Self-repairing material vulcanization extreme pressure agent capable of preventing film damage and preparation method of self-repairing material vulcanization extreme pressure agent

Abstract

The invention relates to a self-repairing material vulcanization extreme pressure agent for preventing film damage and a preparation method thereof, and belongs to the technical field of self-repairing polymer composite materials. The extreme pressure agent comprises the following components: a disulfide bond functionalized polyborate-polysiloxane copolymer, a micro-crosslinked polythiocarbamate-zinc coordination polymer, sulfurized isobutylene, sulfurized olefin cottonseed oil and the like. The disulfide bond functionalized polyborate-polysiloxane copolymer is prepared by the following steps: hydroxyl-terminated polydimethylsiloxane and tributyl borate are subjected to a reaction to generate a prepolymer, and the prepolymer reacts with 2, 2 '-dithiodiethanol and p-toluenesulfonic acid to obtain the disulfide bond functionalized polyborate-polysiloxane copolymer. And the micro-crosslinked polythiocarbamate-zinc coordination polymer is prepared by reacting a thiol-terminated prepolymer with zinc acetate. The thiol-terminated prepolymer is prepared by carrying out a catalytic reaction on polytetrahydrofuran ether glycol and isophorone diisocyanate through dibutyltin dilaurate, and then carrying out a reaction with 2, 2 '-dithiodiethylamine and 3-mercapto-1-propanol.

Description

Technical Field

[0001] This invention belongs to the technical fields of polymer composite materials, self-healing materials, and membrane materials, specifically relating to a self-healing extreme pressure vulcanizing agent for preventing membrane damage and its preparation method. Background Technology

[0002] In fields such as machinery manufacturing, transportation, and industrial production, friction and wear are among the core issues leading to equipment failure and increased energy consumption. Under extreme conditions such as high load, high speed, and high temperature, the surface lubricating film of metal parts is prone to rupture, causing direct contact friction, which in turn leads to failures such as seizing, scratching, and wear, seriously affecting the service life and operational safety of equipment.

[0003] Traditional technologies mainly alleviate friction by adding extreme pressure agents to form a reaction film on the metal surface. Commonly used sulfurized extreme pressure agents, such as isobutylene sulfide and carbon disulfide derivatives, can react with metals under high pressure to form a ferrous sulfide lubricating film. However, the film structure formed by these agents is fragile and lacks toughness. Under impact loads and alternating stress, cracks and peeling are prone to occur. Moreover, once damaged, the agents cannot repair themselves and require continuous replenishment of extreme pressure agents or shutdown maintenance, which seriously restricts the continuous and stable operation of the equipment.

[0004] As industrial equipment develops towards higher parameters, longer lifespan, and lighter weight, the performance requirements for film-forming materials are constantly upgrading. On the one hand, the films formed by traditional extreme pressure agents are no longer sufficient to resist complex stresses and environmental erosion; on the other hand, modern industry has increasingly higher demands for equipment maintenance cost control and energy conservation and emission reduction. Traditional passive protection extreme pressure agents are unable to meet the needs of active repair and long-term protection. Developing new materials that combine extreme pressure anti-wear and self-healing functions has become the key to technological breakthroughs.

[0005] Therefore, it is necessary to develop self-healing materials to achieve autonomous healing of damaged areas and restore the integrity and lubrication performance of the lubricating film. By combining the self-healing function with the extreme pressure and anti-wear properties of sulfurized extreme pressure agents, we can develop self-healing materials that prevent film damage. These sulfurized extreme pressure agents can respond quickly when micro-damage occurs in the lubricating film, filling cracks or rebuilding the film through the migration and reaction of self-healing units, thus preventing increased friction. Summary of the Invention

[0006] To address the problems of poor self-healing ability, low repair efficiency, and poor dispersibility in traditional extreme pressure vulcanizing agents, this invention provides a self-healing extreme pressure vulcanizing agent for preventing membrane damage and its preparation method. It utilizes a combination of disulfide-functionalized polyboronate-polysiloxane copolymer, micro-crosslinked polythiocarbamate-zinc coordination polymer, sulfurized isobutylene, sulfurized olefin cottonseed oil, polyisobutylene bis(succinimide), nano-reinforcing components, and auxiliary functional components. The dual dynamic interaction of disulfide bonds and metal coordination bonds achieves highly efficient self-healing. Combined with the rigid ferrous sulfur film and the mechanical reinforcement of nanomaterials, it achieves high-performance performance. The specific technical solution is as follows:

[0007] A self-healing extreme pressure vulcanizing agent for preventing membrane damage, characterized in that it comprises the following raw materials in parts by weight: 18-22 parts of disulfide-functionalized polyboronate-polysiloxane copolymer, 8-12 parts of micro-crosslinked polythiocarbamate-zinc coordination polymer, 25-30 parts of vulcanized isobutylene, 6-10 parts of vulcanized olefin cottonseed oil, 6-8 parts of polyisobutylene bis(succinimide), 4-7 parts of nano-reinforcing components, 2.5-6 parts of auxiliary functional components, and 90-100 parts of mineral oil; The nano-reinforcing components include 1.5 to 3 parts modified graphene and 2.5 to 4 parts nano tungsten disulfide; the auxiliary functional components include 0.5 to 1.5 parts diphenylthiourea, 0.5 to 1.5 parts antioxidant 1010, 0.5 to 1.5 parts nano cerium oxide and 1 to 1.5 parts triphenyl phosphate. The disulfide-functionalized polyboronic acid ester-polysiloxane copolymer is prepared by reacting hydroxyl-terminated polydimethylsiloxane with tributyl borate in xylene at 80°C–85°C to generate a prepolymer, followed by the addition of 2,2'-dithiodiethanol and p-toluenesulfonic acid at 110°C–115°C; the mass ratio of the hydroxyl-terminated polydimethylsiloxane, tributyl borate, 2,2'-dithiodiethanol, and p-toluenesulfonic acid is (100–110):(85–95):(70–80):(0.3–0.5). The micro-crosslinked polythiocarbamate-zinc coordination polymer is prepared by reacting a thiol-terminated prepolymer with zinc acetate at a mass ratio of (100-110):(7-9) in anhydrous N-methylpyrrolidone at 60-65°C; the thiol-terminated prepolymer is prepared by reacting polytetrahydrofuran ether diol and isophorone diisocyanate in anhydrous N-methylpyrrolidone, catalyzed by dibutyltin dilaurate at 70-80°C. Then, 2,2'-dithiodiethylamine and 3-mercapto-1-propanol were added sequentially and reacted at 50℃ to 60℃ to obtain the product; the mass ratio of the polytetrahydrofuran ether diol, isophorone diisocyanate, dibutyltin dilaurate, 2,2'-dithiodiethylamine and 3-mercapto-1-propanol was (100~110):(30~40):(0.04~0.06):(20~25):(5~6); The modified graphene is obtained by mixing graphene and silane coupling agent KH-550 in an ethanol aqueous solution at a mass ratio of (8-10):(6-8) at pH 4-5 and 60-65℃, resulting in graphene surface modified with silane coupling agent KH-550.

[0008] The preparation method of the above-mentioned disulfide-functionalized polyboronate-polysiloxane copolymer includes: adding 100-110 parts by mass of hydroxyl-terminated polydimethylsiloxane to 150-200 parts by mass of xylene under nitrogen protection; adding 85-95 parts by mass of tributyl borate dropwise under stirring at 80-85°C and 300-400 r / min for 2-3 hours to generate a polyboronate-polysiloxane prepolymer; adding 70-80 parts by mass of 2,2'-dithiodiethanol and 0.3-0.5 parts by mass of p-toluenesulfonic acid; heating to 110-115°C and bubbling under nitrogen for 5-6 hours; distilling under reduced pressure to obtain a concentrated solution; adding the concentrated solution to anhydrous ethanol; allowing it to stand and precipitate; collecting the precipitate; washing; and vacuum drying to obtain the disulfide-functionalized polyboronate-polysiloxane copolymer.

[0009] In the above method for preparing disulfide-functionalized polyboronate-polysiloxane copolymer, the dropping rate of tributyl borate is 0.5 mL / min to 0.8 mL / min; the bubbling speed of nitrogen is 10 mL / min to 15 mL / min; the vacuum distillation is carried out at 45℃ to 55℃ to recover 60 wt% to 70 wt% xylene; the amount of anhydrous ethanol used is 3 to 3.5 times the volume of the concentrated liquid; the washing is carried out 2 to 3 times with anhydrous ethanol; and the vacuum drying is carried out at 75℃ to 85℃ for 8 to 10 hours.

[0010] The preparation method of the above-mentioned micro-crosslinked polythiocarbamate-zinc coordination polymer includes: taking 100-110 parts by mass of the terminal thiol prepolymer and adding it to 140-160 parts by mass of anhydrous N-methylpyrrolidone and stirring to dissolve it, thereby obtaining a terminal thiol prepolymer liquid; dissolving 7-9 parts by mass of zinc acetate in 50-60 parts by mass of anhydrous N-methylpyrrolidone to obtain a zinc acetate solution; adding the zinc acetate solution dropwise to the terminal thiol prepolymer liquid while stirring, heating to 60-65℃, and reacting for 6-8 hours; cooling to room temperature, adding ethyl acetate, allowing it to stand and precipitate, collecting the precipitate, washing it, and vacuum drying to obtain the micro-crosslinked polythiocarbamate-zinc coordination polymer.

[0011] In the above-mentioned preparation method of micro-crosslinked polythiocarbamate-zinc coordination polymer, the amount of ethyl acetate used is 350 to 450 parts; the washing is performed by washing with ethyl acetate 2 to 3 times; the vacuum drying is performed by vacuum drying at 45°C to 50°C for 24 to 30 hours; and the temperature of ethyl acetate is 2°C to 5°C.

[0012] In the preparation method of the above-mentioned micro-crosslinked polythiocarbamate-zinc coordination polymer, the preparation method of the terminal thiol prepolymer includes: adding 30-40 parts of isophorone diisocyanate and 180-220 parts of anhydrous N-methylpyrrolidone to 100-110 parts of polytetrahydrofuran ether diol by mass under nitrogen protection; adding 0.04-0.06 parts of dibutyltin dilaurate dropwise while stirring at 70-80°C, and reacting for 3-4 hours; cooling to 50-60°C, adding 20-25 parts of 2,2'-dithiodiethylamine, and reacting for 2-3 hours; then adding 5-6 parts of 3-mercapto-1-propanol, and reacting for 4-5 hours; cooling to room temperature, adding ethyl acetate, allowing to stand and precipitate, collecting the precipitate, washing with ethyl acetate, and vacuum drying to obtain the terminal thiol prepolymer.

[0013] In the above method for preparing the terminal thiol prepolymer, the stirring speed is 150 r / min to 200 r / min; the amount of ethyl acetate is 400 parts to 500 parts; the washing is performed by washing with ethyl acetate 2 to 3 times; the vacuum drying is performed by vacuum drying at 40℃ to 50℃ for 20h to 28h; and the temperature of the ethyl acetate is 2℃ to 5℃.

[0014] The preparation method of the above-mentioned modified graphene includes: taking 8 to 10 parts by mass of graphene and dispersing it in 100 to 120 parts of ethanol aqueous solution to obtain a uniform graphene suspension; then adding 6 to 8 parts of silane coupling agent KH-550, adjusting the pH to 4 to 5, heating to 60°C to 65°C under nitrogen protection, and stirring; cooling to room temperature, centrifuging or filtration, collecting the precipitate, washing with anhydrous ethanol, then washing with ethyl acetate, and vacuum drying to obtain modified graphene.

[0015] In the above-mentioned method for preparing modified graphene, the concentration of the ethanol aqueous solution is 80 vol% to 85 vol%; the stirring is carried out at 500 r / min to 600 r / min for 5 h to 6 h; and the vacuum drying is carried out at 45 °C to 50 °C for 12 h to 18 h.

[0016] The preparation method of the above-mentioned self-healing material vulcanized extreme pressure agent for preventing membrane damage includes the following steps: According to the formula mass parts, the mineral oil is heated to 60℃~65℃, and antioxidant 1010 and nano-cerium oxide are added under stirring at 400r / min~600r / min. The mixture is stirred and dispersed evenly. Modified graphene, nano-tungsten disulfide and polyisobutylene bis(succinimide) are added and sheared and dispersed evenly at 4000rpm~5000rpm. Vulcanized isobutylene, vulcanized olefin cottonseed oil, diphenylthiourea and triphenyl phosphate are added and stirred at 400r / min~600r / min for 1h~1.5h. Disulfide bond functionalized polyboronate-polysiloxane copolymer and micro-crosslinked polythiocarbamate-zinc coordination polymer are added and stirred at 400r / min~600r / min for 1.5h~2h. The mixture is cooled to room temperature and filtered to obtain the self-healing material vulcanized extreme pressure agent.

[0017] This invention provides a self-healing extreme pressure vulcanizing agent for preventing membrane damage and its preparation method, with the following beneficial effects: I. This invention's extreme pressure agent fundamentally overcomes the technical pain points of traditional extreme pressure agents, which suffer from the inability to simultaneously achieve stability and repairability, and insufficient film strength, by constructing a composite system of a high-temperature resistant dynamic repair core, a rigid extreme pressure bearing layer, and a nano-synergistic reinforcing phase. Its core advantage lies in the dual dynamic effects formed by disulfide bonds, borate ester bonds, and Zn-S coordination bonds, achieving efficient self-healing after lubricant film damage. This ensures rapid crack filling at room temperature while maintaining repair stability in high-temperature environments. Simultaneously, the rapid generation of a high-density ferrous sulfide rigid film using sulfurized isobutylene, combined with sulfurized olefin cottonseed oil to enhance the adhesion between the film and the metal surface, forms a protective substrate with strong load-bearing capacity, resisting the risk of film rupture under high loads. Furthermore, modified graphene and nano-tungsten disulfide optimize the film structure through mechanical strengthening and physical densification, making it suitable for extreme working conditions in fields such as machinery manufacturing and transportation. In addition, polyisobutylene bis(succinimide) solves the problem of nanoparticle agglomeration, while antioxidants and nano-cerium oxide inhibit high-temperature oxidation and corrosion, ultimately achieving comprehensive performance of active repair and long-term protection, reducing equipment maintenance frequency, and improving operational safety and lifespan.

[0018] II. Disulfide bond functionalization (forming PBSi-S2) is key to achieving efficient self-healing: On the one hand, it introduces dual dynamic covalent bonds of borate ester bonds and disulfide bonds into the polymer molecule. The disulfide bonds can be reversibly broken and recombined at medium and low temperatures through thermal or mechanical forces, while the borate ester bonds can stably play an exchange role at high temperatures. The combination of the two greatly broadens the repair temperature window, allowing the material to initiate repair in more complex temperature environments. On the other hand, as crosslinking points, the disulfide bonds can connect linear polyborate-polysiloxane prepolymers into a moderately crosslinked network structure, improving the cohesive strength and toughness of the film layer and avoiding the problem of easy detachment of traditional extreme pressure agent films. At the same time, the disulfide bonds in its molecules can also undergo bond exchange reactions with the disulfide bonds and Zn-S coordination bonds in the micro-crosslinked polythiocarbamate-zinc coordination polymer to form an interpenetrating composite protective network, further enhancing the synergy between repair and load-bearing.

[0019] III. The reaction of zinc acetate with terminal thiol prepolymer to generate HT-PTU-Zn is the core step in constructing dynamic repair and mechanical support: Zn in zinc acetate 2+ It can form Zn-S coordination bonds with the thiol groups on the HT-PTU molecular chain. These coordination bonds act as reversible cross-linking points, transforming the originally linear, viscous liquid or waxy HT-PTU into a three-dimensional micro-cross-linked network structure. This transforms the material from a low-strength state to a tough, elastic solid, significantly improving the film's impact and shear resistance, meeting the mechanical requirements under extreme pressure conditions. At the same time, the Zn-S coordination bonds have dynamic reversibility. They can temporarily break under frictional stress or localized temperature rise to absorb energy and prevent permanent damage to the film. They can reform after the stress is relieved or the temperature recovers. The breakage and recombination process is the microscopic mechanism of the film's self-repair. In addition, zinc itself is a classic extreme pressure anti-wear component. Under high temperature and high pressure on the friction surface, it participates in the formation of a tough chemical reaction film, synergistically enhancing extreme pressure performance with the ferrous sulfide film.

[0020] Fourth, in terms of the synergy between dynamic repair and rigid load-bearing, the dynamic network composed of disulfide bonds and Zn-S coordination bonds can respond quickly when the rigid ferrous sulfide film is slightly damaged, and fill the cracks through bond exchange to avoid failure of the rigid film upon damage; while the ferrous sulfide film provides stable mechanical support for the dynamic repair system, preventing the film structure from collapsing due to excessive flow of the repair unit. The combination of the two achieves the dual guarantee of strong load-bearing and self-repair, solving the contradiction of traditional extreme pressure agents that are either strong in load-bearing but easily damaged, or capable of repair but weak in load-bearing.

[0021] V. Due to its high sulfur content, isobutylene sulfide can react rapidly with metal surfaces under high temperature and high pressure conditions to form a rigid ferrous sulfide film. This film has low shear strength but high load-bearing capacity, effectively preventing direct contact between metal components and serving as the core support for extreme pressure load-bearing performance. Meanwhile, the molecular chain of sulfide olefin cottonseed oil contains polar groups, which can be tightly adsorbed onto the metal surface, improving the adhesion between the ferrous sulfide film and the substrate and preventing the film from falling off under alternating stress. At the same time, the optimized ratio of sulfide to isobutylene further improves the uniformity of the film and reduces local weak points.

[0022] VI. Modified graphene not only enhances the mechanical strength of the film, but also improves thermal conductivity, avoiding local high-temperature heat accumulation during friction that could lead to film decomposition or rupture; the sheet structure of nano-tungsten disulfide can act as a physical rivet, filling the micropores in the film, improving the film density, and reducing abrasive wear during friction, further optimizing anti-wear performance.

[0023] VII. Auxiliary functional components ensure performance from multiple dimensions: Antioxidant 1010 can inhibit the oxidative degradation of base oil and extreme pressure agent components at high temperatures, extending product service life; nano-cerium oxide can fill film defects, enhancing the corrosion resistance and scratch resistance of the film; triphenyl phosphate can assist in the formation of an anti-wear film, synergistically reducing wear with other components; polyisobutylene bis(succinimide) can prevent the agglomeration of modified graphene, nano-tungsten disulfide and other nanoparticles, ensuring that each component is uniformly dispersed in the system and avoiding uneven film structure caused by particle agglomeration; diphenylthiourea can regulate the sulfurization reaction rate, optimize the formation process of ferrous sulfide film, and ensure uniform film structure.

[0024] 8. In the preparation of PBSi-S2, a reaction temperature of 80℃~85℃ ensures that hydroxyl-terminated polydimethylsiloxane and tributyl borate react fully to form a prepolymer, while 110℃~115℃ promotes the reaction between 2,2'-dithiodiethanol and the prepolymer. Simultaneously, nitrogen bubbling removes the byproduct water, driving the reaction forward. During the overall preparation of the extreme pressure agent, the mineral oil is heated to 60℃~65℃. This avoids splashing during cold oil mixing, ensuring the full dissolution and dispersion of antioxidant 1010, nano-cerium oxide, and other components, while also preventing the decomposition of functional groups such as disulfide bonds and Zn-S coordination bonds due to high temperatures.

[0025] 9. The extreme pressure agent of this invention is formulated according to the characteristics of each component, so as to achieve the best effect. Detailed Implementation

[0026] The present invention will be further described below with reference to specific implementation examples, but the present invention is not limited to these embodiments.

[0027] Definitions: PBSi is a polyboronic acid ester-polysiloxane prepolymer; PBSi-S2 is a disulfide-functionalized polyboronate-polysiloxane copolymer; HT-PTU is a prepolymer with terminal thiol groups; HT-PTU-Zn is a micro-crosslinked polythiocarbamate-zinc coordination polymer.

[0028] Example 1 A self-healing extreme pressure vulcanizate agent for preventing membrane damage comprises the following raw materials in parts by weight: 20 parts PBSi-S2, 10 parts HT-PTU-Zn, 23 parts vulcanizate isobutylene, 8 parts vulcanizate olefin cottonseed oil, 7 parts polyisobutylene bis(succinimide), 5.5 parts nano-reinforcing components, 4 parts auxiliary functional components, and 95 parts mineral oil. The nano-reinforcing components include 2.5 parts modified graphene and 3 parts nano-tungsten disulfide. The auxiliary functional components include 1 part diphenylthiourea, 1 part antioxidant 1010, 0.8 parts nano-cerium oxide, and 1.2 parts triphenyl phosphate.

[0029] The preparation method of PBSi-S2 includes: under nitrogen protection, 105 parts by mass of hydroxyl-terminated polydimethylsiloxane are added to 180 parts of xylene. While stirring at 82℃ and 350 r / min, 90 parts of tributyl borate are added dropwise at a rate of 0.6 mL / min. After the addition is complete, the reaction continues for 2.5 h to generate PBSi. The byproduct butanol is separated using a water separator. While maintaining nitrogen protection and stirring rate, 75 parts of 2,2'-dithiodiethanol and 0.4 parts of p-toluenesulfonic acid are added. The temperature is raised to 112℃, and nitrogen bubbling is performed at a rate of 12 mL / min (to remove the byproduct water). The mixture is refluxed for 5.5 h until the hydroxyl value of the product decreases to 5 mg. KOH concentration below 1 g; 65 wt% xylene was recovered by vacuum distillation at 50 °C to obtain a concentrated solution; the concentrated solution was added to 3.2 times its volume of anhydrous ethanol, stirred evenly, and allowed to stand for 14 h to precipitate a white precipitate; the precipitate was collected by filtration and washed twice with anhydrous ethanol (each time with an amount of 2.5 times the mass of the precipitate) to remove unreacted monomers and solvent; the washed precipitate was dried under vacuum at 80 °C for 9 h to obtain PBSi-S2.

[0030] The preparation method of HT-PTU-Zn includes: under nitrogen protection, adding 35 parts isophorone diisocyanate and 200 parts anhydrous N-methylpyrrolidone to 105 parts polytetrahydrofuran ether diol; adding 0.05 parts dibutyltin dilaurate dropwise while stirring at 75℃ and 180 r / min; continuing the reaction for 3.5 h (the isocyanate peak disappears as monitored by FTIR); cooling to 55℃, adding 22 parts 2,2'-dithiodiethylamine; continuing the reaction for 2.5 h; then adding 5.5 parts 3-mercapto-1-propanol; reacting at 55℃ for 4.5 h; determining the thiol group content to be above 0.8 mmol / g by iodometric titration; cooling to room temperature, adding 450 parts ethyl acetate at 3℃; stirring and standing for 2.5 h; a yellow precipitate precipitates; collecting the precipitate by filtration; washing twice with ethyl acetate at 3℃ to remove unreacted monomers and solvent; and then... The precipitate after washing was dried under vacuum at 45℃ for 24 h to obtain HT-PTU; 105 parts of HT-PTU were added to 150 parts of anhydrous N-methylpyrrolidone and stirred at 32℃ and 250 r / min for 40 min until completely dissolved to obtain HT-PTU solution; 8 parts of zinc acetate were dissolved in 55 parts of anhydrous N-methylpyrrolidone to obtain zinc acetate solution; under stirring at 250 r / min, the zinc acetate solution was added dropwise to the HT-PTU solution at a rate of 1.5 mL / min, the temperature was raised to 62℃, and the reaction was continued for 7 h; after cooling to room temperature, 400 parts of ethyl acetate at 3℃ were added, stirred, and allowed to stand for 2.5 h to precipitate a pale yellow precipitate; the precipitate was collected by suction filtration, washed twice with ethyl acetate at 3℃ (each time the amount was 2.5 times the mass of the precipitate) to remove unreacted monomers and solvents, and dried under vacuum at 48℃ for 26 h to obtain HT-PTU-Zn.

[0031] The method for preparing modified graphene includes: taking 9 parts by mass of graphene and dispersing it in 110 parts by mass of 82 vol% ethanol aqueous solution, ultrasonically dispersing it evenly to obtain a uniform graphene suspension; then adding 7 parts by mass of silane coupling agent KH-550, adjusting the pH to 4.5 with 1.5 mol / L hydrochloric acid aqueous solution, heating to 62℃ under nitrogen protection, stirring at 550 r / min for 5.5 h; cooling to room temperature, filtering, collecting the precipitate, washing it 3 times with anhydrous ethanol (each time the amount is 2.5 times the mass of the precipitate), then washing it once with ethyl acetate (each time the amount is 2.5 times the mass of the precipitate), and vacuum drying at 48℃ for 15 h to obtain modified graphene.

[0032] The preparation method of the above-mentioned self-healing material vulcanized extreme pressure agent for preventing membrane damage includes: heating mineral oil to 62°C according to the formula mass parts, adding antioxidant 1010 and nano-cerium oxide under stirring at 500 r / min, and stirring and dispersing for 35 min; adding modified graphene, nano-tungsten disulfide and polyisobutylene bis(succinimide), and dispersing at high speed at 4500 rpm for 25 min; adding sulfurized isobutylene, sulfurized olefin cottonseed oil, diphenylthiourea and triphenyl phosphate, and stirring at 500 r / min for 1 h; adding PBSi-S2 and HT-PTU-Zn, and stirring at 500 r / min for 1.5 h; cooling to room temperature, and filtering through a 3500 mesh sieve to obtain the self-healing material vulcanized extreme pressure agent.

[0033] Example 2 A self-healing extreme pressure vulcanizate agent for preventing membrane damage comprises the following raw materials in parts by weight: 18 parts PBSi-S2, 12 parts HT-PTU-Zn, 25 parts vulcanizate isobutylene, 10 parts vulcanizate olefin cottonseed oil, 6 parts polyisobutylene bis(succinimide), 7 parts nano-reinforcing components, 2.5 parts auxiliary functional components, and 100 parts mineral oil. The nano-reinforcing components include 3 parts modified graphene and 4 parts nano-tungsten disulfide. The auxiliary functional components include 0.5 parts diphenylthiourea, 0.5 parts antioxidant 1010, 0.5 parts nano-cerium oxide, and 1 part triphenyl phosphate.

[0034] The preparation method of PBSi-S2 includes: under nitrogen protection, 100 parts by mass of hydroxyl-terminated polydimethylsiloxane are added to 200 parts of xylene. While stirring at 80℃ and 400 r / min, 95 parts of tributyl borate are added dropwise at a rate of 0.5 mL / min. After the addition is complete, the reaction continues for 2 hours to generate PBSi. The byproduct butanol is separated using a water separator. While maintaining nitrogen protection and stirring rate, 80 parts of 2,2'-dithiodiethanol and 0.3 parts of p-toluenesulfonic acid are added. The temperature is raised to 115℃, and nitrogen bubbling is performed at a rate of 10 mL / min (to remove the byproduct water). The mixture is refluxed for 6 hours until the hydroxyl value of the product decreases to 5 mg. KOH concentration below 1 g; 70 wt% xylene was recovered by vacuum distillation at 45 °C to obtain a concentrated solution; the concentrated solution was added to anhydrous ethanol at 3 times its volume, stirred evenly, and allowed to stand for 16 h to precipitate a white precipitate; the precipitate was collected by filtration and washed twice with anhydrous ethanol (each time the amount of ethanol was 3 times the mass of the precipitate) to remove unreacted monomers and solvent; the washed precipitate was dried under vacuum at 75 °C for 10 h to obtain PBSi-S2.

[0035] The preparation method of HT-PTU-Zn includes: under nitrogen protection, adding 40 parts of isophorone diisocyanate and 180 parts of anhydrous N-methylpyrrolidone to 100 parts of polytetrahydrofuran ether diol, and adding 0.06 parts of dibutyltin dilaurate dropwise while stirring at 80℃ and 150 r / min, and continuing the reaction for 3 h (the isocyanate peak disappears as monitored by FTIR); cooling to 60℃, adding 20 parts of 2,2'-dithiodiethylamine, and continuing the reaction for 3 h; then adding 5 parts of 3-mercapto-1-propanol, and reacting at 60℃ for 4 h, with the thiol group content determined by iodometric titration to be above 0.8 mmol / g; cooling to room temperature, adding 500 parts of ethyl acetate at 2℃, stirring, and letting stand for 3 h, resulting in the precipitation of a yellow precipitate; collecting the precipitate by filtration, washing it three times with ethyl acetate at 2℃ to remove unreacted monomers and solvent; and then... The precipitate was dried under vacuum at 40℃ for 28 h to obtain HT-PTU; 100 parts of HT-PTU were added to 160 parts of anhydrous N-methylpyrrolidone and stirred at 30℃ and 300 r / min for 30 min until completely dissolved to obtain HT-PTU solution; 9 parts of zinc acetate were dissolved in 50 parts of anhydrous N-methylpyrrolidone to obtain zinc acetate solution; under stirring at 300 r / min, the zinc acetate solution was added dropwise to the HT-PTU solution at a rate of 1 mL / min, the temperature was raised to 65℃, and the reaction was continued for 6 h; after cooling to room temperature, 450 parts of ethyl acetate at 2℃ were added, stirred, and allowed to stand for 3 h to precipitate a pale yellow precipitate; the precipitate was collected by filtration, washed 3 times with ethyl acetate at 2℃ (each time the amount was twice the mass of the precipitate) to remove unreacted monomers and solvents, and dried under vacuum at 50℃ for 24 h to obtain HT-PTU-Zn.

[0036] The method for preparing modified graphene includes: taking 8 parts by mass of graphene and dispersing it in 100 parts by mass of 80 vol% ethanol aqueous solution, shearing and dispersing it evenly to obtain a uniform graphene suspension; then adding 6 parts by mass of silane coupling agent KH-550, adjusting the pH to 4 with 1 mol / L hydrochloric acid aqueous solution, heating to 60℃ under nitrogen protection, stirring at 500 r / min for 5 h; cooling to room temperature, centrifuging, collecting the precipitate, washing it 3 times with anhydrous ethanol (each time the amount is twice the mass of the precipitate), then washing it once with ethyl acetate (each time the amount is twice the mass of the precipitate), and vacuum drying at 45℃ for 12 h to obtain modified graphene.

[0037] The preparation method of the above-mentioned self-healing material vulcanized extreme pressure agent for preventing membrane damage includes: heating mineral oil to 60°C according to the formula mass parts, adding antioxidant 1010 and nano-cerium oxide under stirring at 400 r / min, and stirring and dispersing for 30 min; adding modified graphene, nano-tungsten disulfide and polyisobutylene bis(succinimide), and high-speed shearing dispersion at 4000 rpm for 20 min; adding sulfurized isobutylene, sulfurized olefin cottonseed oil, diphenylthiourea and triphenyl phosphate, and stirring at 400 r / min for 1 h; adding PBSi-S2 and HT-PTU-Zn, and stirring at 400 r / min for 1.5 h; cooling to room temperature, and filtering through a 3000 mesh sieve to obtain the self-healing material vulcanized extreme pressure agent.

[0038] Example 3 A self-healing extreme pressure vulcanizate agent for preventing membrane damage comprises the following raw materials in parts by weight: 2 parts PBSi-S22, 8 parts HT-PTU-Zn, 30 parts vulcanizate isobutylene, 6 parts vulcanizate olefin cottonseed oil, 8 parts polyisobutylene bis(succinimide), 4 parts nano-reinforcing components, 6 parts auxiliary functional components, and 90 parts mineral oil. The nano-reinforcing components include 1.5 parts modified graphene and 2.5 parts nano-tungsten disulfide. The auxiliary functional components include 1.5 parts diphenylthiourea, 1.5 parts antioxidant 1010, 1.5 parts nano-cerium oxide, and 1.5 parts triphenyl phosphate.

[0039] The preparation method of PBSi-S2 includes: under nitrogen protection, 110 parts by mass of hydroxyl-terminated polydimethylsiloxane are added to 150 parts of xylene. While stirring at 85°C and 300 r / min, 85 parts of tributyl borate are added dropwise at a rate of 0.8 mL / min. After the addition is complete, the reaction continues for 3 hours to generate PBSi. The byproduct butanol is separated using a water separator. While maintaining nitrogen protection and stirring rate, 70 parts of 2,2'-dithiodiethanol and 0.5 parts of p-toluenesulfonic acid are added. The temperature is raised to 110°C, and nitrogen bubbling is performed at a rate of 15 mL / min (to remove the byproduct water). The mixture is refluxed for 5 hours until the hydroxyl value of the product decreases to 5 mg. KOH concentration below 1 g; 60 wt% xylene was recovered by vacuum distillation at 55 °C to obtain a concentrated solution; the concentrated solution was added to 3.5 times its volume of anhydrous ethanol, stirred evenly, and allowed to stand for 12 h to precipitate a white precipitate; the precipitate was collected by filtration and washed 3 times with anhydrous ethanol (each time the amount of ethanol was twice the mass of the precipitate) to remove unreacted monomers and solvent; the washed precipitate was dried under vacuum at 85 °C for 8 h to obtain PBSi-S2.

[0040] The preparation method of HT-PTU-Zn includes: under nitrogen protection, adding 30 parts of isophorone diisocyanate and 220 parts of anhydrous N-methylpyrrolidone to 110 parts of polytetrahydrofuran ether diol, and adding 0.04 parts of dibutyltin dilaurate dropwise while stirring at 70℃ and 200 r / min, and continuing the reaction for 4 h (the isocyanate peak disappears as monitored by FTIR); cooling to 50℃, adding 25 parts of 2,2'-dithiodiethylamine, and continuing the reaction for 2 h; then adding 6 parts of 3-mercapto-1-propanol, and reacting at 50℃ for 5 h, with the thiol group content determined by iodometric titration to be above 0.8 mmol / g; cooling to room temperature, adding 400 parts of ethyl acetate at 5℃, stirring, and letting stand for 2 h, resulting in the precipitation of a yellow precipitate; collecting the precipitate by filtration, washing twice with ethyl acetate at 5℃ to remove unreacted monomers and solvent; and then... The precipitate was dried under vacuum at 50℃ for 20 h to obtain HT-PTU; 110 parts of HT-PTU were added to 140 parts of anhydrous N-methylpyrrolidone and stirred at 35℃ and 200 r / min for 50 min until completely dissolved to obtain HT-PTU solution; 7 parts of zinc acetate were dissolved in 60 parts of anhydrous N-methylpyrrolidone to obtain zinc acetate solution; under stirring at 200 r / min, the zinc acetate solution was added dropwise to the HT-PTU solution at a rate of 2 mL / min, the temperature was raised to 60℃, and the reaction was continued for 8 h; after cooling to room temperature, 350 parts of ethyl acetate at 5℃ were added, stirred, and allowed to stand for 2 h to precipitate a pale yellow precipitate; the precipitate was collected by suction filtration, washed twice with ethyl acetate at 5℃ (each time the amount was 3 times the mass of the precipitate) to remove unreacted monomers and solvents, and dried under vacuum at 45℃ for 30 h to obtain HT-PTU-Zn.

[0041] The method for preparing modified graphene includes: taking 10 parts by mass of graphene and dispersing it in 120 parts by mass of 85 vol% ethanol aqueous solution, ultrasonically dispersing it evenly to obtain a uniform graphene suspension; then adding 8 parts by mass of silane coupling agent KH-550, adjusting the pH to 5 with 2 mol / L hydrochloric acid aqueous solution, heating to 65℃ under nitrogen protection, stirring at 600 r / min for 6 h; cooling to room temperature, filtering, collecting the precipitate, washing it 4 times with anhydrous ethanol (each time the amount is 3 times the mass of the precipitate), then washing it 2 times with ethyl acetate (each time the amount is 3 times the mass of the precipitate), and vacuum drying at 50℃ for 18 h to obtain modified graphene.

[0042] The preparation method of the above-mentioned self-healing material vulcanized extreme pressure agent for preventing membrane damage includes: heating mineral oil to 65°C according to the formula mass parts, adding antioxidant 1010 and nano-cerium oxide under stirring at 600 r / min, and stirring and dispersing for 40 min; adding modified graphene, nano-tungsten disulfide and polyisobutylene bis(succinimide), and high-speed shearing dispersion at 5000 rpm for 30 min; adding sulfurized isobutylene, sulfurized olefin cottonseed oil, diphenylthiourea and triphenyl phosphate, and stirring at 600 r / min for 1.5 h; adding PBSi-S2 and HT-PTU-Zn, and stirring at 600 r / min for 2 h; cooling to room temperature, and filtering through a 4000 mesh sieve to obtain the self-healing material vulcanized extreme pressure agent.

[0043] The following are some of the raw material specifications or sources involved in the above embodiments: Sulfurized isobutylene, model T321N, sourced from Huihua Technology Co., Ltd.; Sulfurized olefin cottonseed oil, model T405A, sourced from Jiangyin Kangtai Lubricating Oil Additives Co., Ltd.; Polyisobutylene bis(succinimide), model T154, sourced from Jinzhou Jiaduorun Materials Technology Co., Ltd.; Mineral oil, model 350SN, sourced from Shandong Zhongrun New Materials Technology Co., Ltd.; Nano-tungsten disulfide, median particle size 100nm; Diphenylthiourea accelerator DPTU, sourced from Kandis Chemical (Hubei) Co., Ltd., purity 98%; Antioxidant 1010, sourced from Hubei Shixing Chemical Co., Ltd., purity 99%; Nano-cerium oxide, median particle size 50nm; Triphenyl phosphate, sourced from Wuhan Kanos Technology Co., Ltd., purity 99%; Hydroxyl-terminated polydimethylsiloxane, sourced from Guangdong Wengjiang Chemical Reagent Co., Ltd., Mn=1000, density 0.95g / cm³. 3 Xylene purity 99%. Tributyl borate purity 99.5%. 2,2'-Dithiodiethanol is bis(2-hydroxyethyl) disulfide, sourced from Shanghai Mairui Biochemical Technology Co., Ltd., purity 97%. p-Toluenesulfonic acid purity 99%. Polytetrahydrofuran ether diol (PTMEG) is sourced from Shandong Suihua Biotechnology Co., Ltd., Mn=1000, purity 98%. Isophorone diisocyanate purity 99%. Dibutyltin dilaurate purity 99.5%. 2,2'-Dithiodiethylamine is cystamine, purity 98%. 3-Mercapto-1-propanol purity 98%. Ethyl acetate purity 99.9%. Zinc acetate purity 99%. Graphene 1nm-10nm, model XFQ021, sourced from Jiangsu Xianfeng Nanomaterials Technology Co., Ltd. Silane coupling agent KH-550 is 3-aminopropyltriethoxysilane, purity 99%.

[0044] Comparative Example 1 The difference from Example 1 is that PBSi-S2 is changed to 8 parts and HT-PTU-Zn is changed to 22 parts.

[0045] Comparative Example 2 The difference from Example 1 is that the sulfurized isobutylene is changed to 8 parts and the sulfurized olefin cottonseed oil is changed to 23 parts.

[0046] Comparative Example 3 The difference from Example 1 is that HT-PTU-Zn is replaced with 2 parts and sulfurized olefin cottonseed oil with 16 parts.

[0047] Comparative Example 4 The difference from Example 1 is that PBSi-S2 is replaced by PBSi; PBSi is directly obtained through subsequent precipitation steps.

[0048] Comparative Example 5 The difference from Example 1 is that HT-PTU-Zn is replaced by HT-PTU.

[0049] Sample preparation: Accurately weigh 2.00 g of the extreme pressure agent stock solution to be tested, mix with 98.00 g of base oil (150SN mineral oil) to prepare a 2.0 wt% dilution, and stir at 300 r / min at 60℃ for at least 30 min until the sample is completely homogeneous and transparent. A blank control group was also set up, containing only 150SN mineral oil and no extreme pressure agent.

[0050] I. Extreme pressure bearing capacity test: 1. Testing equipment: MQ-800 four-ball friction and wear tester.

[0051] 2. Test steel balls: GCr15 bearing steel balls, 12.7mm in diameter, HRC66 hardness, and surface roughness Ra below 0.02μm.

[0052] 3. Test conditions: Room temperature 25℃, rotation speed 1450 r / min, load increasing in a series of increments of 98, 126, 158, 196, 245, 308, 386, 490, 617, 777, 980, 1235, 1556, 1960... (a geometric series with a common ratio of approximately 1.26), each load increment lasting 10 seconds, until sintering occurs. 20 mL of sample is added, completely submerging the steel ball contact points.

[0053] 4. Test indicators: maximum non-seize load (PB value), sintering load (PD value); 3 parallel samples, average value is taken.

[0054] II. Wear resistance test: 1. Testing equipment: MQ-800 four-ball friction and wear tester.

[0055] 2. Test steel ball: Same extreme pressure bearing capacity test.

[0056] 3. Test conditions: Load 392N, rotation speed 1450r / min, temperature 75℃, test time 60min. Sample volume 20mL, completely submerging the steel ball contact point.

[0057] 4. Test parameters: After the test, the steel balls were cleaned with acetone and dried. Using an optical microscope, the wear scar diameters of the three test steel balls at the bottom were measured. Each wear scar was measured twice in mutually perpendicular directions, for a total of 6 data points. The average value was taken as the wear scar diameter (WSD) of this test. The test was performed in 3 parallel runs, and the average value was taken.

[0058] III. Membrane Damage-Repair Cycle Test: 1. Testing equipment: MQ-800 four-ball friction and wear tester.

[0059] 2. Experimental Procedure: (1) Film preparation and acquisition of reference wear scar (D1): Load 392N, rotation speed 1450r / min, temperature 75℃, run for 30min, stop the machine and measure the standard wear scar diameter at this time according to the above method, and record it as D1. The sample addition amount is 20mL.

[0060] (2) Membrane damage: Increase the load to 1500N within 5s, maintain it for 10s, and confirm the damage through torque mutation; (3) Self-repair stage: restore load of 392N, continue to run for 60min, and measure the final wear scar diameter D2 after the test.

[0061] 3. Repair efficiency calculation: η=(D1) 2 -D2 2 ) / D1 2 ×100%. The test was performed in triplicate, and the average value was taken.

[0062] Table 1. Test Results (Average Values)

[0063] The core of the extreme pressure agents in Examples 1 to 3 lies in the construction of a system comprising a dynamic repair core, a rigid extreme pressure layer, and a nano-reinforcing phase. Disulfide bonds and zinc coordination bonds form a dual dynamic network, enabling rapid and reversible healing of the damaged film. Sulfated isobutylene rapidly generates a dense, rigid ferrous sulfide film, while sulfurized olefin cottonseed oil enhances the adhesion between the film and the metal surface. Modified graphene and nano-tungsten disulfide optimize the film's density and load-bearing capacity through mechanical strengthening and physical anchoring. The performance differences among the three stem from the refined adjustment of raw material ratios and process parameters; when the core component proportions are reasonable, the extreme pressure load-bearing capacity, wear resistance, and self-repair efficiency achieve an optimal balance.

[0064] The dynamic repair core ratio in Comparative Example 1 is unbalanced: disulfide bonds are the core donor for dynamic repair, and their insufficient proportion directly weakens the reversible cross-linking ability of the film layer; excessive zinc coordination polymers are prone to aggregation, which destroys the uniformity of the film layer structure. This leads to discontinuous ferrous sulfide films generated under extreme pressure, reduced load-bearing capacity, and insufficient number of repair units, making it impossible to quickly fill cracks and significantly reducing self-repair efficiency.

[0065] In Comparative Example 2, the rigid extreme pressure agent formulation was reversed: Isobutylene sulfide is a key component in forming a high-strength ferrous sulfide rigid membrane; insufficient proportion of it leads to insufficient membrane thickness and low density under extreme pressure. Sulfated olefin cottonseed oil has lower reactivity than isobutylene sulfide, and its longer molecular chains easily cause the membrane to become porous. The supporting effect of the rigid membrane is weakened, making it unable to withstand membrane rupture under high loads, and the self-healing components are unable to function effectively due to the fragile basic structure of the membrane.

[0066] Comparative Example 3 suffers from a lack of core repair mechanisms: severe deficiency of zinc coordination bonds leads to the collapse of the dynamic repair system, resulting in a significant reduction in film rigidity and self-repair capability; after replacing isobutylene with sulfurized olefin cottonseed oil, not only is the extreme pressure film-forming ability weak, but its molecular chain entanglement also hinders the uniform dispersion of the nano-reinforcing phase. The film is easily damaged under medium and low loads and lacks an effective dynamic repair mechanism.

[0067] Comparative Example 4 shows a lack of dynamic disulfide bonds in its repair core: ordinary polyboronate-polysiloxane prepolymers lack functional disulfide bonds, making it difficult to form an efficient and reversible dynamic cross-linking network. When the film is damaged, there are not enough dynamic bond breaks and recombinations to fill the cracks, and it relies solely on the relatively unstable boronate bonds, making it difficult to achieve efficient self-healing.

[0068] Comparative Example 5 shows a core repair lacking zinc coordination bonds: the absence of zinc ion coordination cross-linking structures makes it difficult to form a dual dynamic network with disulfide bonds. Insufficient integrity of the dynamic network leads to decreased cross-linking degree and toughness of the film layer, making it prone to wear under extreme pressure; after damage, it is difficult to facilitate disulfide bond recombination through metal ion migration, resulting in slow repair speed and incomplete healing.

[0069] The blank control group lacked effective functional components: mineral oil alone could not form a stable lubricating film, leading to direct contact and friction between metal surfaces under high temperature and pressure. It lacked both the rigid film required for extreme pressure bearing and any self-healing components, resulting in extremely poor extreme pressure performance, a tendency to sinter, large wear scars, and no self-healing ability.

Claims

1. A self-healing extreme pressure vulcanizing agent for preventing membrane damage, characterized in that, The raw materials include the following parts by weight: 18 to 22 parts of disulfide-functionalized polyboronate-polysiloxane copolymer, 8 to 12 parts of micro-crosslinked polythiocarbamate-zinc coordination polymer, 25 to 30 parts of sulfurized isobutylene, 6 to 10 parts of sulfurized olefin cottonseed oil, 6 to 8 parts of polyisobutylene bis(succinimide), 4 to 7 parts of nano-reinforcing components, 2.5 to 6 parts of auxiliary functional components, and 90 to 100 parts of mineral oil; The nano-reinforcing components include 1.5 to 3 parts modified graphene and 2.5 to 4 parts nano tungsten disulfide; the auxiliary functional components include 0.5 to 1.5 parts diphenylthiourea, 0.5 to 1.5 parts antioxidant 1010, 0.5 to 1.5 parts nano cerium oxide and 1 to 1.5 parts triphenyl phosphate. The disulfide-functionalized polyboronic acid ester-polysiloxane copolymer is prepared by reacting hydroxyl-terminated polydimethylsiloxane with tributyl borate in xylene at 80°C–85°C to generate a prepolymer, followed by the addition of 2,2'-dithiodiethanol and p-toluenesulfonic acid at 110°C–115°C; the mass ratio of the hydroxyl-terminated polydimethylsiloxane, tributyl borate, 2,2'-dithiodiethanol, and p-toluenesulfonic acid is (100–110):(85–95):(70–80):(0.3–0.5). The micro-crosslinked polythiocarbamate-zinc coordination polymer is prepared by reacting a thiol-terminated prepolymer with zinc acetate at a mass ratio of (100-110):(7-9) in anhydrous N-methylpyrrolidone at 60-65°C; the thiol-terminated prepolymer is prepared by reacting polytetrahydrofuran ether diol and isophorone diisocyanate in anhydrous N-methylpyrrolidone, catalyzed by dibutyltin dilaurate at 70-80°C. Then, 2,2'-dithiodiethylamine and 3-mercapto-1-propanol were added sequentially and reacted at 50℃ to 60℃ to obtain the product; the mass ratio of the polytetrahydrofuran ether diol, isophorone diisocyanate, dibutyltin dilaurate, 2,2'-dithiodiethylamine and 3-mercapto-1-propanol was (100~110):(30~40):(0.04~0.06):(20~25):(5~6); The modified graphene is obtained by mixing graphene and silane coupling agent KH-550 in an ethanol aqueous solution at a mass ratio of (8-10):(6-8) at pH 4-5 and 60-65℃, resulting in graphene surface modified with silane coupling agent KH-550.

2. The self-healing extreme pressure vulcanizing agent for preventing membrane damage according to claim 1, characterized in that, The preparation method of the disulfide-functionalized polyboronate-polysiloxane copolymer includes: adding 100-110 parts by mass of hydroxyl-terminated polydimethylsiloxane to 150-200 parts by mass of xylene under nitrogen protection; adding 85-95 parts by mass of tributyl borate dropwise under stirring at 80-85°C and 300-400 r / min for 2-3 hours to generate a polyboronate-polysiloxane prepolymer; adding 70-80 parts by mass of 2,2'-dithiodiethanol and 0.3-0.5 parts by mass of p-toluenesulfonic acid; heating to 110-115°C and bubbling under nitrogen for 5-6 hours; distilling under reduced pressure to obtain a concentrated solution; adding the concentrated solution to anhydrous ethanol; allowing it to stand and precipitate; collecting the precipitate; washing; and vacuum drying to obtain the disulfide-functionalized polyboronate-polysiloxane copolymer.

3. The self-healing extreme pressure vulcanizing agent for preventing membrane damage according to claim 2, characterized in that, The dropping rate of the tributyl borate is 0.5 mL / min to 0.8 mL / min; the bubbling rate of the nitrogen gas is 10 mL / min to 15 mL / min; the vacuum distillation is carried out at 45℃ to 55℃ to recover 60 wt% to 70 wt% xylene; the amount of anhydrous ethanol used is 3 to 3.5 times the volume of the concentrated liquid; the washing is carried out 2 to 3 times with anhydrous ethanol; the vacuum drying is carried out at 75℃ to 85℃ for 8 to 10 hours.

4. The self-healing extreme pressure vulcanizing agent for preventing membrane damage according to claim 1, characterized in that, The preparation method of the micro-crosslinked polythiocarbamate-zinc coordination polymer includes: taking 100-110 parts by mass of the terminal thiol prepolymer and adding it to 140-160 parts by mass of anhydrous N-methylpyrrolidone and stirring to dissolve, thereby obtaining a terminal thiol prepolymer liquid; dissolving 7-9 parts by mass of zinc acetate in 50-60 parts by mass of anhydrous N-methylpyrrolidone to obtain a zinc acetate solution; adding the zinc acetate solution dropwise to the terminal thiol prepolymer liquid while stirring, heating to 60-65°C, and reacting for 6-8 hours; cooling to room temperature, adding ethyl acetate, allowing it to stand and precipitate, collecting the precipitate, washing it, and vacuum drying to obtain the micro-crosslinked polythiocarbamate-zinc coordination polymer.

5. The self-healing extreme pressure vulcanizing agent for preventing membrane damage according to claim 4, characterized in that, The amount of ethyl acetate used is 350 to 450 parts; the washing is performed by washing with ethyl acetate 2 to 3 times; the vacuum drying is performed by vacuum drying at 45°C to 50°C for 24 to 30 hours; the temperature of the ethyl acetate is 2°C to 5°C.

6. The self-healing extreme pressure vulcanizing agent for preventing membrane damage according to claim 4, characterized in that, The method for preparing the terminal thiol prepolymer includes: adding 30-40 parts of isophorone diisocyanate and 180-220 parts of anhydrous N-methylpyrrolidone to 100-110 parts of polytetrahydrofuran ether diol under nitrogen protection; adding 0.04-0.06 parts of dibutyltin dilaurate dropwise while stirring at 70-80°C; reacting for 3-4 hours; cooling to 50-60°C; adding 20-25 parts of 2,2'-dithiodiethylamine; reacting for 2-3 hours; then adding 5-6 parts of 3-mercapto-1-propanol; reacting for 4-5 hours; cooling to room temperature; adding ethyl acetate; allowing the mixture to stand and precipitate; collecting the precipitate; washing with ethyl acetate; and vacuum drying to obtain the terminal thiol prepolymer.

7. The self-healing extreme pressure vulcanizing agent for preventing membrane damage according to claim 6, characterized in that, The stirring speed is 150 r / min to 200 r / min; the amount of ethyl acetate used is 400 parts to 500 parts; the washing is performed 2 to 3 times with ethyl acetate; the vacuum drying is performed at 40℃ to 50℃ for 20h to 28h; the temperature of the ethyl acetate is 2℃ to 5℃.

8. The self-healing extreme pressure vulcanizing agent for preventing membrane damage according to claim 1, characterized in that, The method for preparing the modified graphene includes: taking 8 to 10 parts by mass of graphene and dispersing it in 100 to 120 parts by mass of an aqueous ethanol solution to obtain a uniform graphene suspension; then adding 6 to 8 parts by mass of silane coupling agent KH-550, adjusting the pH to 4 to 5, heating to 60°C to 65°C under nitrogen protection, and stirring; cooling to room temperature, centrifuging or filtration, collecting the precipitate, washing with anhydrous ethanol, then washing with ethyl acetate, and vacuum drying to obtain the modified graphene.

9. The self-healing extreme pressure vulcanizing agent for preventing membrane damage according to claim 8, characterized in that, The concentration of the ethanol-water solution is 80 vol% to 85 vol%; the stirring is carried out at 500 r / min to 600 r / min for 5 h to 6 h; the vacuum drying is carried out at 45 °C to 50 °C for 12 h to 18 h.

10. The method for preparing a self-healing anti-film damage material vulcanizing extreme pressure agent according to claim 1, characterized in that, The process includes the following steps: According to the formula mass parts, the mineral oil is heated to 60℃~65℃, and antioxidant 1010 and nano-cerium oxide are added while stirring at 400r / min~600r / min. The mixture is stirred and dispersed evenly. Modified graphene, nano-tungsten disulfide and polyisobutylene bis(succinimide) are added and sheared and dispersed evenly at 4000rpm~5000rpm. Sulfurized isobutylene, sulfurized olefin cottonseed oil, diphenylthiourea and triphenyl phosphate are added and stirred at 400r / min~600r / min for 1h~1.5h. Disulfide-functionalized polyboronate-polysiloxane copolymer and micro-crosslinked polythiocarbamate-zinc coordination polymer are added and stirred at 400r / min~600r / min for 1.5h~2h. The mixture is cooled to room temperature and filtered to obtain the self-healing material sulfurized extreme pressure agent.

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