WO2017166917A1 - 一种用于关节轴承的自润滑涂层及其制备方法 - Google Patents

一种用于关节轴承的自润滑涂层及其制备方法 Download PDF

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WO2017166917A1
WO2017166917A1 PCT/CN2017/072325 CN2017072325W WO2017166917A1 WO 2017166917 A1 WO2017166917 A1 WO 2017166917A1 CN 2017072325 W CN2017072325 W CN 2017072325W WO 2017166917 A1 WO2017166917 A1 WO 2017166917A1
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fluorine
self
lubricating coating
parts
epoxy resin
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French (fr)
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戴李宗
吴顺伟
曾碧榕
朱继红
李忠裕
陈国荣
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Xiamen University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C08G83/003—Dendrimers
    • C08G83/004—After treatment of dendrimers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape

Definitions

  • the invention belongs to the technical field of coatings, and relates to a self-lubricating coating for joint bearings and a preparation thereof, in particular to a dendritic polymer self-lubricating coating and a preparation method thereof.
  • Fabric-lined self-lubricating joint bearings are joint bearings that contain self-lubricating materials in the form of fabric liners between the inner and outer rings. They are widely used in aerospace, aerospace, electric power, transportation and textile equipment.
  • the self-lubricating gasket between the inner and outer rings is bonded to the bearing metal ring by the adhesive.
  • the wear phenomenon caused by the gasket during the use process will cause the inner and outer ring gaps to be too large, thus losing the normal lubricating ability.
  • the improvement of the wear resistance of the self-lubricating liner working surface is a hot research topic of the current self-lubricating gasket.
  • Dendrimers are a new type of polymer with three-dimensional structure and high order which has been developed in the past ten years.
  • PAMAM polyamide-amine dendrimer
  • Classes with its simple synthesis, stable quality, unique structural properties, etc., have shown broad application prospects in many fields.
  • PAMAM has a large number of cavities inside, which can encapsulate small molecular compounds and can be used under certain conditions. They are released again.
  • Ye Chunhui et al. (a heat-resistant and wear-resistant self-lubricating coating, Chinese patent, patent publication number CN103992726A) mixes epoxy resin and polyester resin, and adds a small amount of graphite, PTFE powder, Nano-materials such as quartz powder are prepared to obtain a self-lubricating coating, which can quickly remove the heat generated by friction and reduce the friction loss.
  • the compatibility of the PTFE powder with the epoxy resin is poor, and the mechanical properties of the material are lowered.
  • Zhang Qiu Ming et al (a self-lubricating epoxy resin material and its preparation method, Chinese patent, patent publication number CN101348600A), a lubricating oil capsule, an epoxy resin and a curing agent are uniformly mixed and molded to obtain a self-lubricating epoxy resin. material.
  • This material can reduce the friction coefficient to a certain extent, but the lubricating oil capsule is unstable, the durability is poor, and the material can only be used now, and can not be stored for a long time, and the application is limited.
  • the invention provides a self-lubricating coating for a joint bearing and a preparation method thereof, the main feature is that a fluorine-containing dendrimer is added to the epoxy phenolic resin coating.
  • the three-dimensional ordered structure of the fluorine-containing dendrimer can play the role of "micro-bearing" in the friction process, and improve the self-lubricating property of the material; in addition, the fluorine element is easy to migrate and the dendritic polymer is easy to form a film.
  • the surface of the layer is easy to form a film, and the surface friction coefficient of the coating layer is lowered.
  • the inorganic filler can be uniformly dispersed in the resin under the action of the silane coupling agent and the surfactant, and the disadvantage of the poor impact resistance of the conventional epoxy resin coating is solved.
  • the present invention aims to provide a coating material and a preparation method thereof for use in the field of self-lubricating joint bearings.
  • the main features of the preparation of the self-lubricating coating for joint bearings include:
  • the formulation of the self-lubricating coating is as follows: 40-60 parts of epoxy resin, 10-20 parts of fluorine-containing epoxy resin, 30-50 parts of phenolic resin, 5-20 parts of fluorine-containing dendrimer, solvent 30-50
  • the silane coupling agent is 1 to 3 parts
  • the filler is 5 to 15 parts
  • the epoxy resin curing accelerator is 0.1 to 0.3 parts
  • the surfactant is 1 to 3 parts.
  • the dendrimer is a polyamide-amine dendrimer.
  • the fluorine-containing epoxy resin structure is:
  • R 1 and R 2 are both CF 3 or CF 2 CF 3 .
  • the epoxy resin is a commercial epoxy resin, that is, a compound containing two or more epoxy groups in the molecule, such as glycidyl ether, glycidylamine, glycidyl ester, etc.; wherein the glycidyl ether has a bisphenol A type , bisphenol F type, and bisphenol S type; glycidylamine has aniline glycidylamine, diaminodiphenylmethane tetraglycidylamine, etc.; glycidyl ester has diglycidyl pair (o) phthalate, etc. .
  • the phenol resin is a thermosetting type and a thermoplastic phenol resin, and the phenol resin may be used singly or in combination.
  • the solvent is a solvent having a low boiling point, and includes ethyl acetate, ethanol, and acetone, and they may be used singly or in combination of two or more.
  • the filler is talc, kaolin, aluminum hydroxide, clay, silica, or the like, and the fillers may be used singly or in combination.
  • the epoxy resin accelerator is an amine accelerator such as benzyldimethylamine, triethylamine, triethanolamine, dimethylethanolamine or the like, and the accelerator may be used singly or in combination.
  • the surfactant has the structural formula R 4 N + X - , wherein R may be the same or different hydrocarbon group, and X is mostly a halogen atom, or an acid group.
  • the present invention has the following advantages:
  • the fluorine-containing dendrimer has a three-dimensional ordered structure, similar to a "sphere", which acts as a "micro-bearing” during the friction process to enhance the self-lubricating properties of the material;
  • the fluorine-containing dendrimer is easy to form a film, which increases the toughness of the coating and reduces the surface of the coating. Friction coefficient, enhance the wear resistance of the coating;
  • Fluorinated dendrimers use PAMAM's good compatibility to solve the problem of poor compatibility of fluorine elements, and the introduction of fluorine can reduce the friction coefficient of materials and enhance the heat resistance and weather resistance of materials.
  • the fluorine-containing dendrimer structure has an amino group which can react with the epoxy group to increase the crosslinking density of the material and improve the mechanical properties of the material.
  • Figure 1 is a diagram showing the action mechanism of a fluorine-containing dendrimer in a self-lubricating coating of a joint bearing.
  • the fluorine-containing self-lubricating coating compound is smeared on the liner, and then the liner is baked in a blast oven at 110 ° C for 0.5 to 1 h, and then bonded to the treated metal plate for curing. It was pre-cured at 0.5 MPa for 0.5 h at 130 ° C, then heated to 170 ° C and kept for 1.5 h.
  • the friction and wear properties of the coating were tested by reciprocating oscillating friction and wear. The conditions were: normal temperature, the angle of oscillation was ⁇ 10°, the contact stress was 52 Mpa, the oscillation frequency was 2 Hz, and the number of consecutive oscillations per experiment was 2.5 ⁇ 104 times.
  • the measured friction coefficient was 0.032, and the specific wear rate was 4.7 ⁇ 1.3 ( ⁇ 10 -6 mm 3 /Nm).
  • fluorine-containing dendrimer 8 parts of 5.0G PAMAM dendrimer to three-necked flask, 12 parts of fluorine-containing acrylate monomer dissolved in 20 parts of methanol, and then fluorine-containing Acrylate The monomeric methanol solution was added dropwise to a three-necked flask, the temperature was controlled at 40 ° C, and the reaction was stirred for 25 hours under nitrogen atmosphere, and then the methanol was removed under reduced pressure to obtain a fluorine-containing dendrimer.
  • the fluorine-containing self-lubricating coating compound is smeared on the liner, and then the liner is baked in a blast oven at 110 ° C for 1 h, and then bonded to the treated metal plate for curing, and the curing condition is 1 MPa. Under the preheating at 130 ° C for 0.5 h, then the temperature was raised to 170 ° C, and kept for 2 h.
  • the friction and wear properties of the coating were tested by reciprocating oscillating friction and wear. The conditions were: normal temperature, the angle of oscillation was ⁇ 10°, the contact stress was 52 Mpa, the oscillation frequency was 2 Hz, and the number of consecutive oscillations per experiment was 2.5 ⁇ 104 times.
  • the measured friction coefficient was 0.025, and the specific wear rate was 3.9 ⁇ 1.5 ( ⁇ 10 -6 mm 3 /Nm).
  • the fluorine-containing self-lubricating coating compound is scraped on the liner, and then the liner is baked in a blast oven at 100 ° C for 0.5 h, and then bonded to the treated metal plate for curing.
  • the curing condition is Pre-curing at 0.5 MPa for 0.5 h at 120 ° C, then heating to 175 ° C, and keeping warm for 1.5 h.
  • the friction and wear properties of the coating were tested by reciprocating oscillating friction and wear. The conditions were: normal temperature, the angle of oscillation was ⁇ 10°, the contact stress was 52 Mpa, the oscillation frequency was 2 Hz, and the number of consecutive oscillations per experiment was 2.5 ⁇ 104 times.
  • the measured friction coefficient was 0.030, and the specific wear rate was 4.8 ⁇ 1.6 ( ⁇ 10 -6 mm 3 /Nm).
  • the fluorine-containing self-lubricating coating compound is scraped on the liner, and then the liner is baked in a blast oven at 100 ° C for 0.5 h, and then bonded to the treated metal plate for curing.
  • the curing condition is Pre-curing at 0.5 MPa for 0.5 h at 120 ° C, then heating to 175 ° C, and keeping warm for 1.5 h.
  • the friction and wear properties of the coating were tested by reciprocating oscillating friction and wear. The conditions were: normal temperature, the angle of oscillation was ⁇ 10°, the contact stress was 52 Mpa, the oscillation frequency was 2 Hz, and the number of consecutive oscillations per experiment was 2.5 ⁇ 104 times.
  • the measured friction coefficient was 0.027, and the specific wear rate was 5.0 ⁇ 1.5 ( ⁇ 10 -6 mm 3 /Nm).

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  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Sliding-Contact Bearings (AREA)
  • Lubricants (AREA)
  • Inorganic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Paints Or Removers (AREA)

Abstract

一种用于关节轴承的自润滑涂层及其制备方法。涂层以质量计包括：环氧树脂40～60份，含氟环氧树脂10～20份，酚醛树脂30～50份，含氟树枝状高分子5～20份，溶剂30～50份，硅烷偶联剂1～3份，填料5～15份，环氧树脂固化促进剂0.1～0.3份，表面活性剂1～3份。含氟树枝状高分子具有三维有序的结构，并在树枝末端引入大量的氟元素，在摩擦过程中，三维有序的树枝状结构能够起到类似"微轴承"的作用，使涂层具有自润滑的效果。

Description

一种用于关节轴承的自润滑涂层及其制备方法 技术领域
本发明属于涂层技术领域，涉及一种用于关节轴承的自润滑涂层及其制备，尤其是一种含树枝状高分子自润滑型涂层及其制备方法。
背景技术
织物衬垫自润滑关节轴承是指内、外圈间含有织物衬垫形式自润滑材料的关节轴承，广泛应用于航空、航天、电力、交通和纺织等装备中。内、外圈之间的自润滑衬垫通过粘结剂粘结在轴承金属圈上，衬垫在使用过程中产生的磨损现象会使内、外圈间隙过大，从而失去正常润滑能力，严重时会造成相关机构咬合卡死，所以提高自润滑衬垫工作面的耐磨性能是目前自润滑衬垫的研究热点。
树枝状高分子是近十几年发展起来的一类具有三维结构、高度有序的新型高分子，其中聚酰胺-胺树枝状高分子(PAMAM)是树枝状高分子化学中研究较为成熟的一类，以其合成简单、质量稳定、结构性能独特等优势已在多个领域中显示出广阔的应用前景，此外，PAMAM的内部为大量空腔，可以包裹小分子化合物，在一定条件下能使它们再释放出来。
在自润滑涂层领域，叶春会等(一种耐热耐磨自润滑涂料，中国专利，专利公开号CN103992726A)将环氧树脂和聚酯树脂混合，并添加少量的石墨、聚四氟乙烯粉、石英粉等纳米材料制备得到一种自润滑涂料，可快速将摩擦产生的热量导走，减少摩擦损耗，但是聚四氟乙烯粉与环氧树脂的相容性较差，降低材料的力学性能。章秋明等(一种自润滑型环氧树脂材料及其制备方法，中国专利，专利公开号CN101348600A)将润滑油胶囊、环氧树脂和固化剂混合均匀浇模，制得自润滑性环氧树脂材料。这种材料在一定程度上能够降低摩擦系数，但是润滑油胶囊不稳定，耐久性差，且材料只能现配现用，不能长期保存，应用受到限制。
在树枝状分子固化剂领域，苏江勋等(环氧基POSS/PAMAM杂合材料的制备及其性能，精细化工，2011，Vol.28，No.8)以3-缩水甘油基氧丙基三甲氧基硅烷(EPTMS)为原料，合成得到了八官能团缩水甘油醚-多面体低聚倍半硅氧烷(POSS-EP)，采用4代树型端氨基聚酰胺-胺(PAMAM)作为POSS-EP和环氧树脂共混物的固化剂，制备得到环氧基POSS/PAMAM杂化材料，该材料具有 优良的热性能和力学性能，但是该材料的固化温度在200℃以上，固化时间长，生产成本较高，不利于工业生产，而且该材料不具有疏水性能。
目前，利用含氟树枝状高分子制备自润滑型环氧酚醛涂层的相关工作还未见报道。
本发明提供了一种用于关节轴承的自润滑涂层及其制备方法，主要特征是在环氧酚醛树脂涂层中加入含氟树枝状高分子。含氟树枝状高分子的三维有序的结构在摩擦过程中能够起到“微轴承”的作用，提升材料的自润滑性能；此外氟元素易迁移和树枝状高分子易成膜的特点使得涂层表面容易形成薄膜，涂层表面摩擦系数降低；此外，无机填料在硅烷偶联剂和表面活性剂的作用下能够均匀分散在树脂中，解决传统环氧树脂涂料抗冲击性能差的缺点。
发明内容
本发明旨在提供一种应用在自润滑关节轴承领域的涂层材料及其制备方法。
所述的用于关节轴承的自润滑涂层的制备主要特征包括：
(1)首先将30～50份酚醛树脂溶于30～50份有机溶剂中，搅拌0.5～1h，得到透明溶液；其次向溶液中加入40～60份环氧树脂和10～20份含氟环氧树脂，搅拌0.5～1h之后依次加入5～20份含氟树枝状高分子、1～3份硅烷偶联剂、5～15份无机填料、0.1～0.3份环氧树脂固化促进剂和1～3份表面活性剂，快速搅拌2～3h，得到所需要的含氟自润滑涂层胶料。
(2)将含氟自润滑涂层胶料刮涂在衬垫上，然后将衬垫在80～110℃下于鼓风烘箱预先烘0.5～1h，随后粘接在处理过的金属平板上进行固化，固化条件为0.5～1MPa下，120～130℃下保温0.5～1h预固化，然后升温至160～180℃，保温1～3h。
所述自润滑涂层的配方如下：环氧树脂40～60份，含氟环氧树脂10～20份，酚醛树脂30～50份，含氟树枝状高分子5～20份，溶剂30～50份，硅烷偶联剂1～3份，填料5～15份，环氧树脂固化促进剂0.1～0.3份，表面活性剂1～3份。
所述含氟树枝状高分子的制备：取3.0～5.0份的PAMAM树枝状高分子至反应容器中，另取含氟丙烯酸酯类单体溶于甲醇中(摩尔比，PAMAM：含氟丙烯酸酯类单体＝1：(1～64))，然后将含氟丙烯酸酯类单体的甲醇溶液滴加至反应容器中，控制温度30～60℃，氮气保护下搅拌反应20～30h后，减压蒸馏除去甲 醇得到含氟树枝状高分子。
所述的树枝状高分子为聚酰胺-胺类树枝状高分子。
所述的含氟单体为含氟丙烯酸酯类单体，其结构通式为CH2＝CRCOO(CH2)mCnF2nH(R为H或CH3，m≥1,n≥1)，如丙烯酸六氟丁酯，甲基丙烯酸十二氟庚酯等。
所述的含氟环氧树脂结构为：
Figure PCTCN2017072325-appb-000001
其中R1、R2均为CF3或CF2CF3。
所述环氧树脂为商品环氧树脂，即分子中含有两个或多个环氧基团的化合物，如缩水甘油醚，缩水甘油胺，缩水甘油酯等；其中缩水甘油醚有双酚A型、双酚F型、及双酚S型等；缩水甘油胺有苯胺缩水甘油胺、二氨基二苯甲烷四缩水甘油胺等；缩水甘油酯有二缩水甘油对(邻)苯二甲酸酯等。
所述硅烷偶联剂剂采用通式为Y(CH2)nSiX3的硅烷偶联剂，其中，n＝0～3；X为氯基、乙酰氧基等，Y为氨基或环氧基。
所述酚醛树脂为热固型和热塑性酚醛树脂，所述酚醛树脂可单独使用也可混合使用。
所述的溶剂为低沸点的溶剂，包括乙酸乙酯、乙醇、丙酮，可单独使用也可多种混合使用。
所述填料为滑石粉、高岭土、氢氧化铝、粘土、二氧化硅等，所述填料可单独使用也可混合使用。
所述环氧树脂促进剂为胺类促进剂，如苄基二甲胺、三乙胺、三乙醇胺、二甲基乙醇胺等，所述促进剂可单独使用也可混合使用。
所述表面活性剂的结构通式为R4N+X-，其中R可以是相同或不同的烃基，X多为卤素原子，或酸根。
与现有技术相比，本发明具有以下优点：
1)含氟树枝状高分子具有三维有序结构，类似于“球体”，在摩擦过程中起到“微轴承”的作用，提升材料的自润滑性能；
2)含氟树枝状高分子容易成膜，增加了涂层的韧性，且降低了涂层表面的 摩擦系数，增强涂层的耐磨性能；
3)含氟树枝状高分子利用PAMAM良好的相容性解决氟元素相容性差的问题，同时氟元素的引入能够降低材料摩擦系数，增强材料的耐热性和耐候性。
4)含氟树枝状高分子结构中带有氨基，可与环氧基团反应，提高了材料的交联密度，提升了材料的力学性能。
附图说明
图1用于关节轴承的自润滑涂层中含氟树枝状高分子的作用机理图。
具体实施方式
下面结合附图及实施例对本发明作进一步描述：
实施例1：
(1)含氟树枝状高分子的制备：取10份5.0G的PAMAM树枝状高分子至三口烧瓶中，另取15份含氟丙烯酸酯类单体溶于20份甲醇中，然后将含氟丙烯酸酯类单体的甲醇溶液滴加至三口烧瓶中，控制温度在35℃，氮气保护下搅拌反应24h后停止，减压蒸馏除甲醇得到含氟树枝状高分子。
(2)自润滑涂层的制备：
1.将40份对叔丁基酚醛树脂溶于30份乙酸乙酯中，搅拌0.5h之后得到透明溶液，然后向溶液中加入50份环氧树脂和8份含氟环氧树脂，搅拌0.5h之后依次加入1份KH-560、5份滑石粉、1份高岭土、0.1份三乙醇胺、1份十六烷基三甲基溴化铵和5份含氟树枝状高分子，快速搅拌2h之后得到所需要的含氟自润滑涂层胶料
2.将含氟自润滑涂层胶料刮涂在衬垫上，然后将衬垫在110℃下用鼓风烘箱烘0.5～1h，随后粘接在处理过的金属平板上进行固化，固化条件为0.5MPa下，130℃下保温0.5h预固化，然后升温至170℃，保温1.5h。涂层的摩擦磨损性能采用往复摆动摩擦磨损实验，条件为：常温，摆动角度为±10°，接触应力52Mpa，摆动频率2Hz，每次实验连续摆动次数2.5×104次。测得摩擦系数为0.032，比磨损率为4.7±1.3(×10-6mm3/Nm)。
实施例2：
(1)含氟树枝状高分子的制备：取8份5.0G的PAMAM树枝状高分子至三口烧瓶中，另取12份含氟丙烯酸酯类单体溶于20份甲醇中，然后将含氟丙烯酸酯类 单体的甲醇溶液滴加至三口烧瓶中，控制温度在40℃，氮气保护下搅拌反应25h后停止，减压蒸馏除甲醇得到含氟树枝状高分子。
(2)自润滑涂层的制备：
1.将30份对叔丁基酚醛树脂溶于40份乙酸乙酯中，搅拌1h之后得到透明溶液，然后向溶液中加入50份环氧树脂和10份含氟环氧树脂，搅拌1h之后依次加入1份KH-560、4份滑石粉、3份高岭土、0.1份三乙醇胺、1份十六烷基三甲基溴化铵和10份含氟树枝状高分子，快速搅拌2h之后得到所需要的含氟自润滑涂层胶料
2.将含氟自润滑涂层胶料刮涂在衬垫上，然后将衬垫在110℃下用鼓风烘箱烘1h，随后粘接在处理过的金属平板上进行固化，固化条件为1MPa下，130℃下保温0.5h预固化，然后升温至170℃，保温2h。涂层的摩擦磨损性能采用往复摆动摩擦磨损实验，条件为：常温，摆动角度为±10°，接触应力52Mpa，摆动频率2Hz，每次实验连续摆动次数2.5×104次。测得摩擦系数为0.025，比磨损率为3.9±1.5(×10-6mm3/Nm)。
实施例3：
(1)含氟树枝状高分子的制备：取13份3.0G的PAMAM树枝状高分子至三口烧瓶中，另取18份含氟丙烯酸酯类单体溶于20份甲醇中，然后将含氟丙烯酸酯类单体的甲醇溶液滴加至三口烧瓶中，控制温度在35℃，氮气保护下搅拌反应24h后停止，减压蒸馏除甲醇得到含氟树枝状高分子。
(2)自润滑涂层的制备：
1.将40份对叔丁基酚醛树脂溶于30份乙酸乙酯中，搅拌0.5h之后得到透明溶液，然后向溶液中加入60份环氧树脂和8份含氟环氧树脂，搅拌0.5h之后依次加入1份KH-560、4份滑石粉、5份高岭土、0.2份三乙醇胺、1份十六烷基三甲基溴化铵和5份含氟树枝状高分子，快速搅拌2h之后得到所需要的含氟自润滑涂层胶料
2.将含氟自润滑涂层胶料刮涂在衬垫上，然后将衬垫在100℃下用鼓风烘箱烘0.5h，随后粘接在处理过的金属平板上进行固化，固化条件为0.5MPa下，120℃下保温0.5h预固化，然后升温至175℃，保温1.5h。涂层的摩擦磨损性能采用往复摆动摩擦磨损实验，条件为：常温，摆动角度为±10°，接触应力52Mpa，摆动频率2Hz，每次实验连续摆动次数2.5×104次。测得摩擦系数为0.030，比磨损率 为4.8±1.6(×10-6mm3/Nm)。
实施例4：
(1)含氟树枝状高分子的制备：取14份3.0G的PAMAM树枝状高分子至三口烧瓶中，另取15份含氟丙烯酸酯类单体溶于30份甲醇中，然后将含氟丙烯酸酯类单体的甲醇溶液滴加至三口烧瓶中，控制温度在40℃，氮气保护下搅拌反应25h后停止，减压蒸馏除甲醇得到含氟树枝状高分子。
(2)自润滑涂层的制备：
1.将40份对叔丁基酚醛树脂溶于30份乙酸乙酯中，搅拌1h之后得到透明溶液，然后向溶液中加入60份环氧树脂和10份含氟环氧树脂，搅拌1h之后依次加入1份KH-560、8份滑石粉、3份高岭土、0.2份三乙醇胺、1份十六烷基三甲基溴化铵和5份含氟树枝状高分子，快速搅拌2h之后得到所需要的含氟自润滑涂层胶料
2.将含氟自润滑涂层胶料刮涂在衬垫上，然后将衬垫在100℃下用鼓风烘箱烘0.5h，随后粘接在处理过的金属平板上进行固化，固化条件为0.5MPa下，120℃下保温0.5h预固化，然后升温至175℃，保温1.5h。涂层的摩擦磨损性能采用往复摆动摩擦磨损实验，条件为：常温，摆动角度为±10°，接触应力52Mpa，摆动频率2Hz，每次实验连续摆动次数2.5×104次。测得摩擦系数为0.027，比磨损率为5.0±1.5(×10-6mm3/Nm)。

Claims (10)

  1. 一种用于关节轴承的自润滑涂层，其特征在于其按质量比的配方如下：环氧树脂40～60，含氟环氧树脂10～20，酚醛树脂30～50，含氟树枝状高分子5～20，溶剂30～50，硅烷偶联剂1～3，填料5～15，环氧树脂固化促进剂0.1～0.3，表面活性剂1～3。
  2. 如权利要求1所述一种用于关节轴承的自润滑涂层，其特征在于所述环氧树脂采用分子中含有至少两个环氧基团的化合物，所述环氧树脂可选自缩水甘油醚、缩水甘油胺、缩水甘油酯中的一种；所述缩水甘油醚可采用双酚A型缩水甘油醚、双酚F型缩水甘油醚、双酚S型缩水甘油醚中的一种；所述缩水甘油胺可选自苯胺缩水甘油胺、二氨基二苯甲烷四缩水甘油胺中的一种；所述缩水甘油酯可采用二缩水甘油对(邻)苯二甲酸酯。
  3. 如权利要求1所述一种用于关节轴承的自润滑涂层，其特征在于所述含氟环氧树脂的结构式为：
    Figure PCTCN2017072325-appb-100001
    其中R1、R2均为CF3或CF2CF3。
  4. 如权利要求1所述一种用于关节轴承的自润滑涂层，其特征在于所述酚醛树脂采用热固型酚醛树脂或热塑性酚醛树脂，所述酚醛树脂可选自对叔丁基酚醛树脂、对苯基酚醛树脂中的至少一种。
  5. 如权利要求1所述一种用于关节轴承的自润滑涂层，其特征在于所述含氟树枝状高分子采用以下方法制备：
    取3～5份的PAMAM树枝状高分子至反应容器中，另取含氟丙烯酸酯类单体溶于甲醇中，然后将含氟丙烯酸酯类单体的甲醇溶液滴加至容器中，控制温度30～60℃，氮气保护下搅拌反应20～30h后，减压蒸馏除去甲醇得到含氟树枝状高分子；按摩尔比，PAMAM∶含氟丙烯酸酯类单体＝1∶(1～64)；所述树枝状高分子可为聚酰胺-胺类树枝状高分子；
    所述含氟丙烯酸酯类单体的结构通式为CH2＝CRCOO(CH2)mCnF2nH，其中R为H 或CH3，m≥1,n≥1，所述含氟丙烯酸酯类单体可选自丙烯酸六氟丁酯、甲基丙烯酸十二氟庚酯中的一种。
  6. 如权利要求1所述一种用于关节轴承的自润滑涂层，其特征在于所述溶剂采用低沸点溶剂，所述溶剂可选自乙酸乙酯、乙醇、丙酮中的至少一种。
  7. 如权利要求1所述一种用于关节轴承的自润滑涂层，其特征在于所述硅烷偶联剂采用通式为Y(CH2)nSiX3的硅烷偶联剂，其中，n＝0～3；X为氯基或乙酰氧基，Y为氨基或环氧基；
    所述填料可选自滑石粉、高岭土、氢氧化铝、粘土、二氧化硅中的至少一种。
  8. 如权利要求1所述一种用于关节轴承的自润滑涂层，其特征在于所述环氧树脂促进剂采用胺类促进剂，所述环氧树脂促进剂可选自苄基二甲胺、三乙胺、三乙醇胺、二甲基乙醇胺中的至少一种；
    所述表面活性剂的结构通式为R4N+X-，其中R可以是相同或不同的烃基，X多为卤素原子，或酸根。
  9. 如权利要求1所述用于关节轴承的自润滑涂层的制备方法，其特征在于包括以下步骤：
    1)将酚醛树脂溶于有机溶剂中，搅拌后得到透明溶液，在透明溶液中加入环氧树脂和含氟环氧树脂，搅拌后依次加入含氟树枝状高分子、硅烷偶联剂、无机填料、环氧树脂固化促进剂和表面活性剂，搅拌后即得含氟自润滑涂层胶料；
    2)将步骤1)得到的含氟自润滑涂层胶料刮涂在衬垫上，然后将衬垫烘干，再粘接在处理过的金属平板上进行固化，即得用于关节轴承的自润滑涂层。
  10. 如权利要求9所述用于关节轴承的自润滑涂层的制备方法，其特征在于在步骤2)中，所述烘干的条件是将衬垫在80～110℃下于鼓风烘箱烘0.5～1h；所述固化的条件可在0.5～1MPa，120～130℃下保温0.5～1h预固化，然后升温至160～180℃，保温1～3h。
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