A multi-metal oxide cluster lubricating material and its synthesis method and application

Abstract

The application belongs to the technical field of coordination chemistry, and particularly relates to a polyoxometalate lubricating material as well as a synthesis method and application thereof. The polyoxometalate lubricating material provided by the application has a chemical structural formula selected from any one of the following formulas, wherein PIB is a polyisobutenyl group. The polyoxometalate lubricating material is prepared by using an acid-base reaction between a polyoxometalate and a polyisobutenyl monosuccinimide. The polyoxometalate lubricating material has a high molybdenum content, can be stably dispersed in base oil for a long time, and has excellent lubricating performance in an oil solution, and can be applied to a mechanical system as a friction-reducing and wear-resistant lubricating oil.

Description

Technical Field

[0001] This invention belongs to the field of coordination chemistry technology, specifically relating to a polymetallic oxy-cluster lubricating material, its synthesis method, and its application. Background Technology

[0002] Lubricating oil additives include friction modifiers, anti-wear agents, dispersants, detergents, and antioxidants. Classic small-molecule friction modifiers and anti-wear additives have inherent chemical, thermal, or mechanical instabilities, leading to serious emissions of harmful exhaust gases and particulate matter, which do not meet environmental protection requirements. At the same time, there is competitive adsorption between traditional small-molecule metal additives and large-molecule dispersants, and molybdenum-based additives are easily consumed, further reducing the durability of lubricating oils.

[0003] While nanoparticles possess excellent lubrication properties and chemical stability, significantly reducing harmful emissions and toxicity, making them an environmentally friendly green additive, they are insoluble in base oils. Although nanoparticles with surface-modified long-chain alkanes can disperse in base oils, they tend to aggregate and settle over long periods of time, limiting their practical applications.

[0004] Polyoxometalates (POMs) are a class of homopoly and heteropolyoxometalate compounds with a defined structure and a size between 0.5 and 5 nm, whose framework is rich in transition elements such as molybdenum, tungsten, vanadium, niobium, and tantalum. POMs possess diverse topological structures and rich physical and chemical properties, thus showing great application potential in optical, electronic, and magnetic functional materials, medicine, and catalysis. Compared with nanoparticles, these clusters have a defined topological structure and atomic composition. Sun Lei et al. prepared stearic acid / ammonium phosphomolybdate composite nanoparticles, which exhibited good friction reduction and load-bearing capacity as well as excellent wear resistance (Sun Lei, Zhou Jingfang, Zhang Zhijun, et al. Preparation and characterization of stearic acid-modified ammonium phosphomolybdate nanoparticles [J]. Journal of Henan University (Natural Science Edition), 2001, 31(01): 59-62). However, these cluster-based nanoparticles were only dispersed in liquid paraffin and did not truly dissolve; after prolonged standing, they still aggregated and settled.

[0005] Therefore, there is an urgent need in the art to provide a multi-metal-oxygen cluster lubricating material that can be stably dispersed in base oil over a long period of time, so that the resulting oil solution has better lubrication performance and can be used as a friction-reducing and anti-wear lubricating oil in mechanical systems. Summary of the Invention

[0006] This invention addresses the problems existing in the prior art by providing a polymetallic oxy-cluster lubricating material, its synthesis method, and its application, which can improve the dispersibility and stability of lubricating materials.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0008] A multi-metal-oxygen cluster lubricating material, characterized in that the chemical structural formula of the multi-metal-oxygen cluster lubricating material is selected from any one of the following formulas:

[0009]

[0010] In the above formula, PIB stands for polyisobutylene.

[0011] Preferably, the polyoxometalate lubricant has a molybdenum content of 1.5-8.0% and a nitrogen content of 0.5-3.5%.

[0012] The present invention provides a method for synthesizing the above-mentioned polyoxometalate cluster lubricating material, comprising the following steps: under an inert gas atmosphere, the polyoxometalate cluster is reacted with polyisobutylene monosuccinimide in an acid-base reaction to obtain the material.

[0013] Preferably, the inert gas is nitrogen or argon.

[0014] Preferably, the polyoxometalate cluster is a molybdenum-containing cluster compound.

[0015] More preferably, the polymetallic oxy-metal cluster includes molybdic acid (H2MoO4) and phosphomolybdic acid (H3[PMoO4]). 12 O 40 ]), molybdenum silicate (H4[SiMo) 12 O 40 ]) and ammonium heptamolybdate ((NH4)6[Mo7O 24 Any one of the following: [ ]. Among them, the counter cation of molybdic acid, phosphomolybdic acid, and silicomolybdic acid is H... + The counter cation of ammonium heptamolybdate is NH4+. + amine group and H + or NH4 + The molar ratio can be adjusted according to the actual situation, generally between 5 and 1.

[0016] More preferably, the polymetallic oxygen cluster is phosphomolybdic acid.

[0017] Preferably, the polymetallic oxy-oxide cluster needs to be dissolved in water or ethanol first.

[0018] Preferably, the chemical structural formula of the polyisobutylene monosuccinimide is as follows:

[0019]

[0020] In the above formula, PIB stands for polyisobutylene.

[0021] Preferably, the preparation method of the polyisobutylene monosuccinimide includes the following steps: under argon or nitrogen atmosphere, polyisobutylene maleic anhydride, primary amine compound and solvent are subjected to a dehydration reaction under reflux conditions to obtain the product.

[0022] Preferably, the polyisobutylene maleic anhydride has a molecular weight of 800-2500, and the polyisobutylene maleic anhydride needs to be dissolved in a solvent and heated to 90-110°C.

[0023] Preferably, the primary amine compound includes any one of N-(2-hydroxyethyl)ethylenediamine and polyethylenepolyamine.

[0024] Preferably, the solvent is xylene, o-dichlorobenzene, or a base oil.

[0025] Preferably, the molar volume ratio of the polyisobutylene maleic anhydride, the primary amine compound, and the solvent is 0.05-0.12 mol: 0.04-0.08 mol: 300-400 mL.

[0026] Preferably, the temperature of the dehydration reaction is 140-180℃, the time of the dehydration reaction is 7-9h, and after the dehydration reaction is completed, cooling and vacuum distillation are performed to remove the solvent.

[0027] Preferably, the acid-base reaction temperature is 60-140℃, the acid-base reaction time is 12-48h, the acid-base reaction requires the addition of reaction solvents such as xylene, toluene or base oil, and after the acid-base reaction is completed, the reaction solvent is removed by vacuum distillation, petroleum ether is added, and the mixture is centrifuged and rotary evaporated.

[0028] This invention replaces the countercations on the surface of polyoxometalate clusters with amphiphilic cationic block copolymers. The resulting cluster-based composite material can be uniformly dispersed in organic solvents, forming spherical micelles, rod-shaped micelles, worm-like micelles, or vesicles. The star-shaped supramolecular polymer with polyoxometalate clusters as its core can dissolve in organic solvents or base oils as individual clusters. Polyisobutylene monosuccinimide is weakly basic and is a widely used ashless dispersant. Therefore, the polyoxometalate cluster lubricating material prepared by reacting polyoxometalate clusters with polyisobutylene monosuccinimide via an acid-base reaction, when dispersed in base oil, can improve the dispersibility and stability of the lubricating material.

[0029] The present invention also provides the application of the above-mentioned polyoxometalate cluster lubricating material or the polyoxometalate cluster lubricating material synthesized by the above-mentioned synthesis method in the preparation of lubricating oil additives.

[0030] When dispersed in base oil PAO-10, the oil solution exhibits a coefficient of friction of less than 0.14 under the frictional conditions of 300 N load, 50 °C temperature, 120 min time, 1 mm stroke, and 50 Hz frequency, as determined by the SRV test method (NB / SH / T 0847-2010) based on extreme pressure lubricating oil friction and wear performance. Therefore, it can be used as a lubricating oil.

[0031] Preferably, the lubricating oil includes mineral base oil, synthetic base oil, and vegetable oil base oil.

[0032] Mineral base oils are refined from crude oil; synthetic base oils are base oils synthesized through chemical methods, such as polyalphaolefins; vegetable oil base oils are oils obtained from the fruits, seeds, germs, etc. of plants.

[0033] More preferably, the mineral base oil is HVIP6 and the synthetic base oil is PAO10.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] (1) The present invention utilizes the acid-base reaction between polyoxometalate clusters and polyisobutylene monosuccinimide to prepare a polyoxometalate cluster lubricating material. The lubricating material has a high molybdenum content and can be stably dispersed in base oil for a long time.

[0036] (2) The experimental results of this invention confirm that the oil solution formed by dispersing the polymetallic oxygen cluster lubricating material in the base oil has good long-term stability. When the lubricating material is added to a Group II base oil at a dosage of 5%, it is clear and transparent in appearance. After being stored at room temperature for 1 month and at 100°C for 10 days, there is no precipitation or stratification.

[0037] (3) The experimental results of this invention also confirm that, compared with base oil, the oil solution formed by dispersing polymetallic oxygen cluster lubricating materials in base oil has better lubrication performance and can be used as a friction-reducing and anti-wear lubricating oil in mechanical systems. Attached Figure Description

[0038] Figure 1 These are the infrared spectra of PIBS2300-N in Example 1 and PIBS2300-NOH in Example 2.

[0039] Figure 2 These are the infrared spectra of PIBS1000-N in Example 3 and PIBS1000-NOH in Example 4.

[0040] Figure 3 This is the infrared spectrum of PIBS1000-NOH-NMo(Mo-13) in Example 5.

[0041] Figure 4 This is the X-ray photoelectron spectrum of PIBS1000-NOH-NMo(Mo-13) in Example 5.

[0042] Figure 5 This is the infrared spectrum of PIBS2300-N-HMo(Mo-10) in Example 6.

[0043] Figure 6 This is the X-ray photoelectron spectrum of PIBS2300-N-HMo(Mo-10) in Example 6.

[0044] Figure 7 This is the infrared spectrum of PIBS1000-N-PMo(Mo-2) in Example 7.

[0045] Figure 8 This is the X-ray photoelectron spectrum of PIBS1000-N-PMo(Mo-2) in Example 7.

[0046] Figure 9 These are the infrared spectra of PIBS2300-N-PMo(Mo-4) in Example 8, PIBS2300-N-PMo(Mo-5) in Example 9, and PIBS2300-N-PMo(Mo-11) in Example 10.

[0047] Figure 10 This is the X-ray photoelectron spectrum of PIBS2300-N-PMo(Mo-4) in Example 8.

[0048] Figure 11 This is the X-ray photoelectron spectrum of PIBS2300-N-PMo(Mo-5) in Example 9.

[0049] Figure 12 This is the X-ray photoelectron spectrum of PIBS2300-N-PMo(Mo-11) in Example 10.

[0050] Figure 13 This is the infrared spectrum of PIBS2300-NOH-PMo(Mo-9) in Example 11.

[0051] Figure 14 This is the X-ray photoelectron spectrum of PIBS2300-NOH-PMo(Mo-9) in Example 11.

[0052] Figure 15 This is the infrared spectrum of PIBS1000-NOH-PMo(Mo-8) in Example 12.

[0053] Figure 16 This is the X-ray photoelectron spectrum of PIBS1000-NOH-PMo(Mo-8) in Example 12.

[0054] Figure 17 This is the infrared spectrum of PIBS2300-N-SiMo(Mo-3) in Example 13.

[0055] Figure 18This is the X-ray photoelectron spectrum of PIBS2300-N-SiMo(Mo-3) in Example 13.

[0056] Figure 19 This is the infrared spectrum of PIBS1000-N-SiMo(Mo-7) in Example 14.

[0057] Figure 20 This is the X-ray photoelectron spectrum of PIBS1000-N-SiMo(Mo-7) in Example 14.

[0058] Figure 21 This is a schematic diagram of the oil solution stability of the polymetallic oxygen cluster lubricating materials prepared in Examples 5-14 (where a represents 30 min at 100°C; b represents 30 days at room temperature; and c represents 10 days at 100°C).

[0059] Figure 22 The results are the oil friction coefficient test results of PIBS2300-N-HMo(Mo-10) in Example 6 and PIBS2300-N-PMo(Mo-11) in Example 10. Detailed Implementation

[0060] It is worth noting that the raw materials used in this invention are all commercially available products.

[0061] Example 1

[0062] A polyisobutylene monosuccinimide (PIBS2300-N) has the following chemical structural formula:

[0063]

[0064] The preparation method of this polyisobutylene monosuccinimide is as follows: Polyisobutylene maleic anhydride (115 g, 0.05 mol) with a molecular weight of 2300 g / mol is dispersed in 300 mL of xylene. The mixture is heated to 100 °C, and 50 mL of a xylene solution of polyethylenepolyamine (9.3 g, 0.04 mol) is added dropwise under argon atmosphere. After the addition is complete, the reaction is carried out at 160 °C for 8 h. After cooling, the xylene solvent is removed by vacuum distillation to obtain the final product. The synthetic route is as follows:

[0065]

[0066] The infrared spectrum of the polyisobutylene monosuccinimide is as follows: Figure 1 As shown, the successful synthesis of PIBS2300-N is confirmed.

[0067] Example 2

[0068] A polyisobutylene monosuccinimide (PIBS2300-NOH) has the following chemical structural formula:

[0069]

[0070] The preparation method of this polyisobutylene monosuccinimide is as follows: Polyisobutylene maleic anhydride (115 g, 0.05 mol) with a molecular weight of 2300 g / mol is dispersed in 300 mL of xylene. The mixture is heated to 100 °C, and 50 mL of a xylene solution of N-(2-hydroxyethyl)ethylenediamine (5.2 g, 0.05 mol) is added dropwise under argon atmosphere. After the addition is complete, the mixture is reacted at 160 °C for 8 h. After cooling, the xylene solvent is removed by vacuum distillation to obtain the final product. The synthetic route is as follows:

[0071]

[0072] The infrared spectrum of the polyisobutylene monosuccinimide is as follows: Figure 1 As shown, the successful synthesis of PIBS2300-NOH is confirmed.

[0073] Example 3

[0074] A polyisobutylene monosuccinimide (PIBS1000-N) has the following chemical structural formula:

[0075]

[0076] The preparation method of this polyisobutylene monosuccinimide is as follows: 120 g (0.12 mol) of polyisobutylene maleic anhydride with a molecular weight of 1000 g / mol is dispersed in 300 mL of xylene. The mixture is heated to 100 °C, and 50 mL of a xylene solution of polyethylenepolyamine (18.6 g (0.08 mol)) is added dropwise under argon atmosphere. After the addition is complete, the mixture is reacted at 160 °C for 8 h. After cooling, the xylene solvent is removed by vacuum distillation to obtain the final product. The synthetic route is as follows:

[0077] The infrared spectrum of the polyisobutylene monosuccinimide is as follows: Figure 2 As shown, the successful synthesis of PIBS1000-N is confirmed.

[0078] Example 4

[0079] A polyisobutylene monosuccinimide (PIBS1000-NOH) has the following chemical structural formula:

[0080]

[0081] The preparation method of this polyisobutylene monosuccinimide is as follows: 120 g (0.12 mol) of polyisobutylene maleic anhydride with a molecular weight of 1000 g / mol is dispersed in 300 mL of xylene. The mixture is heated to 100 °C, and 50 mL of a xylene solution of N-(2-hydroxyethyl)ethylenediamine (9.36 g (0.09 mol)) is added dropwise under argon atmosphere. After the addition is complete, the mixture is reacted at 160 °C for 8 h. After cooling, the xylene solvent is removed by vacuum distillation to obtain the final product.

[0082] The infrared spectrum of the polyisobutylene monosuccinimide is as follows: Figure 2 As shown, the successful synthesis of PIBS1000-NOH is confirmed.

[0083] Example 5

[0084] A multi-metal-oxygen cluster lubricant (PIBS1000-NOH-NMo) has the following chemical structural formula:

[0085]

[0086] A polymetallic oxy-oxide cluster lubricant (PIBS1000-NOH-NMo) was generated by reacting ammonium heptamolybdate with PIBS1000-NOH from Example 4, and was designated Mo-13.

[0087] The preparation method of this polymetallic oxy-oxide cluster lubricant is as follows: Ammonium heptamolybdate (20.29 g, 0.02 mol) was dissolved in 100 mL of distilled water. Under argon atmosphere, this solution was added dropwise to 300 mL of toluene solution containing PIBS1000-NOH (120 g, 0.11 mol). The reaction was carried out in an oil bath at 120 °C for 16 h. The solvent toluene was removed by vacuum distillation. Petroleum ether was added, and the insoluble matter was removed by centrifugation. The supernatant was precipitated for 12 h and then centrifuged again at 4000 rpm for 10 min. The second supernatant was then removed by rotary evaporation to remove the petroleum ether, yielding PIBS1000-NOH-NMo(Mo-13). This polymetallic oxy-oxide cluster lubricant is blue-green. The synthetic route is as follows:

[0088]

[0089] The infrared spectrum of the polyoxometalate lubricating material is as follows: Figure 3 As shown, the successful synthesis of PIBS1000-NOH-NMo is confirmed; its X-ray photoelectron spectrum is as follows. Figure 4 As shown, the main forms in which molybdenum exists are characterized.

[0090] Example 6

[0091] A multi-metal-oxygen cluster lubricant (PIBS2300-N-HMo) has the following chemical structural formula:

[0092]

[0093] A multimetallic oxide cluster lubricant (PIBS2300-N-HMo) was generated by reacting molybdic acid with PIBS2300-N from Example 1, and was designated Mo-10.

[0094] The preparation method of this polymetallic oxy-oxide cluster lubricating material is as follows: Molybdic acid (5.4 g, 0.03 mol) was dispersed in 100 mL of distilled water. Under argon atmosphere, it was added dropwise to 300 mL of toluene solution containing PIBS2300-N (120 g, 0.05 mol). The reaction was carried out in an oil bath at 120 °C for 16 h. The solvent toluene was removed by vacuum distillation. Petroleum ether was added, and the insoluble matter was removed by centrifugation. The supernatant was precipitated for 12 h and then centrifuged again at 4000 rpm for 10 min. The second supernatant was then evaporated by rotary evaporation to remove the petroleum ether, yielding PIBS2300-N-HMo(Mo-10). This polymetallic oxy-oxide cluster lubricating material is yellowish-brown. The synthetic route is as follows:

[0095]

[0096] The infrared spectrum of the polyoxometalate lubricating material is as follows: Figure 5 As shown, the successful synthesis of PIBS2300-N-HMo is confirmed; its X-ray photoelectron spectrum is as follows. Figure 6 As shown, the main forms in which molybdenum exists are characterized.

[0097] Example 7

[0098] A multi-metal-oxygen cluster lubricant (PIBS1000-N-PMo) has the following chemical structural formula:

[0099]

[0100] A polymetallic oxygen cluster lubricant (PIBS1000-N-PMo) was generated by reacting phosphomolybdic acid with PIBS1000-N from Example 3, and was designated as Mo-2.

[0101] The preparation method of this polymetallic oxy-oxide cluster lubricating material is as follows: Phosphomolybdic acid (26 g, 0.01 mol) was dispersed in 150 mL of distilled water. Under argon atmosphere, it was added dropwise to 300 mL of toluene solution containing PIBS1000-N (130 g, 0.11 mol). The reaction was carried out in an oil bath at 120 °C for 12 h. The solvent toluene was removed by vacuum distillation. Petroleum ether was added, and the insoluble matter was removed by centrifugation. The supernatant was precipitated for 12 h and then centrifuged again at 4000 rpm for 10 min. The second supernatant was then removed by rotary evaporation to remove the petroleum ether, yielding PIBS1000-N-PMo(Mo-2). This polymetallic oxy-oxide cluster lubricating material is deep blue. The synthetic route is as follows:

[0102]

[0103] The infrared spectrum of the polyoxometalate lubricating material is as follows: Figure 7 As shown, the successful synthesis of PIBS1000-N-PMo is confirmed; its X-ray photoelectron spectrum is as follows. Figure 8 As shown, the main forms in which molybdenum exists are characterized.

[0104] Example 8

[0105] A multi-metal oxide cluster lubricant (PIBS2300-N-PMo) has the following chemical structural formula:

[0106]

[0107] A polymetallic oxygen cluster lubricant (PIBS2300-N-PMo) was generated by reacting phosphomolybdic acid with PIBS2300-N from Example 1, and was designated as Mo-4.

[0108] The preparation method of this polymetallic oxy-oxide cluster lubricating material is as follows: Phosphomolybdic acid (26 g, 0.01 mol) was dispersed in 150 mL of ethanol. Under argon atmosphere, this was added dropwise to 300 mL of toluene solution containing PIBS2300-N (120 g, 0.05 mol). The mixture was reacted in an oil bath at 60 °C for 24 h. Ethanol and toluene were removed by vacuum distillation. Petroleum ether was added, and insoluble matter was removed by centrifugation. The supernatant was precipitated for 12 h and then centrifuged again at 4000 rpm for 10 min. The second supernatant was then removed by rotary evaporation to remove petroleum ether, yielding PIBS2300-N-PMo(Mo-4). This polymetallic oxy-oxide cluster lubricating material is deep blue. The synthetic route is as follows:

[0109]

[0110] The infrared spectrum of the polyoxometalate lubricating material is as follows: Figure 9 As shown, the successful synthesis of PIBS2300-N-PMo is confirmed; its X-ray photoelectron spectrum is as follows. Figure 10 As shown, the main forms in which molybdenum exists are characterized.

[0111] Example 9

[0112] A multi-metal oxide cluster lubricant (PIBS2300-N-PMo) has the following chemical structural formula:

[0113]

[0114] A multimetallic oxygen cluster lubricant (PIBS2300-N-PMo) was generated by reacting phosphomolybdic acid with PIBS2300-N from Example 1, and was designated Mo-5.

[0115] The preparation method of this polymetallic oxy-oxide cluster lubricant is as follows: 26 g (0.01 mol) of phosphomolybdic acid was added to 300 mL of toluene solution of PIBS2300-N (120 g, 0.05 mol). The mixture was reacted in an oil bath at 120 °C for 48 h. The solvent toluene was removed by vacuum distillation. Petroleum ether was added, and the insoluble matter was removed by centrifugation. The supernatant was precipitated for 12 h and then centrifuged again at 4000 rpm for 10 min. The second supernatant was removed by rotary evaporation to remove the petroleum ether, yielding PIBS2300-N-PMo(Mo-5). This polymetallic oxy-oxide cluster lubricant is dark blue. The synthetic route is as follows:

[0116]

[0117] The infrared spectrum of the polyoxometalate lubricating material is as follows: Figure 9 As shown, the successful synthesis of PIBS2300-N-PMo is confirmed; its X-ray photoelectron spectrum is as follows. Figure 11 As shown, the main forms in which molybdenum exists are characterized.

[0118] Example 10

[0119] A multi-metal oxide cluster lubricant (PIBS2300-N-PMo) has the following chemical structural formula:

[0120]

[0121] A multimetallic oxygen cluster lubricant (PIBS2300-N-PMo) was generated by reacting phosphomolybdic acid with PIBS2300-N from Example 1, and was designated Mo-11.

[0122] The preparation method of this polymetallic oxy-oxide cluster lubricating material is as follows: Phosphomolybdic acid (26 g, 0.01 mol) was dispersed in 150 mL of distilled water. Under argon atmosphere, it was added dropwise to 300 mL of toluene solution containing PIBS2300-N (120 g, 0.05 mol). The reaction was carried out in an oil bath at 120 °C for 18 h. The solvent toluene was removed by vacuum distillation. Petroleum ether was added, and the insoluble matter was removed by centrifugation. The supernatant was precipitated for 12 h and then centrifuged again at 4000 rpm for 10 min. The second supernatant was then removed by rotary evaporation to remove the petroleum ether, yielding PIBS2300-N-PMo(Mo-11). This polymetallic oxy-oxide cluster lubricating material is deep blue. The synthetic route is as follows:

[0123]

[0124] The infrared spectrum of the polyoxometalate lubricating material is as follows: Figure 9 As shown, the successful synthesis of PIBS2300-N-PMo is confirmed; its X-ray photoelectron spectrum is as follows. Figure 12 As shown, the main forms in which molybdenum exists are characterized.

[0125] Example 11

[0126] A multi-metal-oxygen cluster lubricant (PIBS2300-NOH-PMo) has the following chemical structural formula:

[0127]

[0128] A polymetallic oxy-oxide cluster lubricant (PIBS2300-NOH-PMo) was generated by reacting phosphomolybdic acid with PIBS2300-NOH from Example 2, and was designated Mo-9.

[0129] The preparation method of this polymetallic oxy-oxide cluster lubricating material is as follows: Phosphomolybdic acid (26 g, 0.01 mol) was dispersed in 150 mL of ethanol. Under argon atmosphere, this was added dropwise to 300 mL of toluene solution containing PIBS2300-NOH (120 g, 0.05 mol). The reaction was carried out in an oil bath at 60 °C for 24 h. Ethanol and toluene solvent were removed by vacuum distillation. Petroleum ether was added, and insoluble matter was removed by centrifugation. The supernatant was precipitated for 12 h and then centrifuged again at 4000 rpm for 10 min. 60 g of Group II base oil HVP6 was added to the second supernatant, and petroleum ether was removed by rotary evaporation to obtain PIBS2300-NOH-PMo(Mo-9). This polymetallic oxy-oxide cluster lubricating material is blue-green. The synthetic route is as follows:

[0130]

[0131] The infrared spectrum of the polyoxometalate lubricating material is as follows: Figure 13 As shown, the successful synthesis of PIBS2300-NOH-PMo is confirmed; its X-ray photoelectron spectrum is as follows. Figure 14 As shown, the main forms in which molybdenum exists are characterized.

[0132] Example 12

[0133] A multi-metal oxide cluster lubricant (PIBS1000-NOH-PMo) has the following chemical structural formula:

[0134]

[0135] A polymetallic oxy-oxide cluster lubricant (PIBS1000-NOH-PMo) was generated by reacting phosphomolybdic acid with PIBS1000-NOH from Example 4, and was designated Mo-8.

[0136] The preparation method of this polymetallic oxy-oxide cluster lubricating material is as follows: Phosphomolybdic acid (26 g, 0.01 mol) was dispersed in 150 mL of ethanol. Under argon atmosphere, this was added dropwise to 300 mL of toluene solution containing PIBS1000-NOH (120 g, 0.11 mol). The mixture was reacted in an oil bath at 60 °C for 24 h. Ethanol and toluene were removed by vacuum distillation. Petroleum ether was added, and insoluble matter was removed by centrifugation. The supernatant was precipitated for 12 h and then centrifuged again at 4000 rpm for 10 min. 60 g of Group II base oil HVP6 was added to the second supernatant, and petroleum ether was removed by rotary evaporation to obtain PIBS1000-NOH-PMo(Mo-8). This polymetallic oxy-oxide cluster lubricating material is deep blue. The synthetic route is as follows:

[0137]

[0138] The infrared spectrum of the polyoxometalate lubricating material is as follows: Figure 15 As shown, the successful synthesis of PIBS1000-NOH-PMo is confirmed; its X-ray photoelectron spectrum is as follows. Figure 16 As shown, the main forms in which molybdenum exists are characterized.

[0139] Example 13

[0140] A multi-metal-oxygen cluster lubricant (PIBS2300-N-SiMo) has the following chemical structural formula:

[0141]

[0142] A polymetallic oxygen cluster lubricant (PIBS2300-N-SiMo) was generated by reacting molybdic acid with PIBS2300-N from Example 1, and was designated as Mo-3.

[0143] The preparation method of this polymetallic oxy-oxide cluster lubricating material is as follows: 24 g of molybdic acid solution (20% by mass) was dissolved in 50 mL of ethanol. Under argon atmosphere, this solution was added dropwise to 300 mL of toluene solution containing 120 g of PIBS2300-N (0.05 mol). The mixture was reacted in an oil bath at 60 °C for 24 h. Ethanol and toluene were removed by vacuum distillation. Petroleum ether was added, and insoluble matter was removed by centrifugation. The supernatant was precipitated for 12 h and then centrifuged again at 4000 rpm for 10 min. The second supernatant was then removed by rotary evaporation to remove petroleum ether, yielding PIBS2300-N-SiMo(Mo-3). This polymetallic oxy-oxide cluster lubricating material is deep blue. The synthetic route is as follows:

[0144]

[0145] The infrared spectrum of the polyoxometalate lubricating material is as follows: Figure 17As shown, the successful synthesis of PIBS2300-N-SiMo is confirmed; its X-ray photoelectron spectrum is as follows. Figure 18 As shown, the main forms in which molybdenum exists are characterized.

[0146] Example 14

[0147] A multi-metal-oxygen cluster lubricant (PIBS1000-N-SiMo) has the following chemical structural formula:

[0148]

[0149] A polymetallic oxygen cluster lubricant (PIBS1000-N-SiMo) was generated by reacting molybdic acid with PIBS1000-N from Example 3, and was designated as Mo-7.

[0150] The preparation method of this polymetallic oxy-oxide cluster lubricating material is as follows: 24 g of molybdic acid solution (20% by mass) was dissolved in 50 mL of ethanol. Under argon atmosphere, this solution was added dropwise to 300 mL of toluene solution containing 130 g of PIBS1000-N (0.11 mol). The mixture was reacted in an oil bath at 60 °C for 24 h. Ethanol and toluene were removed by vacuum distillation. Petroleum ether was added, and insoluble matter was removed by centrifugation. The supernatant was precipitated for 12 h and then centrifuged again at 4000 rpm for 10 min. The second supernatant was then removed by rotary evaporation to remove petroleum ether, yielding PIBS1000-N-SiMo(Mo-7). This polymetallic oxy-oxide cluster lubricating material is deep blue. The synthetic route is as follows:

[0151]

[0152] The infrared spectrum of the polyoxometalate lubricating material is as follows: Figure 19 As shown, the successful synthesis of PIBS1000-N-SiMo is confirmed; its X-ray photoelectron spectrum is as follows. Figure 20 As shown, the main forms in which molybdenum exists are characterized.

[0153] Comparative Example 1

[0154] Compared with Example 5, the only difference is that ammonium heptamolybdate is replaced with an equimolar amount of molybdenum trioxide. The product obtained after the reaction is a turbid liquid with a large amount of precipitate at the bottom of the reaction flask.

[0155] Therefore, it is evident that replacing ammonium heptamolybdate with molybdenum trioxide does not result in a clear and transparent product.

[0156] Comparative Example 2

[0157] By replacing N-(2-hydroxyethyl)ethylenediamine in Example 4 with an equimolar amount of ethylenediamine, an intermediate product was prepared, designated PIBS1000-NH. Then, following Example 5, except replacing PIBS1000-NOH with PIBS1000-NH, with all other reactants and reaction conditions remaining the same, the resulting product was a turbid liquid with a large amount of precipitate at the bottom of the reaction flask.

[0158] Therefore, it is evident that replacing N-(2-hydroxyethyl)ethylenediamine with ethylenediamine does not result in a clear and transparent product.

[0159] Comparative Example 3

[0160] By replacing the polyisobutylene maleic anhydride in Example 4 with an equimolar amount of stearic acid, an intermediate product, stearamide, was prepared. Then, following Example 5, only PIBS1000-NOH was replaced with stearamide, while other reactants and reaction conditions remained the same. The product obtained after the reaction was a turbid liquid with a large amount of precipitate at the bottom of the reaction flask.

[0161] Therefore, it is evident that replacing polyisobutylene maleic anhydride with stearic acid does not result in a clear and transparent product.

[0162] Test Example 1

[0163] The elemental content of the polyoxometalate cluster lubricating materials prepared in Examples 5-14 was tested respectively, and the test results are shown in Table 1.

[0164] Table 1 Elemental analysis results

[0165] serial number code name Mo,% N，％ Mo-2 PIBS1000-N-PMo 5.69 3.19 Mo-3 PIBS2300-N-SiMo 1.61 1.89 Mo-4 PIBS2300-N-PMo 7.89 1.76 Mo-5 PIBS2300-N-PMo 4.82 1.82 Mo-7 PIBS1000-N-SiMo 1.56 1.41 Mo-8 PIBS1000-NOH-PMo 3.47 1.41 Mo-9 PIBS2300-NOH-PMo 5.03 0.81 Mo-10 PIBS2300-N-HMo 1.82 2.20 Mo-11 PIBS2300-N-PMo 7.28 1.96 Mo-13 PIBS1000-NOH-NMo 6.12 1.35

[0166] As shown in Table 1, the molybdenum content of the polyoxometalate cluster lubricating materials in Examples 5-14 is 1.5-8.0%, and the nitrogen content is 0.5-3.5%.

[0167] Test Example 2

[0168] The multi-metal oxide cluster lubricating materials prepared in Examples 5-14 were added to base oil at a mass concentration of 5%, and the stability of the oil solution was observed when stored at room temperature (20-25℃) and 100℃.

[0169] Experimental results are as follows Figure 21 As shown (where a represents 30 minutes at 100°C; b represents 30 days at room temperature; c represents 10 days at 100°C), by Figure 21 It can be seen that the oil solutions of Examples 5-14 are clear and transparent in appearance. They show no precipitation or stratification after being stored at room temperature for 1 month and at 100°C for 10 days, and have good stability.

[0170] Test Example 3

[0171] Mo-10 and Mo-11 from Examples 6 and 10 were dissolved in base oil PAO-10 at a concentration of 5%. The test was conducted using the SRV test method (NB / SH / T 0847-2010) for the determination of the tribological properties of extreme pressure lubricating oils, under the frictional conditions of a load of 300 N, a temperature of 50 °C, a time of 120 min, a stroke of 1 mm, and a frequency of 50 Hz.

[0172] Test results are as follows Figure 22 As shown, by Figure 22 It can be seen that the coefficient of friction of the oils is less than 0.14. This indicates that adding polyoxometalate cluster lubricating materials Mo-10 and Mo-11 to PAO-10 base oil can improve its lubrication performance. The polyoxometalate cluster lubricating materials of this invention can be applied to lubricating oils.

[0173] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, and is not intended to limit the scope of protection of the present invention. Simple modifications or equivalent substitutions made by those skilled in the art to the technical solution of the present invention do not depart from the essence and scope of the technical solution of the present invention.

Claims

1. A multi-metal-oxygen cluster lubricating material, characterized in that, Its chemical structural formula is selected from any one of the following: In the above formula, PIB stands for polyisobutylene.

2. The multi-metal-oxygen cluster lubricating material according to claim 1, characterized in that, The polyoxometallic cluster lubricant has a molybdenum content of 1.5-8.0% and a nitrogen content of 0.5-3.5%.

3. A method for synthesizing a polymetallic oxygen cluster lubricating material as described in claim 1 or 2, characterized in that, The process includes the following steps: Under an inert gas atmosphere, a polymetallic oxy-oxide cluster is reacted with polyisobutylene monosuccinimide in an acid-base reaction to obtain the product.

4. The synthesis method according to claim 3, characterized in that, The inert gas is nitrogen or argon.

5. The synthesis method according to claim 3, characterized in that, The polymetallic oxygen cluster is a molybdenum-containing cluster compound.

6. The synthesis method according to claim 5, characterized in that, The polyoxometallic cluster includes any one of molybdic acid, phosphomolybdic acid, silicomolybdic acid, and ammonium heptamolybdate, and the polyoxometallic cluster must first be dissolved in water or ethanol.

7. The synthesis method according to claim 3, characterized in that, The chemical structural formula of the polyisobutylene monosuccinimide is as follows: In the above formula, PIB stands for polyisobutylene.

8. The synthesis method according to claim 7, characterized in that, The preparation method of the polyisobutylene monosuccinimide includes the following steps: under argon or nitrogen atmosphere, polyisobutylene maleic anhydride, primary amine compound and solvent are subjected to dehydration reaction under reflux conditions to obtain the product.

9. The synthesis method according to claim 8, characterized in that, The molecular weight of the polyisobutylene maleic anhydride is 800-2500. The polyisobutylene maleic anhydride needs to be dissolved in a solvent and heated to 90-110℃.

10. The synthesis method according to claim 8, characterized in that, The primary amine compound includes any one of N-(2-hydroxyethyl)ethylenediamine and polyethylenepolyamine.

11. The synthesis method according to claim 8, characterized in that, The solvent is xylene, o-dichlorobenzene, or a base oil.

12. The synthesis method according to claim 8, characterized in that, The molar volume ratio of the polyisobutylene maleic anhydride, the primary amine compound, and the solvent is 0.05-0.12 mol: 0.04-0.08 mol: 300-400 mL.

13. The synthesis method according to claim 8, characterized in that, The dehydration reaction is carried out at a temperature of 140-180℃ for 7-9 hours. After the dehydration reaction is completed, the solvent is removed by cooling and vacuum distillation.

14. The synthesis method according to claim 3, characterized in that, The acid-base reaction is carried out at a temperature of 60-140℃ for 12-48 hours. The reaction solvent, xylene, toluene, or base oil, needs to be added. After the acid-base reaction is completed, the reaction solvent is removed by vacuum distillation, petroleum ether is added, and the mixture is centrifuged and rotary evaporated.

15. The use of a polyoxometalate cluster lubricating material as described in any one of claims 1-2 or a polyoxometalate cluster lubricating material synthesized by the synthesis method of any one of claims 3-14 in the preparation of lubricating oil additives.

16. The application according to claim 15, characterized in that, The base oil of the lubricating oil includes mineral base oil, synthetic base oil, or vegetable oil base oil.

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