CN116082837B - Preparation method of lubricating resin composition - Google Patents
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- CN116082837B CN116082837B CN202310206680.1A CN202310206680A CN116082837B CN 116082837 B CN116082837 B CN 116082837B CN 202310206680 A CN202310206680 A CN 202310206680A CN 116082837 B CN116082837 B CN 116082837B
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- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The invention relates to the technical field of lubrication, and discloses a preparation method of a lubricating resin composition, which is characterized in that polyimide resin, molybdenum disulfide-carbon nano tube grafted polytetrafluoroethylene, polyether ether ketone resin, an antioxidant and a dispersing agent are mixed and melt-blended to obtain the lubricating resin composition, and a molybdenum disulfide-carbon nano tube composite material and polytetrafluoroethylene are connected through a covalent bond, so that the lubricating resin composition has stronger stress transmission capability, the uneven structure of the composite material caused by agglomeration of nano materials is avoided, a large number of stress concentration points are avoided, the service performance of the material is improved, the time for reaching a steady state can be shortened through a synergistic effect between the polyimide resin and the molybdenum disulfide-carbon nano tube grafted polytetrafluoroethylene, the banding damage of the polytetrafluoroethylene resin is prevented, the compatibility between the polyimide resin and the polytetrafluoroethylene resin is improved, the friction and abrasion resistance performance of the lubricating resin composition is further improved, and the mechanical property of the material is improved.
Description
Technical Field
The invention relates to the technical field of lubrication, in particular to a preparation method of a lubricating resin composition.
Background
Lubricity is a substance that characterizes the ability of a lubricant to reduce friction and wear, to lubricate, cool and seal the friction portion of machinery, and has very wide application in a variety of industries, both industrial and civil. With the rapid development of industries such as aerospace, automobiles, mechanical manufacturing and the like, more and more high-bearing friction sliding parts are used in environments such as hydraulic pressure, dry friction and the like, and more severe requirements are put on the quality of lubricating materials. Among them, the self-lubricating technology has been a development trend of the lubricating technology due to its unique advantages, and the wear-resistant self-lubricating material with high strength has become a research hot spot in the friction field.
Polyimide resin (PI) is an engineering material with excellent comprehensive performance, has good structural stability and heat resistance, has excellent lubricity under severe conditions such as vacuum, high and low temperature and the like, and can be widely applied to industries such as aerospace, automobiles, mechanical manufacturing and the like as a solid lubrication part material. However, the pure polyimide material has the advantages of large friction coefficient, poor wear resistance, incapability of meeting severe running conditions such as high bearing capacity, high speed and the like, and poor processability of polyimide resin. Chinese patent application CN103122145A discloses a polyimide self-lubricating composite material, which is prepared by compounding and filling carbon fiber, solid lubricant and nano particles. Chinese patent application CN104927354A also discloses a polyimide self-lubricating composite material and a preparation method thereof, wherein the polyimide is modified by adopting the synergistic combination of the multi-functional filler, so that the friction coefficient and the wear rate of a polyimide matrix are further reduced, and the high-performance polyimide-based self-lubricating composite material is obtained. However, various solid lubricants filled in improve the friction and wear properties of polymers, but generally reduce the mechanical properties of the materials, require that the composite materials reach steady-state equilibrium in a very short time, and simply realize material compounding by filling, have general effects of improving the self-lubricating properties and prolonging the service life, and limit the application fields of the composite materials to a great extent. In summary, it is known that development of a lubricating resin composition having excellent mechanical properties, abrasion resistance, easiness in processing and long service life is a problem to be solved.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a lubricating resin composition, which solves the defects of large friction coefficient, mechanical property to be improved and poor processability of the lubricating resin composition.
In order to achieve the above object, the present invention discloses a method for producing a lubricating resin composition, comprising the steps of:
step (1) molybdenum disulfide (MoS 2 ) Mixing with gamma-aminopropyl triethoxysilane, adding hydrochloric acid solution, heating, reacting, cooling, filtering, washing with absolute ethanol, and vacuum drying at 70-80deg.C for 12-18 hr to obtain amino modified molybdenum disulfide;
uniformly mixing an organic solvent, amino modified molybdenum disulfide, carboxylated carbon nanotubes, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC.HCl), 1-hydroxybenzotriazole (HOBt) and Triethylamine (TEA), reacting, filtering after the reaction is finished, washing with dichloromethane, and vacuum-drying at 60-70 ℃ for 12-18h to obtain a molybdenum disulfide-carbon nanotube composite material;
uniformly mixing tert-butyllithium (t-BuLi), ethylenediamine (EDA) and polytetrafluoroethylene resin (PTFE) in a mass ratio of 620-650:580-610:100, activating for 0.5h in a nitrogen atmosphere at 0 ℃, washing with tetrahydrofuran to obtain activated polytetrafluoroethylene resin, adding the activated polytetrafluoroethylene resin into absolute ethyl alcohol and Glycidyl Methacrylate (GMA), mixing, reacting, filtering after the reaction is finished, washing with absolute ethyl alcohol, and drying for 12-24h at 55-65 ℃ to obtain epoxy modified polytetrafluoroethylene;
uniformly mixing 1, 4-dioxane and deionized water in a volume ratio of 1:3 to obtain a mixed solvent, adding epoxy modified polytetrafluoroethylene and molybdenum disulfide-carbon nanotube composite material into the mixed solvent, mixing, reacting, filtering after the reaction is finished, washing with deionized water, and drying in a vacuum drying oven at 55-65 ℃ for 6-12 hours to obtain molybdenum disulfide-carbon nanotube grafted polytetrafluoroethylene;
and (5) mixing polyimide resin (PI), molybdenum disulfide-carbon nano tube grafted polytetrafluoroethylene, polyether-ether-ketone resin, an antioxidant and a dispersing agent to obtain a mixture, adding the mixture into a double-screw extruder, carrying out melt blending at the rotating speed of 280-320r/min, extruding and granulating after the blending is finished to obtain the lubricating resin composition.
The hydrochloric acid solution in the step (1) is 0.1mol/L hydrochloric acid aqueous solution.
The mass ratio of the molybdenum disulfide, the gamma-aminopropyl triethoxysilane and the hydrochloric acid solution in the step (1) is 100:550-750:6000-9500.
The reaction temperature in the step (1) is 95-105 ℃, and the reaction time is 8-12h.
In the step (2), the mass ratio of the organic solvent, the amino modified molybdenum disulfide, the carboxylated carbon nanotubes, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, the 1-hydroxybenzotriazole and the triethylamine is 3200-6000:100:180-350:18-32:9-16:70-150.
The reaction temperature in the step (2) is 15-25 ℃, and the reaction time is 36-48h.
The organic solvent in the step (2) comprises any one of N, N-dimethylformamide, 1, 4-dioxane and tetrahydrofuran.
The mass ratio of the polytetrafluoroethylene resin, the absolute ethyl alcohol and the glycidyl methacrylate after the activation in the step (3) is 100:3800-5500:750-1200.
The reaction temperature in the step (3) is 75-85 ℃, and the reaction time is 8-10h.
The mass ratio of the mixed solvent, the epoxy modified polytetrafluoroethylene and the molybdenum disulfide-carbon nano tube composite material in the step (4) is 5500-6500:100:58-70.
The reaction temperature in the step (4) is 80-90 ℃, and the reaction time is 36-48h.
In the step (5), the mass ratio of the polyimide resin to the molybdenum disulfide-carbon nano tube grafted polytetrafluoroethylene to the polyether-ether-ketone resin to the antioxidant to the dispersing agent is 100:12-30:5-14:0.1-0.5:0.2-0.6.
The dispersing agent in the step (5) is polyvinylpyrrolidone.
The antioxidant in the step (5) is a composite antioxidant, the composite antioxidant comprises a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester, the auxiliary antioxidant is tri (2, 4-di-tert-butylphenyl) phosphite, and the mass ratio of the main antioxidant to the auxiliary antioxidant is 5:1.
The temperature of the melt blending in the step (5) is 300-350 ℃, and the time of the melt blending is 9-12min.
According to the invention, gamma-aminopropyl triethoxysilane is used for modifying molybdenum disulfide to obtain amino modified molybdenum disulfide, amino on the amino modified molybdenum disulfide and carboxyl on a carboxylated carbon nano tube are subjected to amidation reaction under the action of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1-hydroxybenzotriazole and triethylamine, molybdenum disulfide and carbon nano tube are subjected to chemical bonding to obtain a molybdenum disulfide-carbon nano tube composite material, tert-butyllithium and ethylenediamine are used for activating polytetrafluoroethylene resin, a mixed solution formed by tert-butyllithium and ethylenediamine is used for forming free radicals, the free radicals are transferred onto polytetrafluoroethylene resin, fluorine atoms on the surface of polytetrafluoroethylene resin are removed, tert-butyl groups are introduced to obtain activated polytetrafluoroethylene resin, the carbon center free radicals on the surface of the activated polytetrafluoroethylene resin react with glycidyl methacrylate monomers in absolute ethyl alcohol to obtain epoxy modified polytetrafluoroethylene, the epoxy groups on the epoxy modified polytetrafluoroethylene resin and imine on the molybdenum disulfide-carbon nano tube composite material are subjected to ring opening reaction to obtain molybdenum disulfide-carbon nano tube grafted polytetrafluoroethylene resin, the polytetrafluoroethylene resin and polyimide carbon nano tube composite material are subjected to melt-blending, and the polyester resin is subjected to extrusion, and the polyester resin is subjected to blending, and the polyester resin is subjected to extrusion, and the polyester resin is blended to obtain the composite, and the polytetrafluoroethylene resin is subjected to the anti-dispersing agent.
Compared with the prior art, the invention has the beneficial effects that:
the molybdenum disulfide used in the invention has a layered structure, excellent self-lubricating property and load bearing capacity, a slip plane is easily formed by layering in the friction process, the friction reducing effect is good, the carbon nano tube has excellent wear resistance, mechanical property and self-lubricating property, the carbon nano tube can help the matrix to bear the load, the force is transmitted from one molecular chain to the other molecular chain, and the stress is dispersed in the resin matrix; the molybdenum disulfide-carbon nano tube composite material and polytetrafluoroethylene are connected through covalent bonds, so that the composite material has stronger stress transmission capability, meanwhile, the problem that the nano material is easy to agglomerate to cause uneven structure of the composite material is avoided, the interaction and interface strength between two phases are obviously improved, a large number of stress concentration points are avoided, the service performance of the material is improved, the time for reaching a steady state can be shortened through synergistic effect between the two phases, the band-shaped damage of polytetrafluoroethylene resin can be prevented, the friction and abrasion resistance of the lubricating resin composition is further improved, and meanwhile, the mechanical property of the material is improved.
The polyether-ether-ketone resin with polarity used in the invention can improve the free volume of polyimide molecules, and the nonpolar polytetrafluoroethylene resin is distributed on the interface of polyimide to overcome resistance friction, so as to play a role in reinforcing, avoid the decrease of polyimide performance, ensure that the polytetrafluoroethylene resin has excellent thermal stability, mechanical performance and low friction coefficient performance, ensure that acting force is formed between hydroxyl on the prepared molybdenum disulfide-carbon nano tube grafted polytetrafluoroethylene and imino bonds on the polyimide resin, improve the compatibility, and further improve the mechanical performance, heat resistance and wear resistance of the polyimide resin, and ensure that the obtained lubricating resin composition has excellent processability and further expands the application field.
Drawings
FIG. 1 is a flow chart of the preparation of a lubricating resin composition in the present invention;
FIG. 2 is a schematic diagram of the structure of the preparation of amino modified molybdenum disulfide in the present invention;
FIG. 3 is a schematic structural diagram of a molybdenum disulfide-carbon nanotube composite material prepared in accordance with the present invention;
FIG. 4 is a schematic structural diagram of the preparation of epoxy-modified polytetrafluoroethylene in the present invention;
FIG. 5 is a schematic diagram of the structure of the preparation of molybdenum disulfide-carbon nanotube grafted polytetrafluoroethylene in the present invention;
FIG. 6 is an infrared spectrum of molybdenum disulfide-carbon nanotube grafted polytetrafluoroethylene in the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by those skilled in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
Example 1
A method for producing a lubricating resin composition, comprising the steps of:
(1) Mixing molybdenum disulfide and gamma-aminopropyl triethoxysilane, adding 0.1mol/L hydrochloric acid aqueous solution, wherein the mass ratio of the added molybdenum disulfide to the gamma-aminopropyl triethoxysilane to the hydrochloric acid aqueous solution is 100:550:6000, heating, reacting for 12 hours at 95 ℃, cooling, filtering, washing with absolute ethyl alcohol, and vacuum drying for 18 hours at 70 ℃ to obtain amino modified molybdenum disulfide;
(2) Uniformly mixing N, N-dimethylformamide, amino modified molybdenum disulfide, carboxylated carbon nanotubes, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1-hydroxybenzotriazole and triethylamine according to the mass ratio of 3200:100:180:18:9:70, reacting at 15 ℃ for 48 hours, filtering after the reaction is finished, washing with dichloromethane, and vacuum drying at 60 ℃ for 18 hours to obtain a molybdenum disulfide-carbon nanotube composite material;
(3) Mixing uniformly tert-butyllithium, ethylenediamine and polytetrafluoroethylene resin in a mass ratio of 620:580:100, activating for 0.5h in a nitrogen atmosphere at 0 ℃, washing with tetrahydrofuran to obtain activated polytetrafluoroethylene resin, adding the activated polytetrafluoroethylene resin into absolute ethyl alcohol and glycidyl methacrylate, wherein the mass ratio of the added activated polytetrafluoroethylene resin, absolute ethyl alcohol and glycidyl methacrylate is 100:3800:750, mixing, reacting for 10h at 75 ℃, filtering after the reaction is finished, washing with absolute ethyl alcohol, and drying for 24h at 55 ℃ to obtain epoxy modified polytetrafluoroethylene;
(4) Uniformly mixing 1, 4-dioxane with deionized water in a volume ratio of 1:3 to obtain a mixed solvent, adding epoxy modified polytetrafluoroethylene and molybdenum disulfide-carbon nano tube composite material into the mixed solvent, wherein the mass ratio of the added mixed solvent to the epoxy modified polytetrafluoroethylene to the molybdenum disulfide-carbon nano tube composite material is 5500:100:58, mixing, reacting at 80 ℃ for 48 hours, filtering after the reaction is finished, washing with deionized water, and drying in a 55 ℃ vacuum drying box for 12 hours to obtain molybdenum disulfide-carbon nano tube grafted polytetrafluoroethylene;
(5) Mixing polyimide resin, molybdenum disulfide-carbon nano tube grafted polytetrafluoroethylene, polyether ether ketone resin, an antioxidant and a dispersing agent polyvinylpyrrolidone in a mass ratio of 100:12:5:0.1:0.2 to obtain a mixture, wherein the antioxidant is a composite antioxidant and comprises main antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl alcohol ester and auxiliary antioxidant tris (2, 4-di-tert-butylphenyl) phosphite in a mass ratio of 5:1, adding the mixture into a double screw extruder, carrying out melt blending at 300 ℃ for 12min at the rotating speed of 280r/min, extruding and granulating after the blending is finished to obtain the lubricating resin composition.
Example 2
A method for producing a lubricating resin composition, comprising the steps of:
(1) Mixing molybdenum disulfide and gamma-aminopropyl triethoxysilane, adding 0.1mol/L hydrochloric acid aqueous solution, wherein the mass ratio of the added molybdenum disulfide to the gamma-aminopropyl triethoxysilane to the hydrochloric acid aqueous solution is 100:600:6800, heating, reacting at 100 ℃ for 10 hours, cooling, filtering, washing with absolute ethyl alcohol, and vacuum drying at 75 ℃ for 15 hours to obtain amino modified molybdenum disulfide;
(2) Uniformly mixing N, N-dimethylformamide, amino modified molybdenum disulfide, carboxylated carbon nanotubes, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1-hydroxybenzotriazole and triethylamine according to the mass ratio of 4000:100:225:22:11:88, reacting at 20 ℃ for 42 hours, filtering after the reaction is finished, washing with dichloromethane, and vacuum drying at 65 ℃ for 15 hours to obtain a molybdenum disulfide-carbon nanotube composite material;
(3) Uniformly mixing tert-butyllithium, ethylenediamine and polytetrafluoroethylene resin in a mass ratio of 627:586:100, activating for 0.5h in a nitrogen atmosphere at 0 ℃, washing with tetrahydrofuran to obtain activated polytetrafluoroethylene resin, adding the activated polytetrafluoroethylene resin into absolute ethyl alcohol and glycidyl methacrylate, wherein the mass ratio of the added activated polytetrafluoroethylene resin, absolute ethyl alcohol and glycidyl methacrylate is 100:4300:850, mixing, reacting for 9h at 80 ℃, filtering after the reaction is finished, washing with absolute ethyl alcohol, and drying for 18h at 60 ℃ to obtain epoxy modified polytetrafluoroethylene;
(4) Uniformly mixing 1, 4-dioxane with deionized water in a volume ratio of 1:3 to obtain a mixed solvent, adding epoxy modified polytetrafluoroethylene and molybdenum disulfide-carbon nano tube composite material into the mixed solvent, wherein the mass ratio of the added mixed solvent to the epoxy modified polytetrafluoroethylene to the molybdenum disulfide-carbon nano tube composite material is 5750:100:61, mixing, reacting at 85 ℃ for 40 hours, filtering after the reaction is finished, washing with deionized water, and drying in a vacuum drying oven at 60 ℃ for 10 hours to obtain molybdenum disulfide-carbon nano tube grafted polytetrafluoroethylene;
(5) Mixing polyimide resin, molybdenum disulfide-carbon nano tube grafted polytetrafluoroethylene, polyether ether ketone resin, an antioxidant and a dispersing agent polyvinylpyrrolidone with the mass ratio of 100:15:7:0.2:0.35 to obtain a mixture, wherein the antioxidant is a composite antioxidant and comprises main antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl alcohol ester and auxiliary antioxidant tris (2, 4-di-tert-butylphenyl) phosphite with the mass ratio of 5:1, adding the mixture into a double screw extruder, carrying out melt blending at 320 ℃ for 10min at the rotating speed of 290r/min, extruding and granulating after the blending is finished to obtain the lubricating resin composition.
Example 3
A method for producing a lubricating resin composition, comprising the steps of:
(1) Mixing molybdenum disulfide and gamma-aminopropyl triethoxysilane, adding 0.1mol/L hydrochloric acid aqueous solution, wherein the mass ratio of the added molybdenum disulfide to the gamma-aminopropyl triethoxysilane to the hydrochloric acid aqueous solution is 100:650:7600, reacting for 10 hours at 100 ℃, cooling, filtering, washing with absolute ethyl alcohol, and vacuum drying for 15 hours at 75 ℃ to obtain amino modified molybdenum disulfide;
(2) Uniformly mixing N, N-dimethylformamide, amino modified molybdenum disulfide, carboxylated carbon nanotubes, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1-hydroxybenzotriazole and triethylamine according to the mass ratio of 4800:100:265:25:12.5:105, reacting at 20 ℃ for 42 hours, filtering after the reaction is finished, washing with dichloromethane, and vacuum drying at 65 ℃ for 15 hours to obtain a molybdenum disulfide-carbon nanotube composite material;
(3) Uniformly mixing tert-butyllithium, ethylenediamine and polytetrafluoroethylene resin in a mass ratio of 633:592:100, activating for 0.5h in a nitrogen atmosphere at 0 ℃, washing with tetrahydrofuran to obtain activated polytetrafluoroethylene resin, adding the activated polytetrafluoroethylene resin into absolute ethyl alcohol and glycidyl methacrylate, mixing the added activated polytetrafluoroethylene resin, the absolute ethyl alcohol and the glycidyl methacrylate in a mass ratio of 100:4750:960, reacting for 9h at 80 ℃, filtering after the reaction, washing with absolute ethyl alcohol, and drying for 18h at 60 ℃ to obtain epoxy modified polytetrafluoroethylene;
(4) Uniformly mixing 1, 4-dioxane with deionized water in a volume ratio of 1:3 to obtain a mixed solvent, adding epoxy modified polytetrafluoroethylene and molybdenum disulfide-carbon nano tube composite material into the mixed solvent, wherein the mass ratio of the added mixed solvent to the epoxy modified polytetrafluoroethylene to the molybdenum disulfide-carbon nano tube composite material is 6000:100:64, mixing, reacting at 85 ℃ for 42h, filtering after the reaction is finished, washing with deionized water, and drying in a vacuum drying oven at 60 ℃ for 10h to obtain molybdenum disulfide-carbon nano tube grafted polytetrafluoroethylene;
(5) Mixing polyimide resin, molybdenum disulfide-carbon nano tube grafted polytetrafluoroethylene, polyether ether ketone resin, an antioxidant and a dispersing agent polyvinylpyrrolidone with the mass ratio of 100:20:9.5:0.3:0.45 to obtain a mixture, wherein the antioxidant is a composite antioxidant and comprises main antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester and auxiliary antioxidant tris (2, 4-di-tert-butylphenyl) phosphite with the mass ratio of 5:1, adding the mixture into a double screw extruder, carrying out melt blending at 340 ℃ for 10min at the rotating speed of 305r/min, extruding and granulating after the blending is finished to obtain the lubricating resin composition.
Example 4
A method for producing a lubricating resin composition, comprising the steps of:
(1) Mixing molybdenum disulfide and gamma-aminopropyl triethoxysilane, adding 0.1mol/L hydrochloric acid aqueous solution, wherein the mass ratio of the added molybdenum disulfide to the gamma-aminopropyl triethoxysilane to the hydrochloric acid aqueous solution is 100:700:8500, reacting for 10 hours at 100 ℃, cooling, filtering, washing by using absolute ethyl alcohol, and vacuum drying for 15 hours at 75 ℃ to obtain amino modified molybdenum disulfide;
(2) Uniformly mixing N, N-dimethylformamide, amino modified molybdenum disulfide, carboxylated carbon nanotubes, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1-hydroxybenzotriazole and triethylamine according to the mass ratio of 5600:100:320:30:15:126, reacting at 20 ℃ for 42 hours, filtering after the reaction is finished, washing with dichloromethane, and vacuum drying at 65 ℃ for 15 hours to obtain a molybdenum disulfide-carbon nanotube composite material;
(3) Uniformly mixing tert-butyllithium, ethylenediamine and polytetrafluoroethylene resin in a mass ratio of 642:602:100, activating for 0.5h in a nitrogen atmosphere at 0 ℃, washing with tetrahydrofuran to obtain activated polytetrafluoroethylene resin, adding the activated polytetrafluoroethylene resin into absolute ethyl alcohol and glycidyl methacrylate, wherein the mass ratio of the added activated polytetrafluoroethylene resin, absolute ethyl alcohol and glycidyl methacrylate is 100:5200:1050, mixing, reacting for 9h at 80 ℃, filtering after the reaction is finished, washing with absolute ethyl alcohol, and drying for 18h at 60 ℃ to obtain epoxy modified polytetrafluoroethylene;
(4) Uniformly mixing 1, 4-dioxane with deionized water in a volume ratio of 1:3 to obtain a mixed solvent, adding epoxy modified polytetrafluoroethylene and molybdenum disulfide-carbon nano tube composite material into the mixed solvent, wherein the mass ratio of the added mixed solvent to the epoxy modified polytetrafluoroethylene to the molybdenum disulfide-carbon nano tube composite material is 6250:100:66, mixing, reacting at 85 ℃ for 45 hours, filtering after the reaction is finished, washing with deionized water, and drying in a vacuum drying oven at 60 ℃ for 10 hours to obtain molybdenum disulfide-carbon nano tube grafted polytetrafluoroethylene;
(5) Mixing polyimide resin, molybdenum disulfide-carbon nano tube grafted polytetrafluoroethylene, polyether ether ketone resin, an antioxidant and a dispersing agent polyvinylpyrrolidone with the mass ratio of 100:26:12:0.4:0.55 to obtain a mixture, wherein the antioxidant is a composite antioxidant and comprises main antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl alcohol ester and auxiliary antioxidant tris (2, 4-di-tert-butylphenyl) phosphite with the mass ratio of 5:1, adding the mixture into a double screw extruder, carrying out melt blending at 340 ℃ for 11min at the rotating speed of 315r/min, extruding and granulating after the blending is finished to obtain the lubricating resin composition.
Example 5
A method for producing a lubricating resin composition, comprising the steps of:
(1) Mixing molybdenum disulfide and gamma-aminopropyl triethoxysilane, adding 0.1mol/L hydrochloric acid aqueous solution, wherein the mass ratio of the added molybdenum disulfide to the gamma-aminopropyl triethoxysilane to the hydrochloric acid aqueous solution is 100:750:9500, heating, reacting at 105 ℃ for 8 hours, cooling, filtering, washing with absolute ethyl alcohol, and vacuum drying at 80 ℃ for 12 hours to obtain amino modified molybdenum disulfide;
(2) Uniformly mixing N, N-dimethylformamide, amino modified molybdenum disulfide, carboxylated carbon nanotubes, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1-hydroxybenzotriazole and triethylamine according to the mass ratio of 6000:100:350:32:16:150, reacting at 25 ℃ for 36 hours, filtering after the reaction is finished, washing with dichloromethane, and vacuum drying at 70 ℃ for 12 hours to obtain a molybdenum disulfide-carbon nanotube composite material;
(3) Uniformly mixing tert-butyllithium, ethylenediamine and polytetrafluoroethylene resin in a mass ratio of 650:610:100, activating for 0.5h in a nitrogen atmosphere at 0 ℃, washing with tetrahydrofuran to obtain activated polytetrafluoroethylene resin, adding the activated polytetrafluoroethylene resin into absolute ethyl alcohol and glycidyl methacrylate, wherein the mass ratio of the added activated polytetrafluoroethylene resin, the absolute ethyl alcohol and the glycidyl methacrylate is 100:5500:1200, mixing, reacting for 8h at 85 ℃, filtering after the reaction is finished, washing with absolute ethyl alcohol, and drying for 12h at 65 ℃ to obtain epoxy modified polytetrafluoroethylene;
(4) Uniformly mixing 1, 4-dioxane with deionized water in a volume ratio of 1:3 to obtain a mixed solvent, adding epoxy modified polytetrafluoroethylene and molybdenum disulfide-carbon nano tube composite material into the mixed solvent, wherein the mass ratio of the added mixed solvent to the epoxy modified polytetrafluoroethylene to the molybdenum disulfide-carbon nano tube composite material is 6500:100:70, mixing, reacting at 90 ℃ for 36 hours, filtering after the reaction is finished, washing with deionized water, and drying in a vacuum drying oven at 65 ℃ for 6 hours to obtain molybdenum disulfide-carbon nano tube grafted polytetrafluoroethylene;
(5) Mixing polyimide resin, molybdenum disulfide-carbon nano tube grafted polytetrafluoroethylene, polyether ether ketone resin, an antioxidant and a dispersing agent polyvinylpyrrolidone in a mass ratio of 100:30:14:0.5:0.6 to obtain a mixture, wherein the antioxidant is a composite antioxidant and comprises main antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl alcohol ester and auxiliary antioxidant tris (2, 4-di-tert-butylphenyl) phosphite in a mass ratio of 5:1, adding the mixture into a double screw extruder, carrying out melt blending at 350 ℃ for 9min at the rotating speed of 320r/min, extruding and granulating after the blending is finished to obtain the lubricating resin composition.
Comparative example 1
A method for producing a lubricating resin composition, comprising the steps of:
(1) Uniformly mixing tert-butyllithium, ethylenediamine and polytetrafluoroethylene resin in a mass ratio of 650:610:100, activating for 0.5h in a nitrogen atmosphere at 0 ℃, washing with tetrahydrofuran to obtain activated polytetrafluoroethylene resin, adding the activated polytetrafluoroethylene resin into absolute ethyl alcohol and glycidyl methacrylate, wherein the mass ratio of the added activated polytetrafluoroethylene resin, the absolute ethyl alcohol and the glycidyl methacrylate is 100:5500:1200, mixing, reacting for 8h at 85 ℃, filtering after the reaction is finished, washing with absolute ethyl alcohol, and drying for 12h at 65 ℃ to obtain epoxy modified polytetrafluoroethylene;
(2) Mixing polyimide resin, epoxy modified polytetrafluoroethylene, molybdenum disulfide, carboxylated carbon nano tube, polyether ether ketone resin, antioxidant and dispersing agent polyvinylpyrrolidone with the mass ratio of 100:17.7:2.7:9.6:14:0.5:0.6 to obtain a mixture, wherein the antioxidant is a composite antioxidant and comprises main antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-stearyl propionate and auxiliary antioxidant tri (2, 4-di-tert-butylphenyl) phosphite with the mass ratio of 5:1, adding the mixture into a double screw extruder, carrying out melt blending at the rotating speed of a screw of 320r/min for 9min at the temperature of 350 ℃, extruding and granulating after the blending is finished to obtain the lubricating resin composition.
Comparative example 2
A method for producing a lubricating resin composition, comprising the steps of:
(1) Mixing molybdenum disulfide and gamma-aminopropyl triethoxysilane, adding 0.1mol/L hydrochloric acid aqueous solution, wherein the mass ratio of the added molybdenum disulfide to the gamma-aminopropyl triethoxysilane to the hydrochloric acid aqueous solution is 100:750:9500, heating, reacting at 105 ℃ for 8 hours, cooling, filtering, washing with absolute ethyl alcohol, and vacuum drying at 80 ℃ for 12 hours to obtain amino modified molybdenum disulfide;
(2) Uniformly mixing N, N-dimethylformamide, amino modified molybdenum disulfide, carboxylated carbon nanotubes, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1-hydroxybenzotriazole and triethylamine according to the mass ratio of 6000:100:350:32:16:150, reacting at 25 ℃ for 36 hours, filtering after the reaction is finished, washing with dichloromethane, and vacuum drying at 70 ℃ for 12 hours to obtain a molybdenum disulfide-carbon nanotube composite material;
(3) Mixing polyimide resin, polytetrafluoroethylene resin, molybdenum disulfide-carbon nano tube composite material, polyether ether ketone resin, antioxidant and dispersing agent polyvinylpyrrolidone with the mass ratio of 100:17.7:12.3:14:0.5:0.6 to obtain a mixture, wherein the antioxidant is a composite antioxidant, the antioxidant comprises main antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester and auxiliary antioxidant tri (2, 4-di-tert-butylphenyl) phosphite with the mass ratio of 5:1, adding the mixture into a double screw extruder, carrying out melt blending at the speed of a screw of 320r/min for 9min, extruding and granulating after the blending is finished, and obtaining the lubricating resin composition.
Molybdenum disulfide used in the examples and comparative examples of the present invention was purchased from the Tianjin Fuchen chemical reagent factory, model AR250g, grade analytical grade AR 98.5%, CAS number 1317-33-5; carboxylated carbon nanotubes are carboxylated multiwall carbon nanotubes (MWCNTs) purchased from Nanjing Xianfeng nanomaterial technologies Inc., the pipe diameter is 10-20nm, the length is 0.5-2 mu m, and the purity is more than 95%; gamma-aminopropyl triethoxysilane is available from jekcal chemical limited, hangzhou; the polytetrafluoroethylene resin is purchased from Dajinjin industries, inc., model number M-18; 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride was purchased from Shanghai family ether chemical technologies limited; the polyetheretherketone is purchased from Shanghai Kaijin chemical industry Co., ltd, and the model is KD2150; polyimide resin is purchased from Hui Zhi technology (China) Co., ltd, and the model is PI-0501; the remaining reagents were all commercially available.
The lubricating resin compositions of examples 1-5 and comparative examples 1-2 were subjected to performance test, the lubricating resin compositions were placed in cylinders of an injection molding machine, melted and plasticized at 350℃and injected into a mold at 180℃under the action of a screw, and after cooling, the mold was set and released from the mold to prepare test bars corresponding to examples 1-5 and comparative examples 1-2, specifically tested as follows:
(1) Mechanical property test: the tensile properties and notched impact strength of the bars corresponding to the lubricating resin compositions of examples 1 to 5 and comparative examples 1 to 2 were measured by referring to ASTM D638 and ASTM D256, respectively, and the results are shown in Table 1:
TABLE 1
As can be seen from the test results in table 1, the corresponding lubricating resin compositions of examples 1 to 5 have good mechanical properties, wherein the molybdenum disulfide used has a load-bearing capacity for load, and the carbon nanotubes have good mechanical properties, which can help the matrix to bear load, transfer the force from one molecular chain to the other molecular chain, and disperse stress inside the resin matrix; the molybdenum disulfide-carbon nano tube composite material and polytetrafluoroethylene are connected through covalent bonds, so that the composite material has stronger stress transmission capability, meanwhile, the problem that the nano material is easy to agglomerate to cause uneven structure of the composite material is avoided, the interaction and interface strength between two phases are obviously improved, a large number of stress concentration points are avoided, the service performance of the material is improved, the time for reaching a steady state can be shortened through synergistic effect between the two materials, the band-shaped damage of polytetrafluoroethylene resin can be prevented, and the mechanical property of the lubricating resin composition is further improved. Wherein the tensile strength of the lubricating resin composition corresponding to example 5 was 143.1MPa, and the notched impact strength was 382.4J/m. In comparative example 1, the polytetrafluoroethylene resin was modified, and epoxy-modified polytetrafluoroethylene was added to the lubricating resin composition, which did not chemically bond molybdenum disulfide and carboxylated carbon nanotubes, and the dispersibility of the inorganic particles was poor, and aggregation was likely to occur, which had a great influence on the performance of the lubricating resin composition, and the tensile strength was 104.9MPa, and the notched impact strength was 316.7J/m. The lubricating resin composition in comparative example 2 is added with molybdenum disulfide-carbon nano tube composite material, polytetrafluoroethylene resin is not modified, compatibility between the molybdenum disulfide-carbon nano tube composite material and polyimide resin is reduced to a certain extent, mechanical properties are affected to a certain extent, tensile strength is 124.6MPa, and notch impact strength can reach 341.5J/m.
(2) Abrasion resistance test: the friction coefficient and abrasion loss were measured on the bars corresponding to the lubricating resin compositions of examples 1 to 5 and comparative examples 1 to 2, and the respective measurement standards were referred to ASTM D1894 and ASTM D1044, respectively, and the results are shown in Table 2:
TABLE 2
As can be seen from the test results of table 2, the corresponding lubricating resin compositions of examples 1 to 5 have wear resistance, and the molybdenum disulfide used has a layered structure, has excellent self-lubricity, is susceptible to delamination to form a slip plane during friction, has a good antifriction effect, and carbon nanotubes have excellent wear resistance and self-lubricity, and by synergistic action, the time to reach steady state can be shortened, the belt-like destruction of polytetrafluoroethylene resin can be prevented, the wear resistance of the lubricating resin composition can be further improved, the polyether-ether-ketone resin with polarity used can improve the free volume of polyimide molecules, and the nonpolar polytetrafluoroethylene resin distributed on the interface of polyimide overcomes resistance friction, reduces friction coefficient, plays a role in reinforcement, avoids the decrease in polyimide performance, forms acting force between hydroxyl groups on the prepared molybdenum disulfide-carbon nanotubes grafted polytetrafluoroethylene and imino bonds on polyimide resin, and improves the compatibility, thereby improving the wear resistance of polyimide resin. The friction coefficient of the lubricating resin composition corresponding to example 4 was as low as 0.19, the abrasion of the lubricating resin composition corresponding to example 5 was 3.1mg/1000 cycles, the friction coefficient of the lubricating resin composition corresponding to comparative example 1 was 0.31, the abrasion was 5.4mg/1000 cycles, the friction coefficient of the lubricating resin composition corresponding to comparative example 2 was 0.27, and the abrasion was 4.6mg/1000 cycles.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made hereto without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A method for producing a lubricating resin composition, characterized by comprising: the method comprises the following steps:
step (1) mixing molybdenum disulfide and gamma-aminopropyl triethoxysilane, adding hydrochloric acid solution, heating, reacting, cooling, filtering, washing and drying after the reaction is finished to obtain amino modified molybdenum disulfide;
uniformly mixing an organic solvent, amino modified molybdenum disulfide, carboxylated carbon nanotubes, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1-hydroxybenzotriazole and triethylamine, reacting, filtering, washing and drying to obtain a molybdenum disulfide-carbon nanotube composite material;
uniformly mixing tert-butyllithium, ethylenediamine and polytetrafluoroethylene resin in a mass ratio of 620-650:580-610:100, activating for 0.5h in a nitrogen atmosphere, washing with tetrahydrofuran to obtain activated polytetrafluoroethylene resin, adding the activated polytetrafluoroethylene resin into absolute ethyl alcohol and glycidyl methacrylate, mixing, reacting, filtering, washing and drying to obtain epoxy modified polytetrafluoroethylene;
uniformly mixing 1, 4-dioxane and deionized water in a volume ratio of 1:3 to obtain a mixed solvent, adding epoxy modified polytetrafluoroethylene and molybdenum disulfide-carbon nano tube composite material into the mixed solvent, mixing, reacting, filtering, washing and drying to obtain molybdenum disulfide-carbon nano tube grafted polytetrafluoroethylene;
and (5) mixing polyimide resin, molybdenum disulfide-carbon nano tube grafted polytetrafluoroethylene, polyether-ether-ketone resin, an antioxidant and a dispersing agent to obtain a mixture, carrying out melt blending, extruding after the blending is finished, and granulating to obtain the lubricating resin composition.
2. The method for producing a lubricating resin composition according to claim 1, wherein: in the step (1), the mass ratio of molybdenum disulfide, gamma-aminopropyl triethoxysilane and hydrochloric acid solution is 100:550-750:6000-9500, the reaction temperature is 95-105 ℃, and the reaction time is 8-12h.
3. The method for producing a lubricating resin composition according to claim 1, wherein: in the step (2), the mass ratio of the organic solvent, the amino modified molybdenum disulfide, the carboxylated carbon nanotubes, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, the 1-hydroxybenzotriazole and the triethylamine is 3200-6000:100:180-350:18-32:9-16:70-150.
4. The method for producing a lubricating resin composition according to claim 1, wherein: the reaction temperature in the step (2) is 15-25 ℃, and the reaction time is 36-48h.
5. The method for producing a lubricating resin composition according to claim 1, wherein: the organic solvent in the step (2) comprises any one of N, N-dimethylformamide, 1, 4-dioxane and tetrahydrofuran.
6. The method for producing a lubricating resin composition according to claim 1, wherein: the mass ratio of the activated polytetrafluoroethylene resin to the absolute ethyl alcohol to the glycidyl methacrylate in the step (3) is 100:3800-5500:750-1200, the reaction temperature is 75-85 ℃, and the reaction time is 8-10h.
7. The method for producing a lubricating resin composition according to claim 1, wherein: in the step (4), the mass ratio of the mixed solvent to the epoxy modified polytetrafluoroethylene to the molybdenum disulfide-carbon nano tube composite material is 5500-6500:100:58-70, the reaction temperature is 80-90 ℃, and the reaction time is 36-48h.
8. The method for producing a lubricating resin composition according to claim 1, wherein: in the step (5), the mass ratio of the polyimide resin to the molybdenum disulfide-carbon nano tube grafted polytetrafluoroethylene to the polyether-ether-ketone resin to the antioxidant to the dispersing agent is 100:12-30:5-14:0.1-0.5:0.2-0.6.
9. The method for producing a lubricating resin composition according to claim 1, wherein: the dispersing agent in the step (5) is polyvinylpyrrolidone, the antioxidant is a composite antioxidant, the composite antioxidant comprises a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester, the auxiliary antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite, and the mass ratio of the main antioxidant to the auxiliary antioxidant is 5:1.
10. The method for producing a lubricating resin composition according to claim 1, wherein: the temperature of the melt blending in the step (5) is 300-350 ℃, and the time of the melt blending is 9-12min.
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