrate with 40g of distilled water and heat to 95°C. After the lithium hydroxide is completely dissolved, add it to the reaction vessel. Heat to remove water and continue heating to 210°C. Then add 160g of PAO10 base oil. After cooling, grind into a grease.

[0478] Comparative Example VIII-3

[0479] Mix 200g of PAO10 base oil, 32.5g of stearic acid and 14g of benzoic acid in a reaction vessel and heat to 90°C. Mix 100g of PAO10 base oil with 32g of aluminum isopropoxide trimer and heat. After the aluminum isopropoxide trimer has completely dissolved, add it to the reaction vessel and continue to heat to 210°C and react for 30 minutes. Then add 150g of PAO10 base oil, cool and grind into a grease.

[0480] The performance of the greases in Examples VIII-1-4 and Comparative Examples VIII-1-3 was evaluated using the following methods: wide temperature range dropping point test for greases (GB / T 3498), cone penetration test for greases and petroleum greases (GB / T 269), anti-wear performance test for greases (SH / T 0204), and oil separation test for greases using a stencil (SH / T 0324). The evaluation results are shown in Table VIII-1.

[0481] Table VIII-1 Evaluation Results

[0482]

[0483] Ninth Implementation Method

[0484] A ninth embodiment of the present invention relates to a grease composition containing a tetraphenylethylene compound. Specifically, the grease composition comprises tetraphenylethylene or a derivative thereof, a thickener, and a base oil; the tetraphenylethylene or its derivative comprises 0.0005%-5% (preferably 0.001%-2%) of the total weight of the grease composition, the thickener comprises 5%-30% (preferably 10%-20%) of the total weight of the grease composition, and the base oil constitutes the main component of the grease composition; preferably, the structure of the tetraphenylethylene or its derivative is as follows:

[0485]

[0486] Each R is either the same as or different from the others, and each is independently selected from C. 1-6 Straight-chain or branched alkyl groups (preferably selected from C) 1-4 (Straight-chain or branched alkyl); each x may be the same as or different from each other, and each is independently selected from an integer between 0 and 5 (preferably selected from 0, 1, 2 or 3).

[0487] Preferred tetraphenylethylene or its derivatives include:

[0488]

[0489] The main raw materials used in the examples are as follows:

[0490] The chemical reagents, including tetraphenylethylene, octadecylamine, MDI, stearic acid, benzoic acid, aluminum isopropoxide trimer, tetrahydrofuran, triethylamine, dichloromethane, methanol, and toluene, are from Bailingwei Reagent Company, Inokai Reagent Company, or Sigma Reagent Company; the PAO10 base oil is from ExxonMobil.

[0491] Example IX-1

[0492] Mix 145g of PAO10 base oil with 44.39g of octadecylamine in a reaction vessel and heat to 60°C. Dissolve 2.5g of tetraphenylethylene in 5g of toluene and add it to the reaction vessel. Mix 145g of PAO10 base oil with 20.61g of MDI and heat to 60°C. After the MDI is completely dissolved, add it to the reaction vessel. Heat to 80°C and react for 30 minutes. Continue to heat to 210°C, add another 145g of PAO10 base oil, cool to 100°C, and grind into a grease.

[0493] Example IX-2

[0494] Mix 300g of PAO10 base oil with 39.21g of 12-hydroxystearic acid in a reaction vessel and heat to 85°C. Dissolve 2.5g of tetraphenylethylene in 5g of toluene and add it to the reaction vessel. Mix 6.06g of lithium hydroxide monohydrate with 40g of distilled water and heat to 95°C. After the lithium hydroxide is completely dissolved, add it to the reaction vessel. Heat to remove water and continue to raise the temperature to 210°C. Then add 160g of PAO10 base oil. After cooling, grind into a grease.

[0495] Example IX-3

[0496] Mix 200g of PAO10 base oil, 32.5g of stearic acid and 14g of benzoic acid in a reaction vessel and heat to 90°C. Dissolve 2.5g of tetraphenylethylene in 5g of toluene and add it to the reaction vessel. Mix 100g of PAO10 base oil and 32g of aluminum isopropoxide trimer and heat. After the aluminum isopropoxide trimer is completely dissolved, add it to the reaction vessel and continue to heat to 210°C and react for 30 minutes. Then add 150g of PAO10 base oil, cool and grind into a grease.

[0497] Example IX-4

[0498] Mix 300g of PAO10 base oil with 39.21g of 12-hydroxystearic acid in a reaction vessel and heat to 85°C. Mix 6.06g of lithium hydroxide monohydrate with 40g of distilled water and heat to 95°C. After the lithium hydroxide is completely dissolved, add it to the reaction vessel. Heat to remove water and continue heating to 210°C. Then add 160g of PAO10 base oil. After cooling, add 2.5g of tetraphenylethylene and grind into a grease.

[0499] Example IX-5

[0500] Mix 300g of PAO10 base oil with 39.21g of 12-hydroxystearic acid in a reaction vessel and heat to 85°C. Add 2.5g of tetraphenylethylene directly to the reaction vessel. Mix 6.06g of lithium hydroxide monohydrate with 40g of distilled water and heat to 95°C. After the lithium hydroxide is completely dissolved, add it to the reaction vessel. Heat to remove water and continue heating to 210°C. Add 160g of PAO10 base oil, cool, and grind into a grease.

[0501] Comparative Example IX-1

[0502] Mix 145g of PAO10 base oil with 44.39g of octadecylamine in a reaction vessel and heat to 60°C. Mix 145g of PAO10 base oil with 20.61g of MDI and heat to 60°C. After the MDI is completely dissolved, add it to the reaction vessel, raise the temperature to 80°C and react for 30 minutes. Continue to raise the temperature to 210°C, add another 145g of PAO10 base oil, cool to 100°C, and grind into a grease.

[0503] Comparative Example IX-2

[0504] Mix 300g of PAO10 base oil with 39.21g of 12-hydroxystearic acid in a reaction vessel and heat to 85°C. Mix 6.06g of lithium hydroxide monohydrate with 40g of distilled water and heat to 95°C. After the lithium hydroxide is completely dissolved, add it to the reaction vessel. Heat to remove water and continue heating to 210°C. Then add 160g of PAO10 base oil. After cooling, grind into a grease.

[0505] Comparative Example IX-3

[0506] Mix 200g of PAO10 base oil, 32.5g of stearic acid and 14g of benzoic acid in a reaction vessel and heat to 90°C. Mix 100g of PAO10 base oil with 32g of aluminum isopropoxide trimer and heat. After the aluminum isopropoxide trimer has completely dissolved, add it to the reaction vessel and continue to heat to 210°C and react for 30 minutes. Then add 150g of PAO10 base oil, cool and grind into a grease.

[0507] The performance of the greases in Examples IX-1-5 and Comparative Examples IX-1-3 was evaluated using the following methods: wide temperature range dropping point test for greases (GB / T 3498), cone penetration test for greases and petroleum greases (GB / T 269), anti-wear performance test for greases (SH / T 0204), and oil separation test for greases using a stencil (SH / T 0324). The evaluation results are shown in Table IX-1.

[0508] Table IX-1 Evaluation Results

[0509]

Claims

1. Thiol derivatives having the general formula (I): （I） In general formula (I), each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups, each x is independently selected from an integer between 0 and 5; Each G is independently selected from hydrogen and C. 1-6 Straight-chain or branched alkyl groups, alkynyl groups represented by formula (I-1), alkynyl groups represented by formula (I-2), alkynyl groups represented by formula (I-3), and groups represented by formula (I-1'). （I-1）， （I-2）， （I-3）， In equations (I-1), (I-2), and (I-3), each R1 is independently selected from hydrogen and C. 1-6 Straight-chain or branched alkyl groups; each R2 is independently selected from C 1-6 Straight-chain or branched alkylene groups; each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl; each x is independently selected from an integer between 0 and 5; each y is independently selected from an integer between 0 and 4; each z is independently selected from an integer between 1 and 4; In equation (I-1), one of A and A' is NR, and the other is S, where R is selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups; In equations (I), (I-2), and (I-3), each G' is independently selected from hydrogen and C. 1-6 Straight-chain or branched alkyl groups, groups represented by formula (I-1'), and alkynyl groups represented by formula (I-2'); （I-1’）， （I-2’）， In equations (I-1') and (I-2'), each R is independently selected from hydrogen and C. 1-6 Straight-chain or branched alkyl; each x is independently selected from an integer between 0 and 5; each y' is independently selected from an integer between 0 and 3; each z' is independently selected from an integer between 0 and 3; In general formula (I), at least one G is selected from the alkynyl group shown in formula (I-1), the alkynyl group shown in formula (I-2), and the alkynyl group shown in formula (I-3).

2. The thiophene derivative having general formula (I) according to claim 1, characterized in that... Including the following compounds: ， ， ， ， ， , 。 3. The method for preparing the thiophene derivative having general formula (I) according to claim 1, comprising the step of reacting a thiophene compound of general formula (III-1) with one or more alkyne compounds of general formulas (III-1'), (III-2'), and (III-3'), (III-1), In general formula (III-1), each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups, each x is independently selected from an integer between 0 and 5; each G is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups, groups represented by formula (I-1'), and X groups; each G' is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups, groups represented by formula (I-1'), and X groups; （I-1’）， In equation (I-1'), each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups; each x is independently selected from an integer between 0 and 5; The X group is selected from F, Cl, Br, I, and OH; At least one G or G' is selected from the X group; (III-1’), (III-2’), (III-3’), In equations (III-1'), (III-2'), and (III-3'), each R2 is independently selected from C. 1-6 Straight-chain or branched alkylene groups; each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl; each y is independently selected from an integer between 0 and 4; each z is independently selected from an integer between 1 and 4; In equation (III-1'), one of A and A' is NR, and the other is S, where R is selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups.

4. The preparation method according to claim 3, characterized in that, In the reaction, the molar ratio between the thiophene compound shown in (III-1) and one or more alkyne compounds shown in general formulas (III-1'), (III-2'), and (III-3') is 0.1-10:1; the reaction temperature is 0-50°C.

5. The preparation method according to claim 3, characterized in that, In the reaction, the molar ratio between the thiophene compound shown in (III-1) and one or more alkyne compounds shown in general formulas (III-1'), (III-2'), and (III-3') is 0.2-5:1; the reaction temperature is 15-35°C.

6. The preparation method according to claim 3, characterized in that, In the reaction of the thiophene compound shown in (III-1) with one or more alkyne compounds shown in general formulas (III-1'), (III-2'), and (III-3'), a catalyst is added, said catalyst being selected from one or more of metal phosphine complexes, metal halides, hydrocarbon phosphine compounds, and azo compounds.

7. The preparation method according to claim 3, characterized in that, In the reaction of the thiophene compound shown in (III-1) with one or more alkyne compounds shown in general formulas (III-1'), (III-2'), and (III-3'), a catalyst is added, said catalyst being selected from a mixture of metal phosphine complexes, metal halides, and hydrocarbon phosphine compounds in a molar ratio of 1:0.1-10:0.1-10.

8. The method for preparing the thiophene derivative having general formula (I) according to claim 1, comprising the step of reacting a thiophene compound of general formula (III-1-1) with one or more compounds of general formulas (III-1'-1), (III-2'-1), and (III-3'-1), (III-1-1), In the general formula (III-1-1), each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups, each x is independently selected from an integer between 0 and 5; each G is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups, groups represented by formula (I-1') and Each G' is independently selected from hydrogen and C. 1-6 Straight-chain or branched alkyl groups, groups represented by formula (I-1') and ; （I-1’）， In equation (I-1'), each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups; each x is independently selected from an integer between 0 and 5; At least one G or G' is selected from ; (III-1’-1), (III-2’-1), (III-3’-1), The X group is selected from F, Cl, Br, I, and OH; In equations (III-1'-1), (III-2'-1), and (III-3'-1), each R2 is independently selected from C. 1-6 Straight-chain or branched alkylene groups; each R is independently selected from hydrogen, C 1-6 Straight-chain or branched alkyl; each y is independently selected from an integer between 0 and 4; each z is independently selected from an integer between 1 and 4; in formula (III-1'-1), one of A and A' is NR and the other is S, wherein R is selected from hydrogen, C 1-6 Straight-chain or branched alkyl groups.

9. The preparation method according to claim 8, characterized in that, In the reaction, the molar ratio between the thiophene compound shown in (III-1-1) and one or more compounds shown in general formulas (III-1'-1), (III-2'-1), and (III-3'-1) is 0.1-10:1; the temperature of the reaction is 0-50°C.

10. The preparation method according to claim 8, characterized in that, In the reaction, the molar ratio between the thiophene compound shown in (III-1-1) and one or more compounds shown in general formulas (III-1'-1), (III-2'-1), and (III-3'-1) is 0.2-5:1; the temperature of the reaction is 15-35°C.

11. The preparation method according to claim 8, characterized in that, In the reaction of the thiophene compound shown in (III-1-1) with one or more compounds of general formulas (III-1'-1), (III-2'-1), and (III-3'-1), a catalyst is added, said catalyst being selected from one or more of metal phosphine complexes, metal halides, hydrocarbon phosphine compounds, and azo compounds.

12. The preparation method according to claim 8, characterized in that, In the reaction of the thiophene compound shown in (III-1-1) with one or more compounds of general formulas (III-1'-1), (III-2'-1), and (III-3'-1), a catalyst is added, said catalyst being selected from a mixture of metal phosphine complexes, metal halides, and hydrocarbon phosphine compounds in a molar ratio of 1:0.1-10:0.1-10.

13. Use of the thiophene derivative of general formula (I) of claim 1 or 2, or the thiophene derivative of general formula (I) prepared by the method according to any one of claims 3-12, in luminescent components and devices, fluorescent probes, bioimaging, lubricants and greases.

14. A grease composition comprising a luminescent material, a thickener, and a lubricating base oil; wherein the luminescent material is a photoluminescent material having aggregation-induced emission properties, and the photoluminescent material having aggregation-induced emission properties is selected from thiophene derivatives having general formula (I) according to claim 1 or 2.

15. The grease composition of claim 14, wherein the luminescent material accounts for 0.0005%-5% of the total weight of the grease composition, the thickener accounts for 5%-30% of the total weight of the grease composition, and the lubricating base oil constitutes the main component of the grease composition.

16. The grease composition of claim 14, wherein the luminescent material accounts for 0.001%-2% of the total weight of the grease composition, the thickener accounts for 10%-20% of the total weight of the grease composition, and the lubricating base oil constitutes the main component of the grease composition.

17. A method for preparing the lubricating grease composition according to any one of claims 14-16, comprising: The lubricating base oil, thickener, and luminescent material are mixed, refined, and ground into a grease.

18. The preparation method according to claim 17, characterized in that, The refining operation is performed at a temperature of 160-240℃ for 10-240 minutes.

19. The preparation method according to claim 17, characterized in that, The grease composition is a polyurea grease composition, a lithium-based grease composition, or a composite aluminum-based grease composition.

20. The preparation method according to claim 19, characterized in that, The lubricating grease composition is a polyurea lubricating grease composition. The preparation method of the polyurea lubricating grease composition includes: mixing a portion of the lubricating base oil, the luminescent material, amine, and isocyanate, reacting at 65-95℃ for 10-60 minutes, and after the reaction is complete, continuing to heat to 190-220℃ for high-temperature refining, then adding the remaining base oil and cooling to 60-120℃, and grinding into grease.

21. The preparation method according to claim 20, characterized in that, The amine is C2-C 20 Alkylamines and / or C6-C 20 Aromatic amine; the isocyanate is C2-C 20 Isocyanates.

22. The preparation method according to claim 19, characterized in that, The grease composition is a lithium-based grease composition. The preparation method of the lithium-based grease composition includes: mixing a portion of the lubricating base oil and fatty acids in a reaction vessel and heating the mixture to 40-90°C; adding the luminescent material and an aqueous solution of lithium hydroxide; heating to remove water and then continuing to heat to 190-220°C for high-temperature refining; adding the remaining lubricating base oil and cooling to 60-120°C; and grinding the mixture into grease.

23. The preparation method according to claim 22, characterized in that, The fatty acid is C. 12 -C 20 Fatty acids and / or C 12 -C 20 Hydroxy fatty acids.

24. The preparation method according to claim 19, characterized in that, The grease is a composite aluminum-based grease. The preparation method of the composite aluminum-based grease includes: mixing and heating a portion of base oil, fatty acids and small molecule acids in a reaction vessel to 40-90°C, adding the luminescent material, mixing another portion of lubricating base oil with aluminum alkoxide compound and heating to 40-100°C, adding the aluminum alkoxide compound to the reaction vessel after it has completely dissolved, continuing to heat to 190-220°C for high-temperature refining, adding the remaining lubricating base oil, cooling to 60-120°C, and grinding into grease.

25. The preparation method according to claim 24, characterized in that, The fatty acid is C. 12 -C 20 Fatty acids and / or C 12 -C 20 Hydroxy fatty acids; the small molecule acid is C2-C 11 Organic acids; the aluminum alkoxide compound is selected from aluminum isopropoxide, aluminum isopropoxide dimer, and aluminum isopropoxide trimer.

26. The preparation method according to any one of claims 17-25, characterized in that, The luminescent material is dissolved in a solvent, which is an aromatic solvent, beforehand.

Images