Telechelic polymers, methods for their preparation, supramolecular oleogels and lubricating oils

Abstract

The application provides a telechelic polymer, a preparation method thereof, a supramolecular oil gel and lubricating oil. The telechelic polymer is composed of an oil-soluble central chain and two non-oil-soluble pyrene-functionalized end chain, and can self-assemble into a fully cross-linked, rod-shaped and stable gel network through pi-pi stacking interaction. The addition of the telechelic polymer of the application into base oil can form a stable oil gel, which can not only significantly alleviate the leakage and peristalsis of the base oil, but also improve the lubricating performance and anti-wear performance of the base oil; when graphite or its derivatives are further added, the lubricating performance and anti-wear performance can be further improved, especially when graphite is added, the graphite can be in-situ exfoliated into graphene under the assistance of ultrasonic, which is not only low in cost, simple and easy to implement, but also improves the dispersion stability of the graphite; therefore, the oil gel can be applied to the field of mechanical lubrication as lubricating oil.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of supramolecular chemistry, and particularly relates to a telechelic polymer, a preparation method thereof, a supramolecular oil gel and lubricating oil. BACKGROUND

[0002] Friction and wear are ubiquitous in mechanical systems, causing huge energy loss. The best way to reduce friction and wear is to lubricate the moving parts of the mechanical system. Lubricating oil is an effective medium for lubrication, which can effectively reduce friction and wear, thereby significantly improving the energy efficiency and service life of the machine. Lubricating additives are the key to lubricating oil, and traditional additives include phosphorus and sulfur-containing compounds and organic metal complexes, which can form a protective friction film on the friction surface to prevent direct contact of machine parts. However, the toxicity of these molecular additives themselves and their inherent instability under chemical, thermal and / or mechanical conditions have led to serious harmful emissions, causing environmental problems. Therefore, exploring new types of anti-friction and anti-wear lubricating oil has always been one of the research topics in mechanical systems.

[0003] In contrast, nanoparticles as lubricating oil additives not only have low toxicity and high stability, but also exhibit excellent tribological properties in terms of friction reduction and wear resistance. For example, graphite derivatives such as graphene, graphene oxide and reduced graphene oxide have two-dimensional (2D) nanostructures, weak van der Waals or π-π interactions between layers, and high mechanical strength within the same layer. These characteristics make adjacent layers prone to mutual sliding under shear stress without damaging the structure within the layer. Therefore, they have been recognized as nano-additives in base oil, which can efficiently reduce friction and wear. However, the application of these derivatives requires a series of complex pretreatment processes starting from raw graphite, which makes them more expensive as lubricating additives. Therefore, in practical tribological applications, raw graphite is directly used as a lubricating oil additive. However, the dispersion stability of graphite in base lubricating oil is poor, which reduces its tribological properties. SUMMARY

[0004] In view of the above technical status, the present application provides a telechelic polymer, which has good application prospects in the field of mechanical lubrication.

[0005] The technical scheme provided by the present application is as follows: a telechelic polymer, which is a long-chain alkyl polymethacrylate containing pyrene groups at both ends, denoted as P m S 2n P m , wherein the P block comprises 2-(1-pyrene butyryloxy) ethyl methacrylate monomer, the S block is oil-soluble long-chain alkyl polymethacrylate, m is the polymerization degree of the P block, and 2n is the polymerization degree of the S block.

[0006] m is an integer, and the value is not limited. As preferred, m is selected from an integer in the range of 5 to 10, inclusive.

[0007] 2n is an integer, and the value is not limited. As preferred, 2n is selected from an integer in the range of 10 to 500, inclusive; as further preferred, 2n is selected from an integer in the range of 10 to 100, inclusive, such as 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, etc.

[0008] The long-chain alkyl polymethacrylate is not limited, including dodecyl polymethacrylate and octadecyl polymethacrylate.

[0009] The preparation method of the telechelic polymer is not limited, including using long-chain alkyl polymethacrylate bifunctional macromolecular initiator, obtaining two-end hydroxyl functionalized telechelic polymer by controllable ATRP polymerization, and then obtaining two-end pyrene functionalized telechelic polymer by esterification reaction, which includes the following steps:

[0010] (1) Synthesizing long-chain alkyl polymethacrylate based on bifunctional initiator;

[0011] (2) Synthesizing double-end hydroxyl functionalized telechelic polymer using long-chain alkyl polymethacrylate as macromolecular ATRP initiator;

[0012] The hydroxyl group is not limited, including hydroxyethyl methacrylate and 2-methyl-2-acrylic acid-2,3-dihydroxypropyl (3) by esterification reaction, to obtain the pyrene functionalized telechelic polymer.

[0013] The present inventors found that when the telechelic polymer of the present application is dispersed in base oil, a supramolecular oil gel is formed by π-π stacking interaction, which has good lubricating performance and anti-wear performance, and thus can be used as lubricating oil.

[0014] The base oil is not limited, including mineral oil, synthetic oil and vegetable oil. Mineral oil is refined from crude oil. Synthetic oil is synthesized by chemical methods, such as poly-alpha-olefin, etc. Vegetable oil is obtained from the fruits, seeds, germ, etc. of plants.

[0015] When the telechelic polymer is dispersed in base oil, the mass percentage concentration of the telechelic polymer is not limited, preferably 2-20%, further preferably 5-10%, such as 5%, 6%, 7%, 8%, 9%, 10%, etc.

[0016] As preferred, during the formation of the supramolecular oil gel, the base oil solution is heated, and the heating temperature is 10-40℃, preferably 15-30℃, such as 15℃, 20℃, 25℃, 30℃, etc.

[0017] As preferred, the base oil solution is stirred during the formation of the supramolecular oil gel, and further preferably treated with ultrasonic stirring.

[0018] The supramolecular oil gel has good lubricating performance and anti-wear performance. For example, when dispersed in base oil PAO-10, the friction coefficient of the supramolecular oil gel formed under a friction condition of a load of 200 N and a frequency of 25 Hz is less than 0.125.

[0019] As preferred, a lubricating oil additive is also dispersed in the base oil for further improving the lubricating performance and anti-wear performance.

[0020] The lubricating oil additive is not limited, including graphite and its derivatives, such as graphene, graphene oxide, reduced graphene oxide, etc.

[0021] As preferred, when dispersed in the base oil, the mass percentage concentration of the lubricating oil additive is 0.2-5%, and further preferably 0.5-2.5%, such as 0.5%, 1%, 1.5%, 2%, 2.5%, etc.

[0022] When the lubricating oil additive is graphite, the present inventors have found that, by π-π stacking interaction between the telechelic polymer pyrene group and graphite, the graphite can be ex situ exfoliated into graphene under the assistance of ultrasonic.

[0023] The telechelic polymer of the present application is composed of one oil-soluble central chain and two pyrene-functionalized end group chains, as shown in Figure 1 which can self-assemble into a fully cross-linked, rod-like, stable micellar (gel) network through π-π stacking interaction, having the following beneficial effects:

[0024] (1) The telechelic polymer is mixed with the base oil, and can self-assemble into a fully cross-linked, rod-like, stable oil gel network through π-π stacking interaction, forming a stable oil gel, which on one hand can significantly alleviate the leakage and peristalsis commonly existing in base oils, improving the stability of the base oil, and on the other hand can improve the lubricating performance and anti-wear performance of the base oil, and thus can be applied to mechanical systems as a friction-reducing and anti-wear lubricating oil. For example, when dispersed in base oil PAO-10, the friction coefficient of the supramolecular oil gel formed under a friction condition of a load of 200 N and a frequency of 25 Hz is less than 0.125.

[0025] (2) When the telechelic polymer of the present application is added in base oil, and a lubricating oil additive is added, the lubricating performance and anti-wear performance of the formed lubricating oil can be further improved. The lubricating oil additive includes but is not limited to graphite or its derivatives, such as graphene, graphene oxide, etc. For example, when dispersed in base oil PAO-10, the friction coefficient of the oil gel under the friction condition of a load of 200 N and a frequency of 25 Hz is less than 0.12.

[0026] (3) When the lubricating oil additive is graphite, the π-π stacking interaction between the pyrene-containing group in the telechelic polymer and the graphite can exfoliate the graphite into graphene in situ under the assistance of ultrasonic, which not only has low cost, is simple and easy to implement, but also improves the dispersion stability of graphite in base oil, solves the problem of poor dispersion stability of graphite in base lubricating oil, and the temperature at which aggregation and precipitation occur. Experiments prove that the supramolecular oil gel formed by dispersing the telechelic polymer and graphite in base oil has good long-term stability, and the oil gel does not show any visible flowability after being stored for one year at 20°C; and the lubricating performance and anti-wear performance of the supramolecular oil gel are equivalent to those of the supramolecular oil gel formed by dispersing the telechelic polymer and graphene in base oil. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 is a synthetic route diagram of the telechelic polymer in embodiments 1-3 of the present application.

[0028] Figure 2 is a nuclear magnetic resonance hydrogen spectrum diagram of the telechelic polymer in embodiment 1 of the present application.

[0029] Figure 3 is a nuclear magnetic resonance hydrogen spectrum diagram of the telechelic polymer in embodiment 2 of the present application.

[0030] Figure 4 is a nuclear magnetic resonance hydrogen spectrum diagram of the telechelic polymer in embodiment 3 of the present application.

[0031] Figure 5 is a gel permeation chromatogram of the telechelic polymer in embodiments 1-3 of the present application.

[0032] Figure 6 is a molecular dynamic diagram of the oil gel in embodiments 4-6 of the present application.

[0033] Figure 7 is an inverted appearance diagram of the oil gel in embodiments 5 and 8 of the present application.

[0034] Figure 8 is a morphology diagram of the original graphite in comparative embodiment 1 of the present application and the graphite exfoliated into graphene in embodiments 7-9 of the present application.

[0035] Figure 9 The graph shows the friction coefficient test results of the oleogel samples and PAO-10 base oil samples in Examples 4-9 of this invention.

[0036] Figure 10 These are wear track volume test images of the oleogel samples and PAO-10 base oil samples from Examples 4-9 of this invention under the same friction conditions.

[0037] Figure 11 The graph shows the friction coefficient test results of the oleogel samples and PAO-10 base oil samples in Examples 10-12 of this invention.

[0038] Figure 12 These are wear track volume test images of the oleogel samples and PAO-10 base oil samples in Examples 10-12 of this invention under the same friction conditions.

[0039] Figure 13 The graph shows the friction coefficient test results of the oleogel samples and PAO-10 base oil samples in Examples 13-15 of this invention.

[0040] Figure 14 These are wear track volume test images of the oleogel samples and PAO-10 base oil samples in Examples 13-15 of this invention under the same friction conditions. Detailed Implementation

[0041] The present invention will be further described in detail below with reference to the embodiments and accompanying drawings. It should be noted that the embodiments described below are intended to facilitate the understanding of the present invention and do not limit it in any way.

[0042] Example 1:

[0043] In this embodiment, the telechelic polymer structure is shown below:

[0044]

[0045] Where m = 6 and n = 15, it is a telechelic polymer P6S formed by functionalizing 2-(1-pyrenobutyryloxy)ethyl methacrylate at both ends of polyoctadecyl methacrylate. 30 P6.

[0046] The preparation method of this polymer is as follows: Figure 1 As shown, biheaded polyoctadecyl methacrylate S was synthesized using hydroquinone bifunctional initiator. 30 Then through the macromolecular initiator S 30 Synthesis of telechelic polymer H6S with hydroxyl-terminated ends 30 H6 was finally synthesized as the target product P6S via esterification. 30 P6. Specifically, the steps are as follows:

[0047] (1) Macromolecular initiator S 30 Synthesis:

[0048] First, a Schlenk flask was evacuated with a vacuum pump, purged with argon, and cycled three times. Then, bis(2-bromoisobutyrate)-1,4-phenyl diester (160 mg, 1.23 mmol) and methacrylate octadecyl ester (4 g, 11.8 mmol) were dissolved in a mixture of 6 g of toluene and N,N,N',N',N"-pentamethyldiethylenetriamine (330 μL, 0.79 mmol) and the mixture was added to the flask. Immediately, copper(I) bromide (68 mg, 0.47 mmol) was added quickly under an argon atmosphere. The reaction was deoxygenated by three freeze-vacuum-thaw cycles. The reaction mixture was then stirred in an oil bath preheated to 70 °C for 2 hours. After the reaction was complete, the round bottom flask was placed in ice water and the reaction was left open to air to terminate the reaction. After removal of the copper(I) bromide by passing through a neutral alumina column, the eluent was collected and the solution was concentrated by rotary evaporation to approximately 5 mL. Precipitation was achieved by dropwise addition to 200 mL of cold acetone. This precipitation process was repeated three times to completely remove the methacrylate octadecyl ester monomer and thus purify the polymer. The resulting solid was dried under reduced pressure at room temperature for 12 hours, yielding 3.0 g, 75%.

[0049] (2) H6S 30 Synthesis of H6:

[0050] A Schlenk flask was evacuated with a vacuum pump, then purged with argon, and cycled three times. Macromolecular initiator S 30 (500 mg) was dissolved in 10 mL of THF, then hydroxyethyl methacrylate (0.192 g, 1.47 mmol) and N,N,N',N',N"-pentamethyldiethylenetriamine (40.0 μL, 0.20 mmol) were added, and the mixture was quickly added to the reaction flask. Further copper(I) bromide (20 mg, 0.14 mmol) was added under an argon atmosphere. The reaction was deoxygenated by three freeze-vacuum-thaw cycles. The reaction mixture was then stirred at 65 °C for 10 hours. After the reaction was complete, the round bottom flask was placed in ice water and the reaction was left open to air to terminate the reaction. After removal of the copper(I) bromide by passing through a neutral alumina column, the eluent was collected and the solution was concentrated by rotary evaporation to approximately 5 mL. Precipitation was achieved by dropwise addition to 200 mL of cold acetone, and the polymer was purified. The resulting solid was dried under reduced pressure at room temperature for 12 hours, yielding 513 mg, 74%.

[0051] (3) P6S 30 Synthesis of P6:

[0052] H6S 30H6 (500 mg), 1-pyrenebutyric acid (612 mg) and DMAP (52 mg) were dissolved in 20 mL CH2Cl2, and the mixed solution was placed in an ice bath. Then EDC (412 mg) was dissolved in 10 mL CH2Cl2, and it was added dropwise to the above mixed solution, and stirred for 2 hours. Then the reaction was stirred at room temperature for 24 hours, and the end product P6S was obtained by sedimentation in acetone 30 P6. The obtained solid was dried at room temperature under reduced pressure for 12 hours, and the yield was 410 mg, 81%.

[0053] The nuclear magnetic resonance hydrogen spectrum of this sample is shown in Figure 2 , which confirms that the P6S 30 P6 solid sample was successfully synthesized, and the molecular weight M 30 of the P6S n,NMR solid sample was calculated to be 15400 g / mol.

[0054] The gel permeation chromatogram of this sample is shown in Figure 5 a, which confirms that the molecular weight M n,SEC of the sample is 16400 g / mol, and the P6S 30 solid sample has a molecular weight distribution of 1.18.

[0055] Example 2:

[0056] In this example, the polymer structure is basically the same as that in Example 1, where m = 6, n = 25, and it is a telechelic polymer P6S formed by functionalizing 2-(1-pyrenebutyryloxy) ethyl methacrylate with polyoctadecyl methacrylate at both ends. 50 P6.

[0057] The preparation method of this polymer is shown in Figure 1 , and the double-headed polyoctadecyl methacrylate S 50 is synthesized by a bifunctional initiator of hydroquinone, then the telechelic polymer H6S 50 functionalized with hydroxyl groups at both ends is synthesized by the macromolecular initiator S 50 , and finally the target product P6S 50 P6 is synthesized by esterification. Specifically, it includes the following steps:

[0058] (1) Synthesis of macromolecular initiator S 50 :

[0059] First, a Schlenk flask was evacuated with a vacuum pump, then purged with argon, three times. Then, bis(2-bromoisobutyric acid)-1,4-phenyl diester (95 mg, 0.236 mmol) and octadecyl methacrylate (4 g, 11.8 mmol) were dissolved in a mixture of 6 g of toluene and N,N,N',N',N"-pentamethyldiethylenetriamine (100 μL, 0.47 mmol) and the mixture solution was added to the flask. Immediately, copper bromide (41 mg, 0.28 mmol) was added quickly under argon atmosphere. The oxygen of the reaction system was removed by three freeze-vacuum-thaw cycles. Then the reaction mixture was stirred in an oil bath preheated to 70 °C for 2 hours. After the reaction was completed, the round bottom flask was placed in ice water and the reaction was left open to air to terminate the reaction. After removal of copper bromide by a neutral alumina column, the eluent was collected and the solution was concentrated by rotary evaporation to about 5 mL. Precipitation was performed by dropwise addition of 200 mL of cold acetone. This precipitation process was repeated three times to completely remove the octadecyl methacrylate monomer and thus purify the polymer. The resulting solid was dried under reduced pressure at room temperature for 12 hours, yield: 3.2 g, 81 %.

[0060] (2) H6S 50 Synthesis of H6:

[0061] A Schlenk flask was evacuated with a vacuum pump, then purged with argon, three times. The macroinitiator H6S 50 (500 mg) was dissolved in 10 mL of THF, then hydroxyethyl methacrylate (0.115 g, 0.886 mmol) and N,N,N',N',N"-pentamethyldiethylenetriamine (40.0 μL, 0.20 mmol) were added and the mixture solution was quickly added to the reaction flask. Further, copper bromide (20 mg, 0.14 mmol) was added under argon atmosphere. The oxygen of the reaction system was removed by three freeze-vacuum-thaw cycles. Then the reaction mixture was stirred at 65 °C for 10 hours. After the reaction was completed, the round bottom flask was placed in ice water and the reaction was left open to air to terminate the reaction. After removal of copper bromide by a neutral alumina column, the eluent was collected and the solution was concentrated by rotary evaporation to about 5 mL, precipitated by dropwise addition of 200 mL of cold acetone, and the polymer was purified. The resulting solid was dried under reduced pressure at room temperature for 12 hours, yield: 504 mg, 82 %.

[0062] (3) P6S 50 Synthesis of P6:

[0063] H6S 50H6 (500 mg), 1-pyrene butyric acid (468 mg) and DMAP (40 mg) were dissolved in 20 mL CH2Cl2, and the mixed solution was placed in an ice bath. Then EDC (311 mg) was dissolved in 10 mL CH2Cl2, and it was added dropwise to the above mixed solution, and stirred for 2 hours. Then the reaction was stirred at room temperature for 24 hours, and the end product P6S was obtained by precipitation in acetone 50 P6. The obtained solid was dried at room temperature under reduced pressure for 12 hours, and the yield was 420 mg, 84%.

[0064] The nuclear magnetic resonance hydrogen spectrum of this sample is shown in Figure 3 , which confirms that the P6S 50 solid sample of P6 was successfully synthesized, and the molecular weight M 50 of the P6 solid sample was calculated to be 22200 g / mol. n,NMR

[0065] The gel permeation chromatogram of this sample is shown in Figure 5 b, which confirms that the molecular weight M n,SEC of the sample is 21600 g / mol, and the P6S 50 solid sample of P6 has a molecular weight distribution of 1.11.

[0066] Example 3:

[0067] In this example, the polymer structure is basically the same as that in Example 1, where m = 6, n = 35, and it is a telechelic polymer P6S formed by functionalizing 2-(1-pyrene butyryloxy) ethyl methacrylate with polyoctadecyl methacrylate at both ends. 70 P6.

[0068] The preparation method of this polymer is shown in Figure 1 , and the double-headed polyoctadecyl methacrylate S 70 is synthesized by a bifunctional initiator of hydroquinone, then the macroinitiator S 70 is synthesized, and the telechelic polymer H6S 70 functionalized with hydroxyl groups at both ends is synthesized, and finally the target product P6S 70 P6 is synthesized by esterification. Specifically, it includes the following steps:

[0069] (1) Synthesis of macroinitiator S 70

[0070] ​​First, a Schlenk flask was evacuated with a vacuum pump, then purged with argon, three times. Then, bis(2-bromoisobutyric acid)-1,4-phenyl diester (68 mg, 0.168 mmol) and octadecyl methacrylate (4 g, 11.8 mmol) were dissolved in a mixture of 6 g of toluene and N,N,N',N',N"-pentamethyldiethylenetriamine (70 μL, 0.34 mmol) and the mixture solution was added to the flask. Immediately, copper bromide (28 mg, 0.20 mmol) was added quickly under argon atmosphere. The oxygen of the reaction system was removed by three freeze-vacuum-thaw cycles. Then the reaction mixture was stirred in an oil bath preheated to 70 °C for 2 hours. After the reaction was completed, the round bottom flask was placed in ice water and the reaction was left open to air to terminate the reaction. After removal of copper bromide by a neutral alumina column, the eluent was collected and the solution was concentrated by rotary evaporation to about 5 mL. Precipitation was performed by dropwise addition of 200 mL of cold acetone. This precipitation process was repeated three times to completely remove the octadecyl methacrylate monomer and thus purify the polymer. The resulting solid was dried under reduced pressure at room temperature for 12 hours, yield: 3.1 g, 78%.

[0071] (2) H6S 70 Synthesis of H6:

[0072] A Schlenk flask was evacuated with a vacuum pump, then purged with argon, three times. The macroinitiator H6S 50 (500 mg) was dissolved in 10 mL of THF, then hydroxyethyl methacrylate (0.0823 g, 0.633 mmol) and N,N,N',N',N"-pentamethyldiethylenetriamine (40.0 μL, 0.20 mmol) were added and the mixture solution was quickly added to the reaction flask. Further, copper bromide (20 mg, 0.14 mmol) was added under argon atmosphere. The oxygen of the reaction system was removed by three freeze-vacuum-thaw cycles. Then the reaction mixture was stirred at 65 °C for 10 hours. After the reaction was completed, the round bottom flask was placed in ice water and the reaction was left open to air to terminate the reaction. After removal of copper bromide by a neutral alumina column, the eluent was collected and the solution was concentrated by rotary evaporation to about 5 mL, precipitated by dropwise addition of 200 mL of cold acetone, and the polymer was purified. The resulting solid was dried under reduced pressure at room temperature for 12 hours, yield: 436 mg, 75%.

[0073] (3) P6S 70 Synthesis of P6:

[0074] H6S 70H6 (500 mg), 1-pyrenecarboxylic acid (392 mg) and DMAP (33 mg) were dissolved in 20 mL CH2Cl2, and the mixed solution was placed in an ice bath. Then EDC (261 mg) was dissolved in 10 mL CH2Cl2, and it was added dropwise to the above mixed solution, and stirred for 2 hours. Then the reaction was stirred at room temperature for 24 hours, and the end product P6S was obtained by sedimentation in acetone 70 P6. The obtained solid was dried at room temperature under reduced pressure for 12 hours, and the yield was 425 mg, 85%.

[0075] The nuclear magnetic resonance hydrogen spectrum of this sample is shown in Figure 4 , which confirms that the P6S 70 P6 solid sample was successfully synthesized, and the molecular weight M 70 of the P6S n,NMR solid sample was calculated to be 28900 g / mol.

[0076] The gel permeation chromatogram of this sample is shown in Figure 5 c, which confirms that the molecular weight M n,SEC of the sample is 27800 g / mol, and the H6S 70 calculated is 1.13.

[0077] Examples 4-6:

[0078] In this example, the telechelic polymer P6S 30 P6, P6S 50 P6 and P6S 70 P6 solid samples were dispersed in poly-alpha-olefin-10 (PAO-10) base oil respectively, and the concentration of the telechelic polymer was 6.0 wt%, and the base oil solution was heated and ultrasonically treated, and at 20°C, the π-π stacking interaction between the pyrene groups occurred, forming the oil gel P6S 30 P6, P6S 50 P6, P6S 70 P6, and the dynamic oil gel structure is shown in Figure 6 .

[0079] The appearance of these oil gels shows a gel-like appearance, no flow, and the inversion experiment shows that there is no visible flow at 20°C for one year, which has good stability and can significantly alleviate the leakage and peristalsis commonly existing in base oil. As an example, Figure 7 the left figure in FIG. 1 shows the inversion experiment results of the oil gel P6S 50 P6 in Example 5, and the inversion experiment results of the oil gels in Examples 4 and 6 are similar to them.

[0080] Comparative Example 1:

[0081] This embodiment is a comparative example of the following embodiments 7-9.

[0082] In this embodiment, graphite is uniformly dispersed in poly-alpha-olefin-10 (PAO-10) base oil, the concentration of graphite is 1.2wt%, and the graphite nanoparticles will obviously aggregate and settle at the bottom of the bottle after standing for a certain time at 20°C. As an example, Figure 7 The right graph in FIG. 1 is a still image of graphite in base oil in Comparative Example 1, showing graphite aggregation and sedimentation in the base oil.

[0083] Embodiments 7-9:

[0084] This embodiment is basically the same as Comparative Example 1, except that the telechelic polymer solid sample in Examples 1-3 is also dispersed in poly-alpha-olefin-10 (PAO-10) base oil. The telechelic polymer and graphite have π-π stacking effect, and a supramolecular oil gel is obtained. The specific method is as follows:

[0085] Graphite is dispersed in poly-alpha-olefin-10 (PAO-10) base oil, and the telechelic polymer P6S 30 P6, P6S 50 P6 or P6S 70 P6 solid sample is also dispersed in poly-alpha-olefin-10 (PAO-10) base oil, the concentration of telechelic polymer in the base oil solution is 6.0wt%, the concentration of graphite is 1.2wt%, and the base oil solution is heated and ultrasonically treated to form an oil gel Graphite@P6S 30 P6, Graphite@P6S 50 P6 and Graphite@P6S 70 P6.

[0086] The appearance of these oil gels shows gel-like, no flow, and the inversion experiment shows that there is no visible flow after being stored at 20°C for one year, and it has good stability. As an example, Figure 7 The middle graph in FIG. 1 is the oil gel Graphite@P6S 50 P6 in Example 8, which shows that the addition of telechelic polymer improves the dispersion stability of graphite in base oil, solves the problem of aggregation and sedimentation, and the inversion experiment results of the oil gels in Examples 8 and 9 are similar.

[0087] The morphology of the original graphite is shown in the left graph of FIG. 1, and the morphology of the graphite in Examples 7-9 is shown in the right graph of FIG. 1, which shows that the graphite is exfoliated into graphene after the addition of telechelic polymer in Examples 7-9. Figure 8 Figure 8 The morphology of the original graphite is shown in the left graph of FIG. 1, and the morphology of the graphite in Examples 7-9 is shown in the right graph of FIG. 1, which shows that the graphite is exfoliated into graphene after the addition of telechelic polymer in Examples 7-9. ​

[0088] The oil gels in Examples 4-9 and PAO-10 base oil samples were subjected to SRV-IV oscillating reciprocating friction test, and the test conditions were: load 200 N, frequency 25 Hz, amplitude 1000 pm, cycle 30 min, and temperature 20°C. The test results are shown in Table 1, and are as follows: Figure 9

[0089] (1) Compared with PAO-10 base oil, the friction coefficients of the oil gels in Examples 4-9 are all reduced, indicating that the addition of telechelic polymer P6S 30 P6, P6S 50 P6 and P6S 70 P6 can greatly improve the lubricating performance thereof, i.e., the oil gels in Examples 4-9 can be applied as lubricating oil.

[0090] (2) Compared with the addition of telechelic polymer in base oil, the addition of not only telechelic polymer but also graphite in base oil can further improve the lubricating performance, for example, the friction coefficient of P6S 30 P6 in Example 4 is 0.123, the friction coefficient of Graphite@P6S 30 P6 in Example 5 is 0.119, the friction coefficient of P6S 50 P6 in Example 8 is 0.123, the friction coefficient of Graphite@P6S 50 P6 in Example 6 is 0.118, the friction coefficient of P6S 70 P6 in Example 9 is 0.124, the friction coefficient of Graphite@P6S 70 P6 is 0.119.

[0091] The oil gels in Examples 4-9 and PAO-10 base oil samples were subjected to SRV-IV oscillating reciprocating friction test, and the wear volumes under the same conditions are shown in Table 2, and are as follows: Figure 10

[0092] (1) Under the same conditions, compared with PAO-10 base oil, the wear volumes of the oil gels in Examples 4-9 are greatly reduced by up to 97%, and the wear scars of the wear surfaces are greatly reduced.

[0093] (2) Compared with the oil gel P6S 30 P6, the wear volume of the oil gel Graphite@P6S 30 P6 is reduced, showing smaller wear scars, and the wear resistance is improved;

[0094] Compared with the oil gel P6S 50 P6, the wear volume of the oil gel Graphite@P6S 50 ​​The wear volume of P6 is reduced, showing smaller wear scars, and the anti-wear performance is improved.

[0095] Compared with oil gel P6S 70 Compared with oil gel P6S 70 The wear volume of P6 is reduced, showing smaller wear scars, and the anti-wear performance is improved.

[0096] Therefore, the oil gels in Examples 4-9 can be applied as lubricating oil, and the lubricating performance and anti-wear performance of the oil gels in Examples 7-9 are superior to those of the oil gels in Examples 4-6.

[0097] Examples 10-12:

[0098] This example is basically the same as Examples 7-9, except that graphene nanomaterial is used instead of graphite. That is, specifically as follows:

[0099] The graphene nanomaterial, and the telechelic polymer P6S in Examples 1-3 30 P6, P6S 50 P6 and P6S 70 One of P6 solid samples is dispersed in poly-alpha-olefin-10 (PAO-10) base oil, the concentration of the telechelic polymer is 6.0wt%, and the concentration of the graphene nanomaterial is 1.2wt%, the base oil solution is heated and ultrasonically treated, and the π-π stacking interaction between the pyrene groups occurs at 20°C, forming oil gel Graphene@P6S 30 P6, Graphene@P6S 50 P6 and Graphene@P6S 70 P6.

[0100] The oil gels in Examples 4-6, Examples 10-12, and the PAO-10 base oil sample are subjected to SRV-IV oscillating reciprocating tribology test, and the test conditions are: load is 200N, frequency is 25Hz, amplitude is 1000μm, cycle is 30min, and temperature is 20°C. The test results are shown in Figure 11 as follows:

[0101] (1) Compared with PAO-10 base oil, the friction coefficient of the oil gels in Examples 4-6, 10-12 is reduced, indicating that the addition of telechelic polymer P6S 30 P6, P6S 50 P6 and P6S 70 P6 can greatly improve its lubricating performance, that is, the oil gels in Examples 4-9, and Examples 10-12 can be applied as lubricating oil.

[0102] (2) Compared with adding telechelic polymer in base oil, adding not only telechelic polymer but also graphene nanomaterial in base oil can further improve the lubricating performance, for example, P6S in Example 4 30 The friction coefficient of P6 is 0.123, Graphene@P6S in Example 10 30 The friction coefficient of P6 is 0.118, P6S in Example 5 50 The friction coefficient of P6 is 0.123, Graphene@P6S in Example 11 50 The friction coefficient of P6 is 0.118, P6S in Example 6 70 The friction coefficient of P6 is 0.124, Graphene@P6S in Example 12 70 The friction coefficient of P6 is 0.118.

[0103] (3) Compared with adding telechelic polymer and graphene in base oil in Examples 10-12, the lubricating performance of oil gel formed by adding telechelic polymer and graphene in base oil in Examples 7-9 is equivalent, for example, Graphene@P6S in Example 10 30 The friction coefficient of P6 is 0.118, Graphite@P6S in Example 7 30 The friction coefficient of P6 is 0.119, Graphene@P6S in Example 11 50 The friction coefficient of P6 is 0.118, Graphite@P6S in Example 8 50 The friction coefficient of P6 is 0.118, Graphene@P6S in Example 12 70 The friction coefficient of P6 is 0.117, Graphite@P6S in Example 9 30 The friction coefficient of P6 is 0.119.

[0104] SRV-IV oscillating reciprocating friction tests were performed on the oil gels in Examples 4-6 and Examples 10-12 and PAO-10 base oil samples, and the wear volumes under the same conditions were as shown in the table below: Figure 12 The specific contents are as follows:

[0105] (1) Compared with PAO-10 base oil under the same conditions, the wear volume of the oil gels in Examples 4-6 and Examples 10-12 is greatly reduced by up to 97%, and the wear scar on the wear surface is greatly reduced.

[0106] (2) Compared with oil gel P6S 30 P6, the wear volume of oil gel Graphene@P6S 30 P6 is reduced, showing smaller wear scar and improved wear resistance.

[0107] Compared with oil gel P6S 50 Compared with oil gel P6S 50 The wear volume of P6 is reduced, showing smaller wear scars, and the anti-wear performance is improved.

[0108] Compared with oil gel P6S 70 Compared with oil gel P6S 70 The wear volume of P6 is reduced, showing smaller wear scars, and the anti-wear performance is improved.

[0109] Therefore, the oil gels in Examples 10-12 can be applied as lubricating oil, and the lubricating performance and anti-wear performance of the oil gels of Examples 10-12 are superior to those of the oil gels in Examples 4-6.

[0110] Examples 13-15:

[0111] The graphene oxide nanoparticles, and the telechelic polymer P6S in Examples 1-3 30 P6, P6S 50 P6 and P6S 70 One of the P6 solid samples is dispersed in a polyalphaolefin-10 (PAO-10) base oil, the concentration of the telechelic polymer is 6.0wt%, and the concentration of the graphene oxide nanoparticles is 1.2wt%, the base oil solution is heated and ultrasonically treated, and the π-π stacking interaction between the pyrene groups occurs at 20℃, forming an oil gel GO@P6S 30 P6, GO@P6S 50 P6 and GO@P6S 70 P6.

[0112] The oil gels in Examples 4-6, Examples 13-15, and the PAO-10 base oil sample are subjected to SRV-IV oscillating reciprocating tribology test, and the test conditions are: load is 200N, frequency is 25Hz, amplitude is 1000μm, cycle is 30min, and temperature is 20℃. The test results are shown in Figure 13 as follows:

[0113] (1) Compared with the PAO-10 base oil, the friction coefficients of the oil gels in Examples 4-6, 13-15 are reduced, indicating that the addition of the telechelic polymer P6S 30 P6, P6S 50 P6 and P6S 70 P6 can greatly improve its lubricating performance, that is, the oil gels in Examples 4-9, and Examples 13-15 can be applied as lubricating oil.

[0114] (2) Compared with adding telechelic polymer in base oil, adding not only telechelic polymer but also graphene oxide nanoparticles in base oil can further improve the lubricating performance, for example, P6S in Example 4 00 The friction coefficient of P6 is 0.123, GO@P6S in Example 13 30 The friction coefficient of P6 is 0.12, P6S in Example 5 50 The friction coefficient of P6 is 0.123, GO@P6S in Example 14 50 The friction coefficient of P6 is 0.121, P6S in Example 6 70 The friction coefficient of P6 is 0.124, GO@P6S in Example 15 70 The friction coefficient of P6 is 0.12.

[0115] SRV-IV oscillating reciprocating friction tests were performed on the oil gels in Examples 13-15 and PAO-10 base oil samples, and the wear volumes under the same conditions were as shown in Table 2, and the details are as follows: Figure 14

[0116] (1) Compared with PAO-10 base oil under the same conditions, the wear volume of the oil gels in Examples 13-15 is greatly reduced by up to 97%, and the wear scar on the wear surface is greatly reduced.

[0117] (2) Compared with oil gel P6S 30 P6, the wear volume of oil gel GO@P6S 30 P6 is reduced, showing smaller wear scars, and the wear resistance is improved;

[0118] Compared with oil gel P6S 50 P6, the wear volume of oil gel GO@P6S 50 P6 is reduced, showing smaller wear scars, and the wear resistance is improved;

[0119] Compared with oil gel P6S 70 P6, the wear volume of oil gel GO@P6S 70 P6 is reduced, showing smaller wear scars, and the wear resistance is improved.

[0120] Therefore, the lubricating performance and wear resistance of the oil gels in Examples 13-15 are superior to those of the oil gels in Examples 4-6.

[0121] The above examples have described the technical solutions of the present application in detail, and it should be understood that the above description is only a specific embodiment of the present application and is not intended to limit the present application. Any modification, supplement or similar replacement within the principle range of the present application should be included in the protection scope of the present application.​

Claims

1. A telechelic polymer characterized by: The telechelic polymer is a long-chain alkyl polymethacrylate with pyrene groups at both ends, denoted as P m S 2n P m wherein the P block comprises 2-(1-pyrenecarboxyloxy)ethyl methacrylate monomers, and the S block is an oil-soluble long-chain alkyl polymethacrylate, m is the degree of polymerization of the P block, 2 n is the degree of polymerization of the S block.

2. The telechelic polymer of claim 1, wherein: m An integer selected from 5 to 10, inclusive.

3. The telechelic polymer of claim 1, wherein: ###00002### 2 n An integer selected from 10 to 500, inclusive.

4. The telechelic polymer of claim 3, wherein: 2 n An integer selected from 10 to 100, inclusive.

5. The telechelic polymer as described in claim 4, characterized in that: 2 n is 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100.

6. The telechelic polymer as described in claim 1, characterized in that: The long-chain alkyl polymethacrylate includes polydodecyl methacrylate and polystearyl methacrylate.

7. The method of claim 1 to 6, wherein the method is characterized by: The method comprises the following steps: (1) synthesizing long-chain alkyl polymethacrylate based on a bifunctional initiator; (2) synthesizing a double-end hydroxyl functionalized telechelic polymer by using the long-chain alkyl polymethacrylate as a macromolecular ATRP initiator; (3) obtaining a pyrene functionalized telechelic polymer through esterification.

8. The method for preparing the telechelicer type polymer as described in claim 7, characterized in that: In the step (2), the hydroxyl group includes hydroxyethyl methacrylate and 2-methyl-2-propenoic acid-2,3-dihydroxypropyl ester.

9. A supramolecular oleogel characterized by: The telechelic polymer of any one of claims 1 to 6 is dispersed in a base oil to form a supramolecular oil gel through π-π stacking interaction.

10. The supramolecular ologel of claim 9, characterized by: The base oil includes mineral oil, synthetic oil and vegetable oil.

11. The supramolecular ologel of claim 9, characterized by: The mass percentage concentration of the telechelic polymer is 2-20%.

12. The supramolecular ologel of claim 11, characterized by: The mass percentage concentration of the telechelic polymer is 5-10%.

13. The supramolecular ologel of claim 12, characterized by: The mass percentage concentration of the telechelic polymer is 5%, 6%, 7%, 8%, 9% or 10%.

14. The supramolecular ologel of claim 9, characterized by: During the formation of the supramolecular oil gel, the base oil solution is heated, and the heating temperature is 10-40℃.

15. The supramolecular ologel of claim 14, characterized by: The heating temperature is 15-30℃.

16. The supramolecular ologel of claim 15, characterized by: The heating temperature is 15℃, 20℃, 25℃ or 30℃.

17. The supramolecular ologel of claim 9, characterized by: During the formation of the supramolecular oil gel, the base oil solution is stirred.

18. The supramolecular ologel of claim 17, characterized by: Ultrasonic stirring is adopted.

19. The supramolecular ologel of claim 9, characterized by: The supramolecular oil gel has good lubricating performance and anti-wear performance.

20. The supramolecular ologel of claim 19, wherein: When dispersed in the base oil PAO-10, the friction coefficient of the formed supramolecular oil gel under the friction condition of a load of 200N and a frequency of 25Hz is less than 0.

125.

21. The supramolecular ologel of claim 9, characterized by: A lubricating oil additive is also dispersed in the base oil.

22. The supramolecular ologel of claim 21, wherein: The lubricating oil additive includes graphite and derivatives thereof.

23. The supramolecular ologel of claim 22, wherein: The graphite derivatives include one or more of graphene, graphene oxide and reduced graphene oxide.

24. The supramolecular ologel of claim 21, wherein: When dispersed in the base oil, the mass percentage concentration of the lubricating oil additive is 0.2-5%.

25. The supramolecular oleogel as described in claim 24, characterized in that: The mass percentage concentration of the lubricating oil additive is 0.5-2.5%.

26. The supramolecular ologel of claim 25, wherein: The mass percentage concentration of the lubricating oil additive is 0.5%, 1%, 1.5%, 2% or 2.5%.

27. The supramolecular ologel of any one of claims 21 to 26, wherein: When dispersed in the base oil PAO-10, the friction coefficient of the oil gel under the friction condition of a load of 200N and a frequency of 25Hz is less than 0.

12.

28. The supramolecular ologel of claim 21, wherein: ###0002### When the lubricating oil additive is graphite, ultrasonic assistance is adopted during the dispersion, and the graphite is in-situ exfoliated into graphene through π-π stacking interaction between the pyrene groups of the telechelic polymer and the graphite.

29. A lubricating oil comprising the supramolecular oil gel of claim 9.

30. A lubricating oil comprising the supramolecular oil gel of any one of claims 10 to 28.

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