CN111286391A - High-temperature-resistant self-lubricating capsule and preparation method and application thereof - Google Patents
High-temperature-resistant self-lubricating capsule and preparation method and application thereof Download PDFInfo
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- CN111286391A CN111286391A CN202010099144.2A CN202010099144A CN111286391A CN 111286391 A CN111286391 A CN 111286391A CN 202010099144 A CN202010099144 A CN 202010099144A CN 111286391 A CN111286391 A CN 111286391A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/041—Carbon; Graphite; Carbon black
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/10—Compounds containing silicon
- C10M2201/105—Silica
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/024—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
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Abstract
The invention relates to a method for preparing a high-temperature-resistant self-lubricating capsule, which comprises the following steps: filling the mesoporous silica microspheres with a liquid lubricant to prepare a lubricant-loaded silica capsule; dispersing the lubricant-loaded silicon dioxide capsules in an emulsifier aqueous solution to prepare a capsule emulsion; adding polyethyleneimine-dopamine hydrochloride composite solution into the capsule emulsion to prepare a modified capsule; and adding a graphene aqueous solution into the modified capsule aqueous solution to prepare the silicon dioxide loaded lubricant capsule encapsulated by graphene. The high-temperature-resistant self-lubricating capsule prepared by the method can resist obviously higher temperature, has higher liquid lubricant coating rate and higher friction resistance, has wide selection range of the liquid lubricant, is not limited by a capsule synthesis process, and is simple and easy to implement.
Description
Technical Field
The invention relates to the technical field of lubricating materials, in particular to a high-temperature-resistant self-lubricating capsule and a preparation method and application thereof.
Background
Frictional wear is the primary cause of mechanical component failure and energy loss. The polymer-based self-lubricating material is widely applied to the field of tribology due to the advantages of good self-lubricating property, light weight, excellent environmental adaptability and the like, and is widely applied to mechanical lubricating parts such as aerospace, oilfield chemical engineering and the like. However, under special working conditions or in the long-term use process, the tribological performance of the materials can be reduced, the service life can be shortened, and even the failure of parts and major mechanical accidents can be caused. The high-performance polymer-based self-lubricating composite material prepared by the method can meet the requirements of antifriction and wear resistance of mechanical friction parts under severe conditions, and has important research significance.
The microcapsule self-lubricating polymer material has attracted attention in recent years because of its easy preparation, wide application range and excellent antifriction and wear-resisting performance. The microcapsules reported in the literature usually adopt organic substances as wall materials, the organic substances comprise urea formaldehyde resin, melamine resin, polyurea, polysulfone, polystyrene and the like, and the organic wall materials have the main disadvantage of low heat resistance temperature, usually lower than 300 ℃, which limits the application of the microcapsules in high-temperature environment to a certain extent. Or the organic-inorganic hybrid structure is taken as a wall material, such as polysulfone/carbon nanotube, polystyrene/silicon dioxide and the like, and the hybrid wall material structure can improve the heat-resistant temperature of the wall material to a certain extent, but the effect is not obvious. The method for preparing the self-lubricating microcapsule mainly comprises a solvent volatilization method, an interface polymerization method, an in-situ polymerization method and a sol-gel method, and the methods are difficult to microencapsulate certain lubricants with higher viscosity or special properties, such as ionic liquids, perfluoropolyethers or some commercially available liquid lubricants containing various additives, and have lower microcapsule yield and core material coating rate. Therefore, the development of a high-temperature-resistant self-lubricating microcapsule is imperative to meet the requirements of the polymer on high-temperature forming and high-temperature use conditions.
Disclosure of Invention
In order to solve one or more of the above-mentioned problems of the prior art, the present application provides in a first aspect a method of preparing a high temperature resistant self-lubricating capsule, the method comprising the steps of:
(1) dispersing mesoporous silica microspheres in a liquid lubricant under a reduced pressure condition to enable the liquid lubricant to fill the mesoporous silica microspheres, and separating to obtain a silica-loaded lubricant capsule;
(2) dispersing the silicon dioxide loaded lubricant capsules in an emulsifier aqueous solution to prepare a capsule emulsion;
(3) adding a polyethyleneimine-dopamine hydrochloride composite solution into the capsule emulsion, and reacting while stirring to obtain a polyethyleneimine-polydopamine modified capsule;
(4) and preparing a modified capsule aqueous solution by using the modified capsule, adding a graphene aqueous solution into the modified capsule aqueous solution, and reacting to obtain the silicon dioxide loaded lubricant capsule encapsulated by the graphene.
The present application provides in a second aspect a high temperature resistant self-lubricating capsule made by the method of the first aspect of the invention.
In a third aspect, the present application provides the use of a high temperature resistant self-lubricating capsule as described in the second aspect of the present application in the preparation of a resin-based self-lubricating composite material.
Compared with the prior art, the invention at least has the following technical effects:
(1) the high-temperature-resistant self-lubricating capsule prepared by the invention can tolerate a remarkably high temperature, because the wall material silicon dioxide and the graphene oxide can tolerate a very high temperature, so that the prepared high-temperature-resistant self-lubricating capsule can tolerate a high temperature only by selecting a high-temperature-resistant lubricant.
(2) The high-temperature-resistant self-lubricating capsule prepared by the invention has higher liquid lubricant coating rate, because the hollow mesoporous silica microspheres with small wall thickness can be selected to realize the required high coating rate.
(3) The high-temperature-resistant self-lubricating capsule prepared by the invention has higher friction resistance, because the adopted materials such as the liquid lubricant, the silicon dioxide microspheres, the graphene such as the oxidized graphene or the reduced graphene (namely the graphene in general) and the like all have excellent friction resistance, and the prepared polymer-based self-lubricating composite material containing the capsule shows excellent tribological performance.
(4) The method has wide selection range of the adopted liquid lubricant, because the method avoids the process of preparing the capsule wall material by organic synthesis, directly adopts the mesoporous silica microspheres as the wall material, does not need to consider the influence of additives contained in the liquid lubricant on the organic synthesis process of the wall material, can not strictly consider the influence of the viscosity, the hydrophobicity and the like of the liquid lubricant on the synthesis of the wall material and the coating of the core material, and also ensures that the process steps are simple and easy.
Drawings
FIG. 1 is a schematic diagram of a preparation process of an embodiment of a high temperature resistant self-lubricating capsule prepared from hollow mesoporous silica microspheres.
FIG. 2 is a schematic diagram of a preparation process of one embodiment of preparing a high temperature resistant self-lubricating capsule from non-hollow mesoporous silica microspheres.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
In order to solve one or more of the above-mentioned problems of the prior art, the present application provides in a first aspect a method of preparing a high temperature resistant self-lubricating capsule, the method comprising the steps of:
(1) dispersing mesoporous silica microspheres in a liquid lubricant under a reduced pressure condition to enable the liquid lubricant to fill the mesoporous silica microspheres, and separating to obtain a silica-loaded lubricant capsule;
(2) dispersing the silicon dioxide loaded lubricant capsules in an emulsifier aqueous solution to prepare a capsule emulsion;
(3) adding a polyethyleneimine-dopamine hydrochloride composite solution into the capsule emulsion, and reacting while stirring to obtain a polyethyleneimine-polydopamine modified capsule;
(4) and preparing a modified capsule aqueous solution by using the modified capsule, adding a graphene aqueous solution into the modified capsule aqueous solution, and reacting to obtain the silicon dioxide loaded lubricant capsule encapsulated by the graphene oxide.
In some preferred embodiments, the mesoporous silica microspheres are selected from the group consisting of hollow mesoporous silica microspheres and non-hollow mesoporous silica microspheres.
Preferably, the hollow mesoporous silica microspheres and the non-hollow mesoporous silica microspheres independently have the following properties: (a) a particle size of 200 nanometers to 10 micrometers (e.g., 500 nanometers, 1 micrometer, 2 micrometers, or 5 micrometers); preferably 1 micron to 2 microns, (b) a pore size of 2 nm to 50 nm (e.g. 5 nm, 10 nm or 20 nm), and/or (c) a wall thickness of 10 nm to 200 nm (e.g. 20, 50, 100 or 150 nm). If the particle diameter of the silica microspheres is too small, the silica microspheres are not easily dispersed, and if the particle diameter of the silica microspheres is too large, the mechanical properties of the matrix material may be adversely affected, and therefore, it is preferable to be 1 to 2 μm. The wall thickness of the hollow mesoporous silica microspheres can be smaller so that more liquid lubricant can be filled.
In some preferred embodiments, the liquid lubricant is selected from the group consisting of poly α -olefin lubricant ionic liquid lubricants, perfluoropolyether lubricants, drying oil lubricants, silicone lubricants, isocyanate lubricants, and oleamide lubricants.
Preferably, the polyolefin lubricant is a poly α -olefin lubricant, such as a poly α -butene lubricant, a poly α -hexene lubricant, a poly α -octene lubricant, a poly α -decene lubricant, and the like, the ionic liquid lubricant is selected from the group consisting of 1-butyl-3-methylimidazolium hexafluorophosphate ([ BMIM ] PF6]), 1-ethyl-3-methylimidazolium tetrafluoroborate ([ EMIm ] BF4]), and 1-hexyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide ([ HMIM ] [ NTf2]), the drying oil is selected from the group consisting of tung oil and flax oil, and the perfluoropolyether lubricant may be, for example, a type Z perfluoropolyether lubricant, and the like.
Indeed, the method of the present invention may be equally applicable to the use of relatively low temperature resistant lubricants, so long as the temperature resistance of these lubricants is such that they can be used in the target environment. Thus, in other alternative embodiments, the liquid lubricant may be a petroleum-based lubricant or an isocyanate. The petroleum-based lubricant is selected from the group consisting of paraffin lubricants and lubricating base oils, for example.
Regarding the built lubricant, generally, the lubricant is a built lubricant composed of one or more major lubricant components in a major amount and one or more minor lubricant components in a minor amount used as additives, for example, composed of α -olefin as a major lubricant component (in an amount of, for example, 90 mass% or more) and an ionic liquid such as 1-butyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium tetrafluoroborate and/or 1-hexyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt as a minor lubricant component (in an amount of, for example, 10 mass% or less).
In some preferred embodiments, the liquid lubricant is selected from the group consisting of ionic liquid lubricants and perfluoropolyether lubricants. It is also preferred that the liquid lubricant is capable of withstanding temperatures of from 300 ℃ to 450 ℃, preferably from 380 ℃ to 500 ℃, for example 400 ℃.
In some preferred embodiments, the aqueous emulsifier solution comprises 0.5 to 3 mass% (1.0, 1.5, 2.0, or 2.5 mass%) of an emulsifier.
It is also preferred that the capsule emulsion comprises 1 to 5 mass% (e.g. 2, 3 or 4 mass%) of lubricant-loaded silica capsules.
Preferably, the emulsifier is selected from the group consisting of gelatin, gum arabic, polyvinyl alcohol, lignin 88A, span80, Tween80, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
In some preferred embodiments, the polyethyleneimine-dopamine hydrochloride complex solution is prepared by: adding polyethyleneimine into a Tris (hydroxymethyl) aminomethane (Tris) water solution, uniformly mixing, and then adding dopamine hydrochloride, and uniformly mixing. Preferably, the aqueous tris (hydroxymethyl) aminomethane solution comprises 0.1 to 0.5 mass% (e.g., 0.2, 0.3, or 0.4 mass%) tris (hydroxymethyl) aminomethane at a pH of 8 to 9.
It is also preferred that the concentrations of the polyethyleneimine and the dopamine hydrochloride in the modified capsule solution are independently 0.1 mass% to 0.5 mass% (e.g., 0.2, 0.3, or 0.4 mass%).
In some preferred embodiments, the aqueous modified capsule solution comprises 1 to 5 mass% of modified capsules, and the aqueous graphene solution comprises 0.1 to 0.5 mass% (e.g., 0.2, 0.3, or 0.4 mass%) of graphene.
In some preferred embodiments, step (1) is performed by: according to the mass ratio of 1: 1-5 (e.g., 1:2, 1:3, or 1:4), dispersing the mesoporous silica microspheres in a liquid lubricant, stirring under reduced pressure at a gauge pressure of 0.005MPa to 0.03MPa (e.g., 0.01MPa) for 2 hours to 5 hours (e.g., 3 or 4 hours), and separating by centrifugation or precipitation filtration to obtain lubricant-supported silica capsules.
In other preferred embodiments, step (2) is performed by: the silica-loaded lubricant capsules are dispersed in an aqueous emulsifier solution and stirred at 200rpm to 400rpm (e.g., 300rpm) for 10 minutes to 30 minutes (e.g., 20 minutes).
In other preferred embodiments, step (3) is performed by: adding the capsule emulsion into a polyethyleneimine-dopamine hydrochloride composite solution in a mass ratio of 1:1-3 (such as 1:2), stirring at normal temperature at a speed of 200 rpm-400 rpm (such as 300rpm) for 2 hours to 4 hours, such as 3 hours, reacting, washing, filtering and drying to obtain the polyethyleneimine-polydopamine modified capsule solution. The drying method of the present invention is not limited as long as it does not adversely affect the capsule, and for example, drying at room temperature or drying in an oven, in general, may be carried out at 40 ℃ to 60 ℃, for example, 50 ℃.
In other preferred embodiments, step (4) is performed by: preparing a modified capsule aqueous solution by using the modified capsule, and mixing the modified capsule aqueous solution with the weight ratio of 1: and (3) dropwise adding the graphene aqueous solution into the modified capsule aqueous solution in a mass ratio of 0.2-1 (such as 1:0.5), and stirring or shaking at a speed of 200-400rpm (such as 300rpm) at normal temperature for 6-12 hours (such as 8 or 10 hours) to perform reaction to prepare the silica-encapsulated lubricant capsule.
In some embodiments, the methods of the present invention comprise the steps of:
(1) dispersing hollow mesoporous silica microspheres or non-hollow mesoporous silica microspheres in a liquid lubricant (mass ratio is 1: 1-5), stirring for 2-12 hours under a reduced pressure (pressure range is 0.005 MPa-0.03 MPa, temperature is 20-80 ℃), and centrifuging (2000g, 5 minutes) for separation to obtain the lubricant-loaded silica capsule.
(2) Dispersing the lubricant-loaded silica capsules in an aqueous solution containing an emulsifier (the capsule content is 1 to 5% by mass, and the emulsifier concentration is 0.5 to 3% by mass), and mechanically stirring for 10 to 30 minutes (the stirring speed is 200 to 400rpm) to obtain a capsule emulsion.
(3) Preparing a Tris (hydroxymethyl) aminomethane (Tris) water buffer solution with the concentration of 0.1-0.5 mass%, adjusting the pH value of the aqueous solution to 8-9 with dilute hydrochloric acid, adding Polyethyleneimine (PEI) (the concentration of PEI in the Tris solution is 0.1-0.5 mass%), manually shaking for 5-30 seconds, adding dopamine hydrochloride (DA-HCL) (the concentration of DA-HCL in the Tris solution is 0.1-0.5 mass%), and manually shaking for 5-30 seconds to obtain the polyethyleneimine-dopamine hydrochloride composite solution. And adding the polyethyleneimine-dopamine hydrochloride composite solution into the capsule emulsion, wherein the mass ratio of the polyethyleneimine-dopamine hydrochloride composite solution to the capsule emulsion is 1:1-3, stirring at normal temperature for 2-4h (the stirring speed is 200-400rpm), washing, filtering and drying to obtain the PDA-PEI modified polyethyleneimine-dopamine modified capsule with positive charges on the surface.
(4) Adding the modified capsule into deionized water (the content of the modified capsule is 1-5 mass%), and mechanically stirring or shaking for 2-5 hours; preparing a Graphene (GO) aqueous solution with a concentration of 0.1 to 0.5 mass%; gradually dripping the aqueous solution of GO into deionized water containing the modified capsules (the ratio of the amount of the aqueous solution of GO to the amount of the deionized water containing the modified capsules is 0.2-1:1), and mechanically stirring or shaking for 6-12 hours at normal temperature to prepare the silicon dioxide encapsulated lubricant capsules.
The present application provides in a second aspect a high temperature resistant self-lubricating capsule made by the method of the first aspect of the invention.
In a third aspect, the present application provides the use of a high temperature resistant self-lubricating capsule as described in the second aspect of the present application in the preparation of a resin-based self-lubricating composite material. Preferably, the resin-based self-lubricating composite material is prepared from a high-temperature-resistant self-lubricating capsule and a resin matrix selected from the group consisting of polyimide, polyamide, polytetrafluoroethylene, ultra-high molecular weight polyethylene, epoxy resin, polyetheretherketone and polyphenylene sulfide.
The application provides a high-temperature-resistant self-lubricating capsule, a preparation method thereof and application thereof in a resin-based self-lubricating composite material. The capsule of the invention firstly loads a high temperature resistant lubricant on hollow mesoporous silica microspheres or non-hollow mesoporous silica microspheres, and then wraps the silica microspheres loaded with a liquid lubricant with graphene oxide lamella, and finally prepares the high temperature resistant self-lubricating capsule (see attached figures 1 and 2). The thermal decomposition temperature of the prepared capsule can be obviously higher than 300 ℃, and the capsule can be applied to resin matrixes such as polyimide, polyamide, polytetrafluoroethylene, ultrahigh molecular weight polyethylene, epoxy resin, polyether ether ketone, polyphenylene sulfide and the like, so that the requirement of high-temperature molding of the resin matrixes is met. Meanwhile, the self-lubricating composite material containing the capsule can meet the requirement of high-temperature self-lubrication. In addition, as the three capsule materials of the silicon dioxide, the graphene oxide and the high-temperature-resistant lubricant have excellent friction resistance, the prepared polymer-based self-lubricating composite material containing the capsules shows excellent tribological performance.
Examples
The invention will be further illustrated by the following examples, but it will be understood that the scope of the invention is not limited to these examples.
Preparation of high-temperature-resistant self-lubricating microcapsule
Example 1
Dispersing hollow mesoporous silica microspheres (the particle diameter is 2 microns, the pore diameter is 30 nanometers, and the wall thickness is 20 nanometers) in a liquid lubricant (1-butyl-3-methylimidazolium hexafluorophosphate) (the mass ratio is 1:4), and stirring for 3 hours under a reduced pressure (the gauge pressure is 0.01MPa) state at the temperature of 50 ℃. After centrifugal separation (4000rpm, 5 minutes) silica-supported lubricant capsules (lubricant @ SiO) were obtained2)。
The silica-supported lubricant capsules were dispersed in an aqueous solution containing an emulsifier (gelatin) (capsule content 3% by mass, emulsifier concentration 2% by mass), and mechanically stirred for 20 minutes (stirring speed 300 rpm).
Preparing a Tris (hydroxymethyl) aminomethane (Tris) aqueous buffer solution with the concentration of 0.3 mass%, adjusting the pH of the aqueous solution to 9 with dilute hydrochloric acid, adding Polyethyleneimine (PEI) (the concentration of PEI in the Tris solution is 0.3 mass%), manually shaking for 10 seconds, adding dopamine hydrochloride (DA-HCL) (the concentration of DA-HCL in the Tris solution is 0.3 mass%), and manually shaking for 10 seconds.
Adding a polyethyleneimine-dopamine hydrochloride composite solution into the capsule emulsion, wherein the mass ratio of the polyethyleneimine-dopamine hydrochloride composite solution to the capsule emulsion is 1:2, stirring for 3 hours at normal temperature (stirring speed is 300rpm), washing, filtering, and drying at normal temperature to obtain Polyethyleneimine (PEI) -Polydopamine (PDA) modified capsule SiO2Capsule (PDA-PEI-Lubricant @ SiO)2Capsules).
Adding the polyethyleneimine-polydopamine modified capsule into deionized water (the capsule content is 3 mass%), and mechanically stirring or shaking for 3 hours; the preparation concentration is 0.3An amount% Graphene (GO) aqueous solution; gradually dropwise adding the aqueous solution of GO into deionized water containing capsules (the ratio of the amount of the aqueous solution of GO to the amount of the deionized water containing capsules is 0.6:1), mechanically stirring or vibrating at normal temperature for 9 hours to prepare the silicon dioxide loaded lubricant capsules (lubricant @ SiO) encapsulated by graphene oxide2GO capsule). Then, the lubricant content in the finally prepared capsules and the thermal stability of the capsules were measured by thermogravimetric analysis, and the results are shown in table 1.
Example 2
The procedure was carried out in substantially the same manner as in example 1, except that hollow mesoporous silica microspheres having a particle diameter of 500 nm were used as the silica microspheres.
Example 3
Substantially the same procedure as in example 1 was conducted except that hollow mesoporous silica microspheres having a particle diameter of 1 μm were used as the silica microspheres.
Example 4
Substantially the same procedure as in example 1 was conducted except that hollow mesoporous silica microspheres having a particle size of 5 μm were used as the silica microspheres.
Example 5
The procedure was carried out in substantially the same manner as in example 1 except that non-hollow mesoporous silica microspheres (particle size of 2 μm) were used as the silica microspheres.
Example 6
The procedure was carried out in substantially the same manner as in example 1 except that 1-ethyl-3-methylimidazolium tetrafluoroborate was used as the liquid lubricant.
Example 7
The procedure was carried out in substantially the same manner as in example 1 except that 1-hexyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt was used as the liquid lubricant.
Example 8
The procedure was carried out in substantially the same manner as in example 1 except that a Z-type perfluoropolyether lubricant was used as the liquid lubricant.
Example 9
The procedure was carried out in substantially the same manner as in example 1 except that a poly α -ethylene hydrocarbon lubricant (containing 5% of the ionic liquid 1-hexyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide) was used as the liquid lubricant.
Example 10
This was carried out in substantially the same manner as in example 1 except that silicone oil was used as the liquid lubricant.
Example 11
The microcapsule with silicon dioxide as a wall material and coated with silicone oil is prepared by a sol-gel method, and the reaction process is realized by hydrolysis and polycondensation of Tetraethoxysilane (TEOS) under an acidic condition. 0.5g of polyvinyl alcohol is dissolved in 50ml of deionized water to prepare a polyvinyl alcohol aqueous solution as an aqueous phase, and 0.3g of Span80, 0.3g of Tween80 and 5g of silicone oil are mixed to form a uniform oil phase. Adding the oil phase into the aqueous solution of polyvinyl alcohol, and emulsifying at 25 deg.C and 500rpm for 30min to obtain stable emulsion. 0.15g of sodium chloride was added thereto and emulsification was continued for 30 min. And adjusting the pH value to 3 by using dilute hydrochloric acid, dropwise adding 5g of ethyl orthosilicate, raising the temperature to 55 ℃, reacting for 3 hours, washing, filtering and drying to obtain the silicon dioxide-coated silicone oil microcapsule.
Example 12(1) to an aqueous solution of graphene oxide, an ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate was added, the pH of the system was adjusted to 3, the concentration of the aqueous solution of graphene oxide was 0.05 wt%, and the mass ratio of the ionic liquid to water was 1: 10. And ultrasonically dispersing the mixed solution for 5min, and ultrasonically performing in an ice bath to prepare the GO stable emulsion.
(2) Adding isophorone isocyanate into the GO stable emulsion, wherein the mass ratio of isocyanate to 1-butyl-3-methylimidazole hexafluorophosphate is 1:1, mechanically stirring for 5min (the rotating speed is 300r/min), adding 10 wt% of triethylene tetramine aqueous solution, wherein the mass ratio of isocyanate to triethylene tetramine is 1:1, heating the system to 40 ℃, and reacting for 4h to prepare the polyurea/graphene oxide (PU/GO) double-wall micro-nano capsule coated with the ionic liquid.
(3) Preparing a Tris (hydroxymethyl) aminomethane (Tris) water solution with the concentration of 0.1 wt%, adjusting the pH of the water solution to 9 with diluted hydrochloric acid, adding Polyethyleneimine (PEI), wherein the concentration of polyethyleneimine in the Tris solution is 0.1 wt%, manually shaking for 5s, adding dopamine hydrochloride (DA-HCL), wherein the concentration of dopamine hydrochloride in the Tris solution is 0.1 wt%, manually shaking for 5s, adding 1 wt% (referring to the mass percentage content in the Tris solution) of the micro-nano capsule prepared in the step (2), reacting for 3h at room temperature, filtering, washing and drying to obtain the dopamine-polyethyleneimine modified micro-nano capsule with positive charges on the surface.
(4) And (3) mixing the micro-nano capsule obtained in the step (3) with a GO aqueous solution with the concentration of 0.1 wt%, wherein the mass fraction of the micro-nano capsule in the GO aqueous solution is 1 wt%, mechanically stirring at normal temperature for 200r/min, and reacting for 1h to prepare the PU/GO/PEI/GO multi-wall micro-nano capsule.
Example 13
The procedure was carried out in substantially the same manner as in example 12 except that a Z-type perfluoropolyether lubricant was used as the liquid lubricant in place of the ionic liquid.
TABLE 1 Properties of the lubricant capsules prepared in the examples.
Preparation of resin-based self-lubricating composite material
Preparation example 1
Adding the silicon dioxide encapsulated lubricant capsule prepared in the example 1 into a resin matrix (the addition amount of the microcapsule is 3 wt%), wherein the resin matrix is polyimide, uniformly mixing, adding into a mold, placing the mold into a vacuum hot mold press, heating to 380 ℃ under 20MPa, and naturally cooling to room temperature to prepare the resin-based self-lubricating composite material.
Preparation example 2
Substantially the same procedure as in example 1 was conducted except that polyether ether ketone was used in place of the polyimide resin, and pressing was conducted in a vacuum hot die press with the temperature raised to 370 ℃.
Preparation example 3
Adding 5 mass% of the graphene oxide encapsulated silica-supported lubricant capsule prepared in the example 8 into epoxy resin, adding 12 mass% of triethylene tetramine curing agent, uniformly stirring, placing in a vacuum oven for 2 hours to remove bubbles, curing at room temperature for 24 hours, heating to 120 ℃, and curing for 5 hours to prepare the self-lubricating epoxy resin composite material.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for preparing a high temperature resistant self-lubricating capsule, comprising the steps of:
(1) dispersing mesoporous silica microspheres in a liquid lubricant under a reduced pressure condition to enable the liquid lubricant to fill the mesoporous silica microspheres, and separating to obtain a lubricant-loaded silica capsule;
(2) dispersing the silicon dioxide loaded lubricant capsules in an emulsifier aqueous solution to prepare a capsule emulsion;
(3) adding a polyethyleneimine-dopamine hydrochloride composite solution into the capsule emulsion, and reacting while stirring to obtain a polyethyleneimine-polydopamine modified capsule;
(4) and preparing a modified capsule aqueous solution by using the modified capsule, adding a graphene aqueous solution into the modified capsule aqueous solution, and reacting to obtain the silicon dioxide encapsulated lubricant capsule.
2. The method of claim 1, wherein:
the mesoporous silica microspheres are selected from hollow mesoporous silica microspheres and non-hollow mesoporous silica microspheres;
preferably, the hollow mesoporous silica microspheres and the non-hollow mesoporous silica microspheres independently have the following properties: (a) a particle size of 200 nm to 10 microns, more preferably 1 micron to 2 microns, (b) a pore size of 2 nm to 50 nm, and/or (c) a wall thickness of 10 nm to 200 nm.
3. The method of claim 1, wherein:
the liquid lubricant is selected from the group consisting of poly α -olefin lubricant ionic liquid lubricants, perfluoropolyether lubricants, polyolefin lubricants, drying oil lubricants, silicone lubricants, isocyanate lubricants, and oleamide lubricants;
preferably, the polyolefin lubricant is a poly α -olefin lubricant, the ionic liquid lubricant is selected from the group consisting of 1-butyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium tetrafluoroborate and 1-hexyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt, and the drying oil is selected from the group consisting of tung oil and flax oil;
it is also preferred that the liquid lubricant is a lubricant comprising an additive, preferably the additive is selected from the group consisting of silica, molybdenum disulphide and built lubricants including ionic liquids.
4. The method of claim 1, wherein:
the liquid lubricant is selected from the group consisting of ionic liquid lubricants and perfluoropolyether lubricants; and/or the liquid lubricant is capable of withstanding 300 ℃ to 500 ℃, preferably 380 ℃ to 500 ℃.
5. The method of claim 1, wherein:
the aqueous emulsifier solution comprises 0.5 to 3 mass% of an emulsifier; and/or
The capsule emulsion comprises 1 to 5 mass% of silica-loaded lubricant capsules;
preferably, the emulsifier is selected from the group consisting of gelatin, gum arabic, polyvinyl alcohol, lignin 88A, span80, Tween80, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
6. The method of claim 1, wherein:
the polyethyleneimine-dopamine hydrochloride composite solution is prepared by the following method: adding polyethyleneimine into a tris (hydroxymethyl) aminomethane aqueous solution, uniformly mixing, and then adding dopamine hydrochloride, and uniformly mixing; preferably, the aqueous tris (hydroxymethyl) aminomethane solution comprises 0.1 to 0.5 mass% tris (hydroxymethyl) aminomethane, and has a pH of 8 to 9; and/or
In the modified capsule solution, the concentration of the polyethyleneimine and the dopamine hydrochloride is independently 0.1 to 0.5 mass%.
7. The method of claim, wherein:
the aqueous modified capsule solution contains 1 to 5 mass% of modified capsules, and the aqueous graphene solution contains 0.1 to 0.5 mass% of graphene.
8. The method of claim 1, wherein:
the step (1) is carried out in the following way: according to the mass ratio of 1: 1-5, dispersing the mesoporous silica microspheres in a liquid lubricant, stirring for 2-12 hours under a reduced pressure state with the gauge pressure of 0.005-0.03 MPa, and separating at the temperature of 25-80 ℃ by a centrifugal mode or a precipitation filtration mode to obtain silica-loaded lubricant capsules;
the step (2) is carried out in the following way: dispersing the lubricant-loaded silica capsules in an aqueous emulsifier solution, stirring at 200 to 400rpm for 10 to 30 minutes;
the step (3) is carried out in the following way: adding the capsule emulsion into a polyethyleneimine-dopamine hydrochloride composite solution in a mass ratio of 1:1-3, stirring at the normal temperature at a speed of 200 rpm-400 rpm for 2-4 hours for reaction, washing, filtering and drying to obtain a polyethyleneimine-polydopamine modified capsule solution;
the step (4) is carried out in the following way: preparing a modified capsule aqueous solution by using the modified capsule, and mixing the modified capsule aqueous solution with the weight ratio of 1: and (2) dropwise adding the graphene aqueous solution into the modified capsule aqueous solution according to the mass ratio of 0.2-1, and stirring or shaking at the speed of 200-400rpm for 6-12 hours at normal temperature to perform reaction to prepare the silicon dioxide encapsulated lubricant capsule.
9. A high temperature resistant self-lubricating capsule made by the process of any one of claims 1 to 8.
10. Use of the high temperature resistant self-lubricating capsules according to claim 9 for the preparation of resin-based self-lubricating composite materials; preferably, the resin-based self-lubricating composite material is prepared from a high-temperature-resistant self-lubricating capsule and a resin matrix selected from the group consisting of polyimide, polyamide, polytetrafluoroethylene, ultra-high molecular weight polyethylene, epoxy resin, polyetheretherketone and polyphenylene sulfide.
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