Photo-thermal dual-curing system lubricant as well as preparation method and use method thereof

Abstract

The invention provides a photo-thermal dual-curing system lubricant as well as a preparation method and a use method thereof, and belongs to the technical field of lubricants. According to the invention, the epoxy modified acrylic resin prepolymer is used as matrix resin of the photo-thermal dual-curing system lubricant, when the lubricant is used, a photo-crosslinking reaction can be carried out under the action of a photoinitiator, and a thermal crosslinking reaction can be carried out on residual epoxy groups under the action of a thermal curing agent; therefore, the lubricant provided by the invention is a photo-thermal dual-curing reaction system, and has the advantages of quicker photo-curing reaction and high mechanical strength of a thermal curing reaction coating; by adding boron nitride and molybdenum disulfide, the lubricating coating is endowed with an excellent lubricating effect; by adding the main antioxidant and the auxiliary antioxidant, the weather resistance of the lubricating layer can be improved, and the property of high mechanical strength is kept. Results of the embodiment show that the lubricant provided by the invention can greatly shorten the repair time of a lubricating system, and a formed coating has excellent lubricity and mechanical strength.

Description

Technical Field

[0001] The present invention relates to the technical field of lubricants, and in particular to a photothermal dual-curing system lubricant and a preparation method and a use method thereof. Background Art

[0002] Lubrication systems play a vital role in mechanical equipment. They not only ensure the efficient operation of equipment, but also extend the service life of equipment and reduce unnecessary expenses and accidents caused by wear or failure. Common lubricants include liquid lubricants and dry film lubricants. Dry film lubricants use adhesives to firmly bond solid lubricants, wear-resistant additives, etc. to the friction surface where relative motion occurs, playing a role of wear-resistant lubrication protection. Dry film lubricants can be applied to the surface of the friction substrate by spraying, brushing, dipping, etc., and solidify after drying at a certain temperature to form a solid lubricating dry film. Compared with traditional liquid lubricants, dry film lubricants have the advantages of good environmental protection and high stability and have attracted much attention from researchers. However, the curing of dry film lubricants requires certain conditions, which leads to complex and time-consuming repair methods when using dry film lubricants, and the mechanical operation cannot be restored in a short time, resulting in mechanical loss of control, safety threats and economic losses.

[0003] The emergence of photocurable acrylate resins, especially modified acrylate resins, can achieve instant curing of coatings by utilizing the rapid polymerization reaction of photoinitiators under light conditions. This feature greatly improves processing efficiency and makes instant assembly possible. In scenarios such as emergency repairs, field operations, or rapid prototyping, photocurable modified acrylate resins have demonstrated their incomparable advantages, significantly improving emergency response capabilities and operational flexibility. More importantly, the photocurable resin mixture has good stability before exposure, which is convenient for transportation and storage, and extends the effective service life of the dry film lubricant. However, the mechanical strength of a pure acrylate resin coating is insufficient, and is significantly lower than that of an epoxy resin coating, and cannot meet the lubrication needs of equipment in harsh working conditions. In addition, photocurable acrylate resins have high requirements for the light transmittance of the resin system, and their curing efficiency is significantly reduced in filler-rich colored resin systems, which greatly limits their application in the field of solid lubricating coatings.

[0004] Therefore, there is an urgent need to provide a lubricant that can obtain a lubricating and wear-resistant coating with high mechanical strength, good lubricity and fast curing efficiency. Summary of the invention

[0005] The purpose of the present invention is to provide a photothermal dual-curing system lubricant and a preparation method and a use method thereof. The photothermal dual-curing system lubricant provided by the present invention can obtain a lubricating and wear-resistant coating with high mechanical strength, good lubricity and fast curing efficiency.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions: The present invention provides a light-heat dual-curing system lubricant, comprising the following components in parts by weight: 100 parts of epoxy-modified acrylic resin prepolymer, 120-180 parts of reactive diluent, 0.5-3 parts of photoinitiator, 1-10 parts of thermal curing agent, 10-30 parts of boron nitride, 0.5-1 parts of molybdenum disulfide, 0.3-0.5 parts of primary antioxidant and 0.3-0.5 parts of auxiliary antioxidant; The epoxy value of the epoxy-modified acrylic resin prepolymer is 0.2-0.6 mol / 100g.

[0007] Preferably, the epoxy-modified acrylic resin prepolymer is obtained by mixing and polymerizing the following raw materials, based on weight: 100 parts of epoxy resin, 10-60 parts of acrylic monomer, 0.1-3 parts of catalyst and 0.01-1 parts of polymerization inhibitor.

[0008] Preferably, the epoxy resin includes one or more of bisphenol A epoxy resin, bisphenol F epoxy resin and polyphenol glycidyl ether epoxy resin.

[0009] Preferably, the acrylic monomer includes one or more of acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, isooctyl acrylate and butyl acrylate.

[0010] Preferably, the photoinitiator is a free radical photoinitiator.

[0011] Preferably, the thermal curing agent is an imidazole curing agent.

[0012] Preferably, the particle size of the boron nitride is 50-100 nm.

[0013] Preferably, the particle size of the molybdenum disulfide is 1-20 μm.

[0014] The present invention also provides a method for preparing the photothermal dual-curing system lubricant described in the above technical scheme, comprising: mixing epoxy-modified acrylic resin prepolymer, active diluent, photoinitiator, thermal curing agent, boron nitride, molybdenum disulfide, primary antioxidant and auxiliary antioxidant in a dark environment to obtain the photothermal dual-curing system lubricant.

[0015] The present invention also provides a method for using the photothermal dual-cure system lubricant described in the above technical solution or the photothermal dual-cure system lubricant prepared by the preparation method described in the above technical solution, comprising: coating the photothermal dual-cure system lubricant on the surface of a substrate, performing a curing reaction under ultraviolet light, and obtaining a photothermal dual-cure system lubricating coating.

[0016] The invention provides a light-heat dual-curing system lubricant, comprising the following components in parts by weight: 100 parts of epoxy-modified acrylic resin prepolymer, 120-180 parts of reactive diluent, 0.5-3 parts of photoinitiator, 1-10 parts of thermal curing agent, 10-30 parts of boron nitride, 1-5 parts of molybdenum disulfide, 0.3-0.5 parts of primary antioxidant and 0.3-0.5 parts of auxiliary antioxidant; the epoxy value of the epoxy-modified acrylic resin prepolymer is 0.2-0.6 mol / 100g. The present invention adopts epoxy-modified acrylic resin prepolymer as the base resin of the photothermal dual-curing system lubricant, so that the lubricant can undergo a photocrosslinking reaction under the action of a photoinitiator when in use; at the same time, due to the presence of the residual epoxy group of the epoxy-modified acrylic resin prepolymer, a thermal crosslinking reaction can occur under the action of a thermal curing agent; therefore, the lubricant provided by the present invention is a photothermal dual-curing reaction system, which has the advantages of fast photocuring reaction and high strength of the coating formed by thermal curing; the present invention adds boron nitride and molybdenum disulfide, and the two-dimensional sheet material gives the lubricating coating an excellent lubricating effect; the present invention can improve the weather resistance of the lubricating layer by adding a primary antioxidant and an auxiliary antioxidant, so that it maintains the property of high mechanical strength. The results of the embodiment show that the curing time of the photothermal dual-curing system lubricant provided by the present invention is 20~80s, the friction coefficient is 0.2~0.5, and the mechanical strength is 20Mpa. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 The infrared spectra of AG-80, MAA, a mixed sample of AG-80 and MAA, and the prepared epoxy-modified acrylic resin prepolymer used in Example 1 of the present invention are shown. DETAILED DESCRIPTION

[0018] The present invention provides a light-heat dual-curing system lubricant, comprising the following components in parts by weight: 100 parts of epoxy-modified acrylic resin prepolymer, 120-180 parts of reactive diluent, 0.5-3 parts of photoinitiator, 1-10 parts of thermal curing agent, 10-30 parts of boron nitride, 1-5 parts of molybdenum disulfide, 0.3-0.5 parts of primary antioxidant and 0.3-0.5 parts of auxiliary antioxidant; The epoxy value of the epoxy-modified acrylic resin prepolymer is 0.2-0.6 mol / 100g.

[0019] In the present invention, unless otherwise specified, the raw materials used in the present invention are all commercially available products well known in the art.

[0020] In parts by weight, the photothermal dual-curing system lubricant provided by the present invention includes 100 parts of epoxy-modified acrylic resin prepolymer. In the present invention, the epoxy value of the epoxy-modified acrylic resin prepolymer is 0.2~0.6mol / 100g, preferably 0.26~0.6mol / 100g. The present invention uses epoxy-modified acrylic resin prepolymer as the base resin of the photothermal dual-curing system lubricant, so that the lubricant can undergo a photocrosslinking reaction in the presence of a photoinitiator when in use; at the same time, the presence of the remaining epoxy group can undergo a thermal crosslinking reaction under the action of a thermal curing agent; therefore, the lubricant provided by the present invention is a photothermal dual-curing reaction system, which has the advantage of a faster photocuring reaction, and also has the advantage of high strength of the thermally cured coating.

[0021] In the present invention, the epoxy-modified acrylic resin prepolymer is preferably obtained by mixing and polymerizing the following raw materials, based on weight: 100 parts of epoxy resin, 10-60 parts of acrylic monomer, 0.1-3 parts of catalyst and 0.01-1 parts of polymerization inhibitor.

[0022] The raw materials for preparing the epoxy-modified acrylic resin prepolymer of the present invention preferably include 100 parts of epoxy resin by weight. In the present invention, the epoxy resin preferably includes one or more of bisphenol A epoxy resin, bisphenol F epoxy resin and polyphenol glycidyl ether epoxy resin, more preferably polyphenol glycidyl ether epoxy resin. The present invention adopts the above epoxy resin, which has excellent mechanical strength after curing.

[0023] In an embodiment of the present invention, the polyphenol type glycidyl ether epoxy resin can be AG-80, with an epoxy equivalent of 117~134g / mol and an epoxy value of 0.75~0.85mol / 100g. The polyphenol type glycidyl ether epoxy resin used in the present invention is a type of multifunctional epoxy resin, which has three or more epoxy groups in its molecules, and can make the lubricating layer after the lubricant is cured have a large cross-linking density, excellent heat resistance, strength, modulus, electrical insulation, water resistance and corrosion resistance. In addition, the main chain of the AG-80 molecule contains multiple epoxy groups and has high reactivity. The benzene ring is used as the main chain skeleton to provide good mechanical properties. The monomer methacrylic acid is used to react with it for esterification, and a C=C double bond that can be subjected to free radical polymerization is introduced. While increasing the chain length, the concentrated stress during curing is dispersed, the cross-linking density of the system is reduced, and a certain toughness is provided. The introduced double bonds can undergo free radical polymerization with the photoinitiator under ultraviolet light. The heat generated causes the remaining epoxy groups to open their rings under the action of the thermal curing agent, further deepening the resin curing and obtaining a highly curable, high-strength solid lubricating coating in a colored system.

[0024] Based on 100 parts by weight of epoxy resin, the raw materials for preparing the epoxy-modified acrylic resin prepolymer of the present invention preferably include 10 to 60 parts of acrylic monomers, preferably 15 to 55 parts. In the present invention, the acrylic monomers preferably include one or more of acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, isooctyl acrylate and butyl acrylate, more preferably methacrylic acid. In the present invention, the ester group of the acrylic monomer causes the epoxy group to partially open the ring, so that while retaining a part of the epoxy group, it also introduces a C=C double bond, which is convenient for subsequent photoinitiated polymerization. When the present invention uses the above-mentioned acrylic monomers, it has a larger alkyl substituent and is relatively less active, which is more conducive to retaining a part of the epoxy group when preparing the epoxy-modified acrylic resin prepolymer.

[0025] Based on 100 parts by weight of epoxy resin, the raw materials for preparing the epoxy-modified acrylic resin prepolymer of the present invention preferably include 0.1 to 3 parts of catalyst, preferably 0.1 to 1 parts, and more preferably 0.5 parts. In the present invention, the catalyst preferably includes triethylamine, N,N-dimethylbenzylamine, triphenylphosphine or tetraethylammonium bromide, more preferably N,N-dimethylbenzylamine. The present invention uses the above catalyst to have high catalytic activity and low chroma.

[0026] Based on 100 parts by weight of epoxy resin, the raw materials for preparing the epoxy-modified acrylic resin prepolymer of the present invention preferably include 0.01 to 1 part of polymerization inhibitor, preferably 0.01 to 0.05 part, and more preferably 0.05 part. In the present invention, the polymerization inhibitor preferably includes p-hydroxybenzyl methane, hydroquinone, 2,5-dimethylhydroquinone or 2,6-di-tert-butyl-p-quinone, more preferably hydroquinone. The present invention uses the above-mentioned polymerization inhibitor to prevent the prepolymer from being excessively cross-linked.

[0027] In the present invention, the preparation method of the epoxy-modified acrylic resin prepolymer preferably comprises the following steps: (1) dissolving a catalyst, a polymerization inhibitor and an acrylic monomer in an organic solvent to obtain a mixed solution; (2) After preheating the epoxy resin, the mixed solution obtained in step (1) is added dropwise to the preheated epoxy resin to carry out a crosslinking reaction so that the epoxy group content in the system is 25% to 75%, thereby obtaining an epoxy-modified acrylic resin prepolymer.

[0028] In the present invention, the catalyst, the polymerization inhibitor and the acrylic monomer are preferably dissolved in an organic solvent to obtain a mixed solution.

[0029] In the present invention, the organic solvent preferably includes acetone, ethyl acetate, isopropanol or tetrahydrofuran, and more preferably acetone. The present invention uses the above organic solvents, which have excellent solubility for each component.

[0030] The present invention has no particular limitation on the method for dissolving the catalyst, polymerization inhibitor and acrylic monomer in the organic solvent, as long as the catalyst, polymerization inhibitor and acrylic monomer can be completely dissolved in the organic solvent.

[0031] After obtaining the mixed solution, the present invention preferably preheats the epoxy resin, and then drops the mixed solution into the preheated epoxy resin to carry out a cross-linking reaction so that the epoxy group content in the system is 25% to 75% of the initial content, thereby obtaining an epoxy-modified acrylic resin prepolymer.

[0032] In the present invention, the preheating temperature of the epoxy resin is preferably 60-80° C., more preferably 80° C. In the present invention, the epoxy resin is preheated to the above range, so that a cross-linking reaction can occur directly after the epoxy resin is added to the mixed solution.

[0033] The present invention has no special limitation on the rate of the dripping, and it can be adjusted according to the volume of the mixed solution so that the mixed solution and the epoxy resin can be evenly mixed. The present invention can make the reaction product of the epoxy resin and the acrylic monomer more sufficient by dripping. In an embodiment of the present invention, the dripping time can be 2 hours.

[0034] In the present invention, the temperature of the cross-linking reaction is preferably 80-120° C., more preferably 100° C. The present invention has no particular limitation on the time of the cross-linking reaction, and the cross-linking reaction can be stopped when the epoxy content in the system is 25%-75% of the initial content.

[0035] The present invention has no special limitation on the method for testing the epoxy content in the system, and any conventional epoxy content testing method can be used. In an embodiment of the present invention, the method for measuring the epoxy content in the system can be: during the cross-linking reaction, sampling is performed every 60 minutes, the acid value is measured, and titration is performed with a standard KOH solution. The volume of the consumed KOH solution is determined by the color change of the phenolphthalein indicator, and the residual epoxy content in the system is determined.

[0036] Based on 100 parts by weight of epoxy-modified acrylic resin prepolymer, the photothermal dual-curing system lubricant provided by the present invention includes 120 to 180 parts of active diluent, preferably 120 to 170 parts. In an embodiment of the present invention, the weight of the active agent can be 120 parts, 150 parts or 180 parts. In the present invention, the active diluent preferably includes a monofunctional monomer HEMA or a difunctional monomer HDDA, more preferably a compounded active diluent, and the compounded active diluent is preferably a mixture of HEMA and HDDA, and the mass ratio of HEMA to HDDA is preferably 2 to 4: 8 to 6, more preferably 4: 6. In the compounded active dilution used in the present invention, HDDA is a difunctional monomer, and the viscosity of HDDA is relatively low, and the viscosity at room temperature is only 80mPa·s. It can also be effectively sprayed without using a volatile solvent for dilution. In addition, the crosslinking density of HDDA is relatively large, and the compounded monofunctional monomer effectively improves the brittleness of the resin and has a toughening effect. The present invention controls the mass ratio of HEMA to HDDA within the above range, so that the lubricating layer can have both high tensile strength and high impact strength.

[0037] Based on 100 parts by weight of the epoxy-modified acrylic resin prepolymer, the photothermal dual-curing system lubricant provided by the present invention includes 0.5 to 3 parts of a photoinitiator. In an embodiment of the present invention, the weight of the photoinitiator may be 0.5, 2 or 3 parts. In the present invention, the photoinitiator is preferably a free radical photoinitiator. In the present invention, the free radical photoinitiator preferably includes one or more of 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide (TPO), 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide (TPO-L), phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide (819) and benzophenone (BP), and more preferably a composite photoinitiator obtained by mixing phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide (819) and benzophenone (BP). In the present invention, in the composite photoinitiator, the mass ratio of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (819) and benzophenone (BP) is preferably 4-6:6-4, more preferably 1:1. When the photoinitiator added in the present invention is irradiated by ultraviolet (UV) of appropriate wavelength, the molecule absorbs photon energy, transitions from the ground state to the excited state, and rapidly decomposes to generate free radicals, which then attack the double bonds (usually C=C double bonds) in the oligomers to carry out chain growth reaction, and as the chain length continues to grow, the reaction ends; the present invention uses the above-mentioned photoinitiator to be able to quickly dissolve in the active diluent at 60-80°C, and the composite photoinitiator 819 has efficient ultraviolet initiation performance and a wide ultraviolet absorption wavelength, and can carry out deep curing, while BP is a small molecule curing agent, which helps to improve the surface curing property.

[0038] Based on 100 parts by weight of the epoxy-modified acrylic resin prepolymer, the light-heat dual-curing system lubricant provided by the present invention includes 1 to 10 parts of a thermal curing agent, preferably 2 to 8 parts. In an embodiment of the present invention, the weight of the thermal curing agent may be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts or 10 parts. In the present invention, the thermal curing agent is preferably an imidazole curing agent. In the present invention, the imidazole curing agent preferably includes 1-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole or 1,2-diethylimidazole, more preferably 2-ethyl-4-methylimidazole. The present invention adopts the above-mentioned thermosetting agent to react with epoxy resin at a relatively low temperature, and is suitable for applications requiring low-temperature curing conditions, and the cured epoxy resin has a relatively high thermal stability, which can improve the high temperature resistance of the epoxy resin system; the thermosetting agent is uniformly dispersed in the reactive diluent, and a large amount of reactive diluent can play an isolation effect, and before light exposure, the contact between the curing agent and the resin prepolymer is reduced to extend the storage period of the lubricant. The imidazole epoxy curing agent, the nitrogen atom on the ring, has good nucleophilicity, and can quickly start the ring-opening polymerization of the epoxy resin at a relatively low content, improve the curing speed, and has a relatively wide temperature range, which is suitable for low-temperature to high-temperature curing processes, and it can be well compatible with the resin system, suitable for use in complex systems, 2-ethyl-4-methylimidazole can react with epoxy resin at a relatively low temperature, and is suitable for applications requiring low-temperature curing conditions, and the cured epoxy resin has a relatively high thermal stability, which can improve the high temperature resistance of the epoxy resin system.

[0039] Based on 100 parts by weight of the epoxy-modified acrylic resin prepolymer, the photothermal dual-curing system lubricant provided by the present invention includes 10 to 30 parts of boron nitride, preferably 20 to 30 parts. In an embodiment of the present invention, the weight parts of the boron nitride may be 5 parts, 20 parts or 30 parts. In the present invention, the particle size of the boron nitride is preferably 50 to 100 nm, more preferably 60 to 80 nm. In the present invention, the boron nitride is preferably hexagonal boron nitride. The boron nitride used in the present invention has a layered structure similar to graphite, and there are weak van der Waals forces between layers, so that it has good lubrication properties in a high temperature, dry friction environment, giving the lubricating layer a lubricating effect.

[0040] Based on 100 parts by weight of the epoxy-modified acrylic resin prepolymer, the photothermal dual-curing system lubricant provided by the present invention includes 1 to 5 parts of molybdenum disulfide, preferably 0.5 to 4 parts. In an embodiment of the present invention, the weight of the molybdenum disulfide may be 0.5 parts, 1 parts, 2 parts, 3 parts, 4 parts or 5 parts. In the present invention, the particle size of the boron nitride is preferably 1 to 20 μm, more preferably 5 to 15 μm. The molybdenum disulfide used in the present invention has a layered structure, which can impart a lubricating effect to the lubricating layer, provide effective lubrication in a very wide temperature range (-200°C to 400°C), and maintain low friction even in a vacuum.

[0041] In the present invention, nano-sized boron nitride and micron-sized molybdenum disulfide are used together as lubricating fillers. The fillers of the two sizes can act synergistically to improve the lubricating effect of the lubricating layer.

[0042] Based on 100 parts by weight of the epoxy-modified acrylic resin prepolymer, the light-heat dual-curing system lubricant provided by the present invention includes 0.3 to 0.5 parts of a primary antioxidant, preferably 0.5 parts. In the present invention, the primary antioxidant preferably includes one or more of hindered phenol antioxidants tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] pentaerythritol ester (1010), β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate octadecyl ester (1076), semi-hindered phenols such as 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (1790) and 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane (AO-80).

[0043] Based on 100 parts by weight of the epoxy-modified acrylic resin prepolymer, the light-heat dual-curing system lubricant provided by the present invention includes 0.3 to 0.5 parts of auxiliary antioxidant, preferably 0.5 parts. In the present invention, the auxiliary antioxidant preferably includes a thioester antioxidant and / or a phosphite antioxidant; the thioester antioxidant is preferably dilauryl dipropionate (DLTP) or distearyl dipropionate (DSTP); the phosphite antioxidant is preferably triphenyl phosphite. The present invention uses a primary antioxidant and an auxiliary antioxidant to improve the weather resistance of the lubricating layer and maintain good mechanical strength.

[0044] The lubricant provided by the present invention is a photothermal dual-curing system, which has the advantages of a faster photocuring reaction and also has the advantage of high strength of a thermally cured coating. The present invention adds boron nitride and molybdenum disulfide, and the two-dimensional sheet material gives the lubricating coating an excellent lubricating effect. The present invention can improve the weather resistance of the lubricating layer by adding a primary antioxidant and a secondary antioxidant, so that it maintains the property of high mechanical strength.

[0045] The present invention also provides a method for preparing the photothermal dual-curing system lubricant described in the above technical scheme, comprising: mixing epoxy-modified acrylic resin prepolymer, active diluent, photoinitiator, thermal curing agent, boron nitride, molybdenum disulfide, primary antioxidant and auxiliary antioxidant in a dark environment to obtain the photothermal dual-curing system lubricant.

[0046] In the present invention, the preparation method of the epoxy-modified acrylic resin prepolymer is the same as the preparation method of the epoxy-modified acrylic resin prepolymer described in the above technical solution, and will not be described in detail here.

[0047] In the present invention, the method for mixing the epoxy-modified acrylic resin prepolymer, reactive diluent, photoinitiator, thermal curing agent, boron nitride, molybdenum disulfide, primary antioxidant and secondary antioxidant in the dark preferably comprises: mixing the photoinitiator, thermal curing agent and reactive diluent to obtain a mixed liquid; mixing molybdenum disulfide, boron nitride, epoxy-modified acrylic resin prepolymer, primary antioxidant and secondary antioxidant to obtain a resin material; mixing the mixed material with the resin material in the dark to obtain a light-heat dual-curing system lubricant.

[0048] In the present invention, a photoinitiator, a thermal curing agent and a reactive diluent are preferably mixed to obtain a mixed solution. In the present invention, the temperature for mixing the photoinitiator, the thermal curing agent and the reactive diluent is preferably 80-100°C, more preferably 90-100°C; the mixing is preferably carried out under stirring, and the stirring speed is preferably 300-500rpm, more preferably 300-500rpm; the stirring time is preferably 20-40min, more preferably 30-40min.

[0049] In the present invention, the molybdenum disulfide, boron nitride, epoxy-modified acrylic resin prepolymer, primary antioxidant and secondary antioxidant are preferably mixed by grinding, and the grinding device is preferably a three-roll mill. The present invention has no special limitation on the grinding device, as long as it can mix the components uniformly.

[0050] In the present invention, the mixing of the mixed material and the resin material is preferably carried out under light protection, the mixing method is preferably stirring, the stirring temperature is preferably 80-90°C, more preferably 80°C; the stirring speed is preferably 400-700rpm, more preferably 500-700rpm; the stirring time is preferably 10-15min, more preferably 12-15min.

[0051] The method provided by the present invention is simple and can evenly mix the components to obtain a stably dispersed photothermal dual-curing system lubricant.

[0052] The present invention also provides a method for using the photothermal dual-cure system lubricant described in the above technical solution, comprising: applying the photothermal dual-cure system lubricant to the surface of a substrate, performing a curing reaction under ultraviolet light, and obtaining a photothermal dual-cure system lubricating coating.

[0053] The present invention has no special limitation on the material of the substrate, and any conventional substrate may be used.

[0054] The present invention preferably cleans the substrate first to remove impurities on the surface. The present invention has no special limitation on the cleaning method, and any conventional cleaning method can be used. The present invention can clean the damaged wound surface of the substrate by cleaning so that it is not covered by other impurities.

[0055] The present invention does not specifically limit the coating method, and any conventional coating method can be used. In the present invention, the coating method is preferably spraying, or pouring the lubricant on the surface of the lubrication system substrate component, starting the system, so that a resin film of a certain thickness is formed on the entire friction surface including the damaged part, and the excess coating flows away from the damaged part. The present invention does not specifically limit the spraying method, and it is sufficient to make the thickness of the lubricant reach the required thickness. In the present invention, the thickness of the lubricant is preferably 5~30μm, more preferably 10~20μm.

[0056] In the present invention, the power of the ultraviolet lamp is preferably 1-10W, more preferably 5-10W; the wavelength of the ultraviolet lamp is preferably 320-400nm, more preferably 350-400nm; the irradiation time is preferably 30-80s. Under the above conditions, the present invention can fully cure the lubricant with a thickness of 5-30μm.

[0057] Since the lubricant provided by the present invention is a light-heat dual-curing system, the curing speed is fast, and the obtained lubricating layer has good lubricity and high mechanical strength, so it can be used for lubrication of mechanical devices requiring high wear resistance.

[0058] The technical solutions in the present invention will be described clearly and completely below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0059] Raw materials and sources used in the examples: The epoxy resin: AG-80 and methacrylic acid are both from Changxing Materials Industry Co., Ltd.; Active diluent: HEMA comes from Evonik, HDDA comes from Changxing Materials Industry Co., Ltd.; Photoinitiator and thermal curing agent: both from Shanghai Aladdin Biochemical Technology Co., Ltd.; Boron nitride: Hexagonal boron nitride, particle size 50~100nm, from Zhenhan New Materials (Suzhou) Co., Ltd.; Molybdenum disulfide: Model No. 0, particle size 1~20μm, from Zhenhan New Materials (Suzhou) Co., Ltd. Catalysts, antioxidants (primary and secondary antioxidants) and inhibitors were all sourced from Shanghai Aladdin Biochemical Technology Co., Ltd.; The preparation method of the epoxy modified acrylic resin prepolymer in the embodiment is: (1) Dissolve 0.5 g of catalyst N,N-dimethylbenzylamine, 0.05 g of inhibitor hydroquinone and 50 g of MAA in 60 mL of acetone and stir at 40 °C for 30 min to obtain a mixed solution; (2) After preheating 100g of AG-80 to 100°C, the mixed solution obtained in step (1) is added dropwise to the preheated epoxy resin for 2h. The addition is completed and a cross-linking reaction is carried out at 80°C. During the reaction, samples are taken every 60min to determine the acid value. The solution is titrated with a standard KOH solution. The volume of the consumed KOH solution is determined by the color change of the phenolphthalein indicator. When the epoxy group content is 25% to 75% of the initial content, the cross-linking reaction is stopped. By controlling the degree of reaction, an epoxy-modified acrylic resin prepolymer having an epoxy value of 0.2 to 0.6 mol / 100g can be obtained. The epoxy values ​​of the epoxy-modified acrylic resin prepolymers used in the embodiments of the present invention are 0.26 mol / 100g and 0.6 mol / 100g, respectively. The infrared spectra of AG-80, MAA, the mixed sample of AG-80 and MAA, and the prepared epoxy-modified acrylic resin prepolymer used in this example are shown in FIG. Figure 1 As shown. Figure 1It can be seen that the preparation method is based on the infrared spectra analysis of the products before and after the reaction of AG-80 epoxy resin, methacrylic acid and their mixture, that is, the unreacted mixed sample and the epoxy-modified acrylic prepolymer. -1 The peak at the position is the stretching vibration of the C=C double bond on the benzene ring. Taking the peak area as a reference, it is found that the peak area at 906 cm before and after the reaction is -1 The characteristic absorption peak area ratio of the epoxy group at the position is 3:1, 3420cm -1 The characteristic absorption peak area of ​​-OH at the position increased significantly, indicating that during the reaction, the epoxy group on AG-80 was partially ring-opened to generate hydroxyl groups, which in turn caused the characteristic absorption peak of the epoxy group to be significantly weakened, while the -OH peak area increased significantly. For methacrylic acid, 810cm -1 The C=C peak at 2931 cm -1 There is a broad and strong peak at 1697cm -1 The peak at the position is -COOH. After the reaction, the peak at this position shifts to the high band, which is consistent with the -COOR feature, proving that the carboxyl group of methacrylic acid reacts with the epoxy group. The comparison with the unreacted mixed sample also shows the occurrence of the reaction.

[0060] Example 1 A photothermal dual-curing system lubricant, comprising the following components in parts by weight: 100 g of epoxy-modified acrylic resin prepolymer prepared by the above method, 150 g of active diluent HDDA, 1 g of photoinitiator 819 and 1 g of BP, 5 g of thermal curing agent 2-ethyl-4-methylimidazole, 20 g of boron nitride, 0.5 g of molybdenum disulfide, 0.5 g of primary antioxidant tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester (1010), and 0.5 g of secondary antioxidant dilauryl dipropionate (DLTP); The epoxy value of the epoxy-modified acrylic resin prepolymer is 0.26 mol / 100 g; The preparation method of the photothermal dual-curing system lubricant is as follows: in the dark, a photoinitiator, a thermal curing agent and a reactive diluent are mechanically stirred at 80° C. and 400 rpm for 30 minutes to obtain a mixed solution; molybdenum disulfide, boron nitride, an epoxy-modified acrylic resin prepolymer, a primary antioxidant and an auxiliary antioxidant are ground by a three-roll grinder to fully mix them to obtain a resin material; the mixed material and the resin material are mechanically stirred at 80° C. and 400 rpm for 30 minutes in the dark to obtain the photothermal dual-curing system lubricant.

[0061] Example 2 A photothermal dual-curing system lubricant, comprising the following components in parts by weight: 100 g of epoxy-modified acrylic resin prepolymer prepared by the above method, 150 g of active diluent HDDA / HEMA (4:6), 1 g of photoinitiator 819 and 1 g of BP, 5 g of thermal curing agent 2-ethyl-4-methylimidazole, 20 g of boron nitride, 0.5 g of molybdenum disulfide, 0.5 g of primary antioxidant tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester (1010), and 0.5 g of secondary antioxidant dilauryl dipropionate (DLTP); The epoxy value of the epoxy-modified acrylic resin prepolymer is 0.26 mol / 100 g; The preparation method of the photothermal dual-curing system lubricant is the same as that in Example 1.

[0062] Example 3 A photothermal dual-curing system lubricant, comprising the following components in parts by weight: 100 g of epoxy-modified acrylic resin prepolymer prepared by the above method, 120 g of active diluent HDDA / HEMA (4:6), 1 g of photoinitiator 819 and 1 g of BP, 5 g of thermal curing agent 2-ethyl-4-methylimidazole, 20 g of boron nitride, 0.5 g of molybdenum disulfide, 0.5 g of primary antioxidant tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester (1010), and 0.5 g of secondary antioxidant dilauryl dipropionate (DLTP); The epoxy value of the epoxy-modified acrylic resin prepolymer is 0.26 mol / 100 g; The preparation method of the photothermal dual-curing system lubricant is the same as that in Example 1.

[0063] Example 4 A photothermal dual-curing system lubricant, comprising the following components by weight: 100 g of epoxy-modified acrylic resin prepolymer prepared by the above method, 180 g of active diluent HDDA / HEMA (4:6), 1 g of photoinitiator 819 and 1 g of BP, 5 g of thermal curing agent 2-ethyl-4-methylimidazole, 20 g of boron nitride, 0.5 g of molybdenum disulfide, 0.5 g of primary antioxidant tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester (1010), and 0.5 g of secondary antioxidant dilauryl dipropionate (DLTP); The epoxy value of the epoxy-modified acrylic resin prepolymer is 0.26 mol / 100 g; The preparation method of the photothermal dual-curing system lubricant is the same as that in Example 1.

[0064] Example 5 A photothermal dual-curing system lubricant, comprising the following components in parts by weight: 100 g of epoxy-modified acrylic resin prepolymer prepared by the above method, 150 g of active diluent HDDA / HEMA (4:6), 2 g of photoinitiator 819, 5 g of thermal curing agent 2-ethyl-4-methylimidazole, 20 g of boron nitride, 0.5 g of molybdenum disulfide, 0.5 g of primary antioxidant tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester (1010), and 0.5 g of secondary antioxidant dilauryl dipropionate (DLTP); The epoxy value of the epoxy-modified acrylic resin prepolymer is 0.26 mol / 100 g; The preparation method of the photothermal dual-curing system lubricant is the same as that in Example 1.

[0065] Example 6 A photothermal dual-curing system lubricant, comprising the following components in parts by weight: 100 g of epoxy-modified acrylic resin prepolymer prepared by the above method, 150 g of active diluent HDDA / HEMA (4:6), 0.25 g of photoinitiator 819 and 0.25 g of BP, 5 g of thermal curing agent 2-ethyl-4-methylimidazole, 20 g of boron nitride, 0.5 g of molybdenum disulfide, 0.5 g of primary antioxidant tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester (1010), and 0.5 g of secondary antioxidant dilauryl dipropionate (DLTP); The epoxy value of the epoxy-modified acrylic resin prepolymer is 0.26 mol / 100 g; The preparation method of the photothermal dual-curing system lubricant is the same as that in Example 1.

[0066] Example 7 A photothermal dual-curing system lubricant, comprising the following components in parts by weight: 100 g of epoxy-modified acrylic resin prepolymer prepared by the above method, 150 g of active diluent HDDA / HEMA (4:6), 1.5 g of photoinitiator 819 and 1.5 g of BP, 5 g of thermal curing agent 2-ethyl-4-methylimidazole, 20 g of boron nitride, 0.5 g of molybdenum disulfide, 0.5 g of primary antioxidant tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester (1010), and 0.5 g of secondary antioxidant dilauryl dipropionate (DLTP); The epoxy value of the epoxy-modified acrylic resin prepolymer is 0.26 mol / 100 g; The preparation method of the photothermal dual-curing system lubricant is the same as that in Example 1.

[0067] Example 8 A photothermal dual-curing system lubricant, comprising the following components in parts by weight: 100 g of epoxy-modified acrylic resin prepolymer prepared by the above method, 150 g of active diluent HDDA / HEMA (4:6), 1 g of photoinitiator 819 and 1 g of BP, 5 g of thermal curing agent 2-ethyl-4-methylimidazole, 5 g of boron nitride, 0.5 g of molybdenum disulfide, 0.5 g of primary antioxidant tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester (1010), and 0.5 g of secondary antioxidant dilauryl dipropionate (DLTP); The epoxy value of the epoxy-modified acrylic resin prepolymer is 0.26 mol / 100 g; The preparation method of the photothermal dual-curing system lubricant is the same as that in Example 1.

[0068] Example 9 A photothermal dual-curing system lubricant, comprising the following components by weight: 100 g of epoxy-modified acrylic resin prepolymer prepared by the above method, 150 g of active diluent HDDA / HEMA (4:6), 1 g of photoinitiator 819 and 1 g of BP, 5 g of thermal curing agent 2-ethyl-4-methylimidazole, 30 g of boron nitride, 0.5 g of molybdenum disulfide, 0.5 g of primary antioxidant tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester (1010), and 0.5 g of secondary antioxidant dilauryl dipropionate (DLTP); The epoxy value of the epoxy-modified acrylic resin prepolymer is 0.26 mol / 100 g; The preparation method of the photothermal dual-curing system lubricant is the same as that in Example 1.

[0069] Example 10 A photothermal dual-curing system lubricant, comprising the following components in parts by weight: 100 g of epoxy-modified acrylic resin prepolymer prepared by the above method, 150 g of active diluent HDDA / HEMA (4:6), 1 g of photoinitiator 819 and 1 g of BP, 5 g of thermal curing agent 2-ethyl-4-methylimidazole, 20 g of boron nitride, 1 g of molybdenum disulfide, 0.5 g of primary antioxidant tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester (1010), and 0.5 g of secondary antioxidant dilauryl dipropionate (DLTP); The epoxy value of the epoxy-modified acrylic resin prepolymer is 0.26 mol / 100 g; The preparation method of the photothermal dual-curing system lubricant is the same as that in Example 1.

[0070] Embodiment 11 A photothermal dual-curing system lubricant, composed of the following components in parts by weight: 100g of epoxy-modified acrylic resin prepolymer, 150g of active diluent HDDA / HEMA (4:6), 1g of photoinitiator 819 and 1g of BP, 5g of thermal curing agent 2-ethyl-4-methylimidazole, 20g of boron nitride, 1g of molybdenum disulfide, 0.5g of primary antioxidant tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester (1010), and 0.5g of secondary antioxidant dilauryl dipropionate (DLTP); The epoxy value of the epoxy-modified acrylic resin prepolymer is 0.6 mol / 100 g; The preparation method of the photothermal dual-curing system lubricant is the same as that in Example 1.

[0071] Comparative Example 1 A lubricant, comprising the following components in parts by weight: 100 g of cyclo AG-80 prepared by the above method, 50 g of MAA, 150 g of HDDA as an active diluent, 1 g of 819 and 1 g of BP as a photoinitiator, 5 g of 2-ethyl-4-methylimidazole as a thermal curing agent, 20 g of boron nitride, 0.5 g of molybdenum disulfide, 0.5 g of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (1010) as a primary antioxidant, and 0.5 g of dilauryl dipropionate (DLTP) as an auxiliary antioxidant; The preparation method of the photothermal dual-curing system lubricant is the same as that in Example 1.

[0072] Example 12 The method of using the light-heat dual-curing system lubricant obtained in Examples 1 to 11 is as follows: (1) Use ethanol to treat the surface of the lubrication failure substrate, clean the residual oil film on the surface, and keep it in a dry state; (2) The photothermal dual-curing system lubricant obtained in the embodiment is evenly coated on the surface of the lubrication failure substrate by spraying, and the coating thickness is about 5-30 μm; a handheld UV lamp with a power of 1-10 W and a wavelength of 320-400 nm is used to irradiate the coated surface to achieve complete curing, thereby obtaining a photothermal dual-curing system lubricating coating.

[0073] Comparative Example 2 The lubricant obtained in Comparative Example 1 was used by the method of Example 12 to obtain a lubricating coating.

[0074] The test results of the lubricating coating obtained by using the above method for the photothermal dual-curing lubricants of Examples 1 to 11 and the lubricant obtained in Comparative Example 1 are shown in Table 1. Among them, the curing time is obtained by Fourier infrared spectrometer test; the adhesion is evaluated according to GB / T9286-2021 standard and obtained by the cross-cut method; the friction coefficient is evaluated according to GB / T3960-2016 standard and obtained by the M2000 friction and wear tester; the mechanical strength is evaluated according to GB / T 7124-2008 standard and obtained by the tensile tester.

[0075] Table 1 Test results of lubricating coatings obtained using different photothermal dual-curing lubricants

[0076] It can be seen from the above results that the photothermal dual-curing system lubricant obtained by the present invention has fast curing, and the obtained lubricating layer has excellent lubricity and mechanical strength. This is because the present invention uses epoxy-modified acrylic resin prepolymer as the base resin of the coating, realizes rapid curing through photoinitiation, and uses the heat released by ultraviolet light curing to initiate deep curing of the epoxy resin thermal system, further improving the mechanical properties of the coating, and is combined with boron nitride and molybdenum disulfide to improve the lubrication effect, greatly reducing the repair time and cost of the lubrication system.

[0077] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A light-heat dual-curing system lubricant, comprising the following components in parts by weight: 100 parts of epoxy-modified acrylic resin prepolymer, 120-180 parts of reactive diluent, 0.5-3 parts of photoinitiator, 1-10 parts of thermal curing agent, 5-30 parts of boron nitride, 0.5-1 parts of molybdenum disulfide, 0.3-0.5 parts of primary antioxidant and 0.3-0.5 parts of auxiliary antioxidant; The epoxy value of the epoxy-modified acrylic resin prepolymer is 0.2-0.6 mol / 100g.

2. The light-heat dual-curing system lubricant according to claim 1, characterized in that: The epoxy-modified acrylic resin prepolymer is obtained by mixing and polymerizing the following raw materials by weight: 100 parts of epoxy resin, 10-60 parts of acrylic monomer, 0.1-3 parts of catalyst and 0.01-1 parts of polymerization inhibitor.

3. The light-heat dual-curing system lubricant according to claim 2, characterized in that: The epoxy resin includes one or more of bisphenol A epoxy resin, bisphenol F epoxy resin and polyphenol glycidyl ether epoxy resin.

4. The light-heat dual-curing system lubricant according to claim 2, characterized in that: The acrylic monomer includes one or more of acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, isooctyl acrylate and butyl acrylate.

5. The light-heat dual-curing system lubricant according to claim 1, characterized in that: The photoinitiator is a free radical photoinitiator.

6. The light-heat dual-curing system lubricant according to claim 1, characterized in that: The thermal curing agent is an imidazole curing agent.

7. The light-heat dual-curing system lubricant according to claim 1, characterized in that: The particle size of the boron nitride is 50-100 nm.

8. The light-heat dual-curing system lubricant according to claim 1, characterized in that: The particle size of the molybdenum disulfide is 1-20 μm.

9. The method for preparing the photothermal dual-curing system lubricant according to any one of claims 1 to 8, comprising: The epoxy modified acrylic resin prepolymer, active diluent, photoinitiator, thermal curing agent, boron nitride, molybdenum disulfide, primary antioxidant and auxiliary antioxidant are mixed under light-proof condition to obtain a light-heat dual curing system lubricant.

10. A method for using the photothermal dual-cure lubricant according to any one of claims 1 to 8 or the photothermal dual-cure lubricant prepared by the preparation method according to claim 9, comprising: The photothermal dual-curing system lubricant is coated on the surface of the substrate and subjected to a curing reaction under ultraviolet light to obtain a photothermal dual-curing system lubricating coating.

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