CN107254169B - Heat-resistant electric brush and preparation method thereof - Google Patents

Heat-resistant electric brush and preparation method thereof Download PDF

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CN107254169B
CN107254169B CN201710471313.9A CN201710471313A CN107254169B CN 107254169 B CN107254169 B CN 107254169B CN 201710471313 A CN201710471313 A CN 201710471313A CN 107254169 B CN107254169 B CN 107254169B
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CN107254169A (en
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梁国正
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Suzhou University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R39/00—Rotary current collectors, distributors or interrupters
    • H01R39/02—Details for dynamo electric machines
    • H01R39/18—Contacts for co-operation with commutator or slip-ring, e.g. contact brush
    • H01R39/20—Contacts for co-operation with commutator or slip-ring, e.g. contact brush characterised by the material thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3009—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • 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

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Motor Or Generator Current Collectors (AREA)

Abstract

The invention provides a heat-resistant electric brush and a preparation method thereof, wherein the electric brush prepared by taking phenolic resin and bismaleimide resin as a base, combining epoxy resin, selecting and matching a resin matrix, combining a reasonable preparation process, extruding, granulating and then molding has excellent heat resistance and wear resistance, and simultaneously has good electrical property; can be used for high-quality and high-requirement motors and engines.

Description

Heat-resistant electric brush and preparation method thereof
Technical Field
The invention belongs to the technical field of electric tool accessories, and particularly relates to a heat-resistant electric brush and a preparation method thereof.
Background
The current potentiometer products, particularly aerospace, weaponry and the like have very strict technical requirements on special organic solid potentiometers and glass glaze potentiometers, the output voltage signal of the potentiometer is required to be very accurate and reliable to adjust, the technical requirements are closely related to electric brushes of the potentiometers, and therefore the requirements of the potentiometers on the electric brushes must simultaneously meet the requirements of multiple indexes such as appearance size, resistance, wear resistance coefficient, compressive strength, smoothness coefficient, collision, vibration and the like.
The existing electric brush has poor service performance, poor stability, over-high unit pressure of the electric brush, large resistance and high hardness, so that the abrasion of the electric brush for the motor is aggravated, the unit pressure is too small, the contact is unstable, the reversing performance is poor, and mechanical sparks are easy to occur; in particular, the wear resistance, the commutation performance, the anti-interference ability and the heat resistance are poor, and various requirements of a high-performance motor on the electric brush cannot be met.
The electric brushes can be divided into soft electric brushes, medium hard electric brushes and hard electric brushes according to the hardness of the materials; the electric brush is divided into a black electric brush (made of pure carbon graphite material) and a colored electric brush (made of metal material such as copper and graphite) according to the color of the electric brush; according to different materials of the electric brush, the electric brush can be divided into the following parts: (1) graphite brush, (2) electrochemical graphite brush, (3) metal graphite brush. In the prior art, carbon and graphite powder are generally used as base materials, and resin is used as a bonding material, and the brush is manufactured through kneading, grinding, molding and curing.
Disclosure of Invention
The invention provides a heat-resistant electric brush and a preparation method thereof, wherein the electric brush prepared by taking phenolic resin and bismaleimide resin as a base, combining epoxy resin, selecting and matching a resin matrix, combining a reasonable preparation process, extruding, granulating and then molding has excellent heat resistance and wear resistance, and simultaneously has good electrical property; can be used for high-quality and high-requirement motors and engines.
In order to achieve the purpose, the invention adopts the following technical scheme: a method of making a heat resistant brush comprising the steps of:
(1) under the protection of nitrogen, mixing ammonium hexachloroiridate, dioctyltin, zinc acetate, ethanol and cyclohexane; then refluxing and stirring for 1 hour, then adding a potassium hydroxide methanol solution, stirring for 30 minutes, and then adding tert-butyl hydroperoxide; reacting for 2 hours, naturally cooling to room temperature, adding ethyl acetate for coagulation and centrifugation; washing the centrifugal precipitate with water, and dispersing in ethanol to obtain a dispersion system; adding polyvinyl alcohol and ammonia water into a dispersion system, stirring for 1 hour at 50 ℃, then adding 3, 5-dimethylpyrazole and iron tetraphenylporphyrin, stirring for 3 hours at 60 ℃, then adding carbon nanotubes, stirring for 3 hours under reflux, and then concentrating to obtain a concentrate with the solid content of 80%; carrying out hypergravity treatment on the concentrate; then freeze-drying to obtain nanometer powder; the rotating speed of the supergravity treatment is 35000-40000 rpm; the flow rate of the concentrate is 80-90 mL/min;
(2) adding hexamethylenetetramine into the organic silicon phenolic resin, stirring for 25 minutes at 140 ℃, then adding glyceryl monostearate, and stirring for 10 minutes at 90 ℃; addition of a derivative of a phenanthrolineThe resulting mixture and 1, 8-octanedithiol were stirred for 30 minutes, and bismaleimide and lanthanum cobalt oxide (LnCoO) were added thereto3) Continuously stirring for 1 hour, then adding triethanolamine at 115 ℃, and stirring for 35 minutes to obtain a polymer matrix; adding graphene oxide into epoxy resin, stirring for 1 hour at 160 ℃, adding diphenylphosphine oxide and fatty amine polyoxyethylene ether, stirring for 2 hours at 120 ℃, then adding paraffin, stirring for 1 hour, adding a polymer matrix, and stirring for 10 minutes to obtain a heat-resistant resin system;
the chemical structural formula of the phenanthroline derivative is as follows:
Figure 100002_DEST_PATH_IMAGE001
(3) uniformly dry-grinding polyester resin, molybdenum disulfide, nano powder, a heat-resistant resin system, polystyrene, polyphenylene sulfide, zinc dimethyldithiocarbamate and an ethylene-vinyl acetate copolymer, adding the mixture into an extruder, and extruding the mixture at 175 ℃ to obtain electric brush composition particles; the brush composition particles are hot-pressed, cut and polished to obtain the heat-resistant brush.
The invention also discloses a nanometer conductive powder and a preparation method thereof, and the nanometer conductive powder comprises the following steps of mixing ammonium hexachloroiridate, dioctyltin, zinc acetate, ethanol and cyclohexane under the protection of nitrogen; then refluxing and stirring for 1 hour, then adding a potassium hydroxide methanol solution, stirring for 30 minutes, and then adding tert-butyl hydroperoxide; reacting for 2 hours, naturally cooling to room temperature, adding ethyl acetate for coagulation and centrifugation; washing the centrifugal precipitate with water, and dispersing in ethanol to obtain a dispersion system; adding polyvinyl alcohol and ammonia water into a dispersion system, stirring for 1 hour at 50 ℃, then adding 3, 5-dimethylpyrazole and iron tetraphenylporphyrin, stirring for 3 hours at 60 ℃, then adding carbon nanotubes, stirring for 3 hours under reflux, and then concentrating to obtain a concentrate with the solid content of 80%; carrying out hypergravity treatment on the concentrate; then freeze-drying to obtain nanometer powder; the rotating speed of the supergravity treatment is 35000-40000 rpm; the flow rate of the concentrate is 80-90 mL/min.
The invention also discloses a polymer matrix and a preparation method thereof, which comprises the following stepsAdding hexamethylenetetramine into organic silicon phenolic resin, stirring for 25 minutes at 140 ℃, then adding glyceryl monostearate, and stirring for 10 minutes at 90 ℃; adding a phenanthroline derivative and 1, 8-octanedithiol, stirring for 30 minutes, and adding bismaleimide and lanthanum cobalt oxide (LnCoO)3) And stirring for 1 hour, adding triethanolamine at 115 ℃, and stirring for 35 minutes to obtain a polymer matrix.
The invention also discloses an electric brush composition and a preparation method thereof, and the electric brush composition comprises the following steps:
(1) under the protection of nitrogen, mixing ammonium hexachloroiridate, dioctyltin, zinc acetate, ethanol and cyclohexane; then refluxing and stirring for 1 hour, then adding a potassium hydroxide methanol solution, stirring for 30 minutes, and then adding tert-butyl hydroperoxide; reacting for 2 hours, naturally cooling to room temperature, adding ethyl acetate for coagulation and centrifugation; washing the centrifugal precipitate with water, and dispersing in ethanol to obtain a dispersion system; adding polyvinyl alcohol and ammonia water into a dispersion system, stirring for 1 hour at 50 ℃, then adding 3, 5-dimethylpyrazole and iron tetraphenylporphyrin, stirring for 3 hours at 60 ℃, then adding carbon nanotubes, stirring for 3 hours under reflux, and then concentrating to obtain a concentrate with the solid content of 80%; carrying out hypergravity treatment on the concentrate; then freeze-drying to obtain nanometer powder; the rotating speed of the supergravity treatment is 35000-40000 rpm; the flow rate of the concentrate is 80-90 mL/min;
(2) adding hexamethylenetetramine into the organic silicon phenolic resin, stirring for 25 minutes at 140 ℃, then adding glyceryl monostearate, and stirring for 10 minutes at 90 ℃; adding a phenanthroline derivative and 1, 8-octanedithiol, stirring for 30 minutes, and adding bismaleimide and lanthanum cobalt oxide (LnCoO)3) Continuously stirring for 1 hour, then adding triethanolamine at 115 ℃, and stirring for 35 minutes to obtain a polymer matrix; adding graphene oxide into epoxy resin, stirring for 1 hour at 160 ℃, adding diphenylphosphine oxide and fatty amine polyoxyethylene ether, stirring for 2 hours at 120 ℃, then adding paraffin, stirring for 1 hour, adding a polymer matrix, and stirring for 10 minutes to obtain a heat-resistant resin system;
the chemical structural formula of the phenanthroline derivative is as follows:
Figure 953915DEST_PATH_IMAGE001
(3) the polyester resin, the molybdenum disulfide, the nano powder, the heat-resistant resin system, the polystyrene, the polyphenylene sulfide, the zinc dimethyldithiocarbamate and the ethylene-vinyl acetate copolymer are added into an extruder after being dry-ground uniformly, and the electric brush composition is obtained by extrusion at 175 ℃.
The invention also discloses a heat-resistant resin system and a preparation method thereof, and the heat-resistant resin system comprises the following steps of adding hexamethylenetetramine into the organic silicon phenolic resin, stirring for 25 minutes at 140 ℃, then adding glyceryl monostearate, and stirring for 10 minutes at 90 ℃; adding a phenanthroline derivative and 1, 8-octanedithiol, stirring for 30 minutes, and adding bismaleimide and lanthanum cobalt oxide (LnCoO)3) Continuously stirring for 1 hour, then adding triethanolamine at 115 ℃, and stirring for 35 minutes to obtain a polymer matrix; adding graphene oxide into epoxy resin, stirring for 1 hour at 160 ℃, adding diphenylphosphine oxide and fatty amine polyoxyethylene ether, stirring for 2 hours at 120 ℃, then adding paraffin, stirring for 1 hour, adding a polymer matrix, and stirring for 10 minutes to obtain a heat-resistant resin system.
In the technical scheme, the mass ratio of ammonium hexachloroiridate, dioctyltin, zinc acetate, ethanol, cyclohexane, potassium hydroxide methanol solution, tert-butyl hydroperoxide, polyvinyl alcohol, ammonia water, 3, 5-dimethylpyrazole, iron tetraphenylporphyrin and carbon nano tube is 15: 30: 55: 200: 150: 20: 15: 10: 8: 5: 3; the mass ratio of hexamethylene tetramine, organic silicon phenolic resin, glyceryl monostearate, a phenanthroline derivative, 1, 8-octanedithiol, bismaleimide, lanthanum cobalt trioxide, triethanolamine, graphene oxide, epoxy resin, diphenylphosphine, fatty amine polyoxyethylene ether and paraffin is 11: 20: 6: 5: 8: 100: 0.5: 10: 3: 30: 12: 8: 6; the mass ratio of the terylene resin, the molybdenum disulfide, the nano powder, the heat-resistant resin system, the polystyrene, the polyphenylene sulfide, the zinc dimethyldithiocarbamate and the ethylene-vinyl acetate copolymer is 12: 3: 28: 100: 5: 6: 2: 12.
In the invention, the mass concentration of potassium hydroxide in the potassium hydroxide methanol solution is 4.5%; the molecular weight of the fatty amine polyoxyethylene ether is 2500-3500; the molecular weight of the polyvinyl alcohol is 1500-2000. According to the invention, the surface activity of the conductive powder is increased by adding the ammonia water while adding the polyvinyl alcohol, and the tetraphenylporphyrin iron is added after mixing, more importantly, the molecular weight of the polyvinyl alcohol is reduced to a certain extent, namely, the molecular chain of the polyvinyl alcohol is degraded to a certain extent, so that the key help is provided for improving the dispersion property and the continuity property of the metal oxide after the subsequent conductive nano powder is mixed with the resin, especially the influence of the polyvinyl alcohol with poor thermal property and wear resistance on the whole performance is avoided, the advantages that the activity of the polyvinyl alcohol is improved by combining other compounds on the surface of the conductive powder and the compatibility is increased are fully exerted, the good electrical property is embodied, and the problem that the heat resistance and the wear resistance are reduced by the polyvinyl alcohol participating.
The hot pressing condition of the invention is 1MPa/150 ℃ curing for 2.5-3.0 h +2MPa/190 ℃ curing for 1.5-2.0 h +1.5MPa/220 ℃ curing for 3.5-4.5 h, and the modified resin with excellent performance can be obtained by gradually curing in three sections along with the temperature rise; the unmodified resin has low elongation and large brittleness, and the prepared brush is not suitable for use because the brush is not fatigue-resistant, and the heat resistance or the moist heat resistance is reduced by adding a diallyl compound, diamine and epoxy resin. The modified epoxy/phenolic aldehyde/bismaleimide resin has greatly improved toughness on the premise that the heat resistance and the flexural modulus are not influenced, and particularly reduces the risk of friction cracking of an electric brush.
The invention also discloses a product prepared by the preparation method and a motor brush structure, wherein the brush structure comprises the brush prepared by the preparation method and a brush holder.
In the invention, besides high-performance resin, a plurality of small molecular compounds are designed, and a polymerization reaction process is combined, so that a system can form a bicontinuous phase structure in the process of phase separation induced by polymerization reaction, and a phase inversion phenomenon can occur under certain conditions, namely the system is used as a small amount of components to react to form a thermoplastic unit to become an auxiliary continuous phase of the system. The reverse phase structure is composed of a small amount of thermoplastic units to form a net-shaped continuous phase, the mechanical property, the thermal property and the electrical property of the system are mainly the main continuous phase, and the small amount of thermoplastic units are controlled through parameter design, so that the structure is favorable for greatly improving the performance of the system.
The existing toughening agent has certain toughening and plasticizing effects, but due to the structural limitation, the crosslinking density, the mechanical property and the heat resistance of a thermosetting resin system are reduced after the thermosetting resin system is added, and the original purpose of a high-performance heat-resistant polymer is violated; according to the technical scheme of the invention, glyceryl monostearate and 1, 8-octanedithiol have stronger activity, can react with phenolic aldehyde firstly, then carry out grafting reaction with epoxy resin, introduce long chains with good toughness and heat resistance (breaking phenol ring and needing higher heat energy) and benzene ring structures into the epoxy resin, play a role of internal toughening and can reduce hardness, thereby achieving the aim of purposefully modifying matrix resin, and the combination of hexamethylenetetramine and diphenylphosphine avoids excessive flexibility, so that a cured product has high heat resistance and mechanical strength, and the technical requirements of heat resistance, easy processability, friction resistance and water resistance of an electric brush material are met.
According to the invention, the composite conductive filler is obtained by modifying metal iridium for the first time, then the resin matrix is combined to manufacture the brush material, powder with different properties, organic micromolecules and polymers form a uniform network structure through the chemical activity of iridium, so that the interaction and mutual wetting of all components at an interface are facilitated, the whole material system is in the most thermodynamically stable state, and the carbonized substances and micromolecule substances generated under the high-temperature working condition of the brush material are few, so that the heat fading of the friction coefficient is small, particularly, the modified rare earth metal is added into the resin system, the influence on the polymerization of the resin matrix is avoided, and the conductivity level of the system can be improved; the product of the invention has high friction coefficient and stable electrical property.
Various indexes of the electric brush in practical application are greatly influenced mutually, and it is very difficult for multiple indexes to simultaneously meet the requirements, for example, the smaller the resistance of the electric brush is, the better the resistance is, but the smaller the resistance is, the lower the strength is, and the influence is lowered. The variety, the proportion, the granularity and the size of the electric brush material, the dispersion uniformity in the processing process, the method in the processing process and the like all have influence on the technical indexes, the key for solving the problem is a scheme capable of meeting the requirements of all the technical indexes simultaneously, and the technical effect can be achieved through the combination of the formula and the process.
According to the invention, the organic silicon phenolic resin is added into the bismaleimide, and the double bonds and the hydroxymethyl of the organic silicon phenolic resin are subjected to addition reaction in the curing process, so that the heat resistance and the bonding strength of the organic silicon phenolic resin are improved, and the toughness of the organic silicon phenolic resin is maintained; the addition of the epoxy resin avoids the reduction of the storage period at normal temperature, and solves the problem caused by the condensation of a small amount of carboxyl and amido with the hydroxymethyl of the organic silicon phenolic resin at normal temperature.
With the implementation of the forbidden hazardous substance prevention method (RoHS), environmental friendly materials have become a basic property requirement rather than a requirement, and although the regulations in different countries are different, they are generally not changed. In the existing environment-friendly halogen-free material formula composition, phosphide is generally selected as a flame retardant to replace halogen compounds, but when a phosphorus flame retardant material is used, the UL-94 test specification can be passed only by matching inorganic powder, the matched inorganic powder is usually hydroxide, and the commonly used hydroxide is respectively silicon dioxide and aluminum hydroxide, so that the obvious defects exist when the flame retardant material is used for an electric brush, and besides the influence on the electrical property, the wear resistance and the heat resistance are influenced; the invention limits the dosage proportion of a plurality of compounds through the coordination among organic matters, such as the synergistic action of P-Si-N elements, realizes the halogen-free flame retardance of the electric brush and reaches V0 level.
Under the conditions of smaller volume and higher running speed, the heat generated by the electric brush is also increased, and if the heat cannot be timely discharged to the external environment, the reliability of the product is affected and the service life of the product is reduced due to overhigh temperature of the electric brush assembly. Therefore, how to dissipate heat while improving heat resistance to maintain stable operation of the system becomes more and more important, because the rate of damage or loss of function due to high temperature is much higher than that due to other factors such as vibration, friction, etc., among the causes of damage to the brush device; therefore, the development of highly heat-resistant substrate materials having various required characteristics is one of the major points of continuous research and development in the brush industry for a long time.
Phenolic and bismaleimide resins have good heat resistance, but are not brittle and have insufficient water absorption, and epoxy resins are generally modified by epoxy resins, but epoxy resins can cause remarkable reduction of thermal properties. According to the invention, through the use of the phenanthroline derivative and the polyphenylene sulfide, the hydrophobic property of the modified thermosetting resin composition is increased, in addition, the reactive thiol group, amino group and pyrazole are introduced into a system, so that the crosslinking density of the resin composition can be reduced, and the toughness can be increased by matching with polystyrene and an ethylene-vinyl acetate copolymer, so that the obtained modified resin composition has higher mechanical strength and processing stability; in addition, the small molecular compounds with a certain proportion do not influence the final crosslinking and curing of the modified resin into a network structure, but avoid the generation of low molecular weight condensation polymers; therefore, the bismaleimide resin, the epoxy resin and the phenolic resin are modified by a plurality of compounds, the heat resistance and the strength of the resin are maintained, the moisture resistance and the toughness are effectively improved, meanwhile, the generation of low molecular weight polycondensate in the thermosetting resin curing process is reduced by micromolecules, the friction defect and the stress defect are reduced, and the wear resistance is improved to a certain extent.
The content of rigid groups such as benzene rings and the like in a molecular structure is controlled within a certain range through ratio limitation, so that the melt viscosity of the resin is reduced, and the process processability is improved; and maintains good heat resistance due to the rigid structure of the resin skeleton, and has good moisture resistance, flame retardancy and reliability, and a low in-plane thermal expansion coefficient. In the prior art, the epoxy can play a certain role in catalyzing the curing reaction of bismaleimide and the like, thereby being beneficial to improving the conversion rate of monomers in the curing process and promoting the completion of the curing reaction; however, the existing modified resin system has the manufacturability problems of larger reactivity and short working period, which can generate adverse effects on the mechanical property, the electrical property and the practical application of the resin system. According to the invention, 1, 8-octanedithiol, zinc dimethyldithiocarbamate and paraffin are introduced into the bismaleimide/phenolic aldehyde/epoxy modified resin, so that the technological properties of the uncured resin can be improved, and the mechanical and heat-resistant properties of the cured resin can be improved; the phenanthroline derivative and the 1, 8-octanedithiol can be subjected to polymerization reaction with a resin monomer, so that a certain flexible unit can be conveniently introduced into a thermosetting curing network structure. The chemical chain structure is beneficial to improving the performances of toughness, electricity, wear resistance, water resistance and the like of the resin material under the condition of small heat resistance loss, for example, the water absorption is less than 0.8 percent after boiling for 96 hours.
The invention creatively adopts the composite metal oxide iridium-tin-zinc oxide nano particles as the conductive material, not only provides excellent conductivity of the electric brush, but also can promote a resin matrix to form a good network structure, thereby being beneficial to improving the comprehensive performance of the electric brush, and particularly solves the problems that the prior carbon material as a conductive agent has uneven dispersion and poor compatibility with a resin system in combination with rare earth metal added during resin prepolymerization, so that the electric brush cannot better achieve excellent comprehensive performance. Meanwhile, a small amount of carbon material is added, so that the special structure of the carbon material can be facilitated, the stability and smoothness of a conductive network are improved, and the electrical property of the electric brush is further improved.
The invention carries out resin modification at the middle and low temperature in extrusion for the first time, not only solves the defects of nonuniform polymerization and easy occurrence of oligomers in a melting method, but also solves the problem that the extrusion method has weak reactivity and cannot be used for melting and mixing a plurality of high polymers of compounds with different properties by the action of an addition process and small molecules; the thermoplastic resin with good thermal property is added into the thermosetting resin main body, so that the processability of the prepolymer is improved, excessive polymerization is avoided, particularly, the electric brush obtained by adding the thermoplastic resin is easy to polish and process, the mechanical property is good, and the electrical property and the thermal property are still good; after the modified resin prepared by the invention is used for preparing the electric brush, the modified resin can be well mixed with conductive powder and can be combined with a curing process to obtain an electric brush product with uniform and stable texture and good performance, particularly electrical performance, thermal performance, wear resistance and flame retardance.
The particles are small in particle size, large in specific surface area and high in surface energy, and are easy to agglomerate, so that the particles are difficult to uniformly disperse in a high polymer material. According to the invention, firstly, metal iridium is added to improve the activity of the composite metal oxide, if the composite metal oxide is not further treated, the composite metal oxide is not beneficial to mixing of the conductive powder and the resin matrix, then the surface of the particle is treated by utilizing polyvinyl alcohol, meanwhile, 3, 5-dimethylpyrazole and iron tetraphenylporphyrin are added, and the inorganic filler is treated differently from other coupling agents, the polyvinyl alcohol is slightly degraded under a certain condition, so that the composite metal oxide has two benefits, namely, the condition that the complete coverage of a macromolecular chain structure on the particle influences the conductivity is avoided, the reactivity of the 3, 5-dimethylpyrazole and the carbon nano tube can be increased, so that the surface of the particle is provided with an active organic matter, and particularly, the contact level and effect of the metal oxide and a small molecular compound can be improved in; finally, the problem of particle agglomeration is thoroughly solved through the supergravity treatment, and meanwhile, active groups on the surface of the particles are reserved. Therefore, the conductive nano powder obtained by the invention can effectively improve the agglomeration phenomenon of nano particles, and functional groups on the surfaces of the nano particles can be copolymerized and polymerized with polymers such as epoxy resin, phenolic resin, bismaleimide resin and the like, so that the dispersibility and stability of the nano particles in the polymers are greatly improved, and the electrical property, the heat resistance and the wear resistance can be obviously seen.
Detailed Description
Example one
A method of making a heat resistant brush comprising the steps of:
(1) under the protection of nitrogen, mixing ammonium hexachloroiridate, dioctyltin, zinc acetate, ethanol and cyclohexane; then refluxing and stirring for 1 hour, then adding a potassium hydroxide methanol solution, stirring for 30 minutes, and then adding tert-butyl hydroperoxide; reacting for 2 hours, naturally cooling to room temperature, adding ethyl acetate for coagulation and centrifugation; washing the centrifugal precipitate with water, and dispersing in ethanol to obtain a dispersion system; adding polyvinyl alcohol and ammonia water into a dispersion system, stirring for 1 hour at 50 ℃, then adding 3, 5-dimethylpyrazole and iron tetraphenylporphyrin, stirring for 3 hours at 60 ℃, then adding carbon nanotubes, stirring for 3 hours under reflux, and then concentrating to obtain a concentrate with the solid content of 80%; carrying out hypergravity treatment on the concentrate; then freeze-drying to obtain nanometer powder; the rotating speed of the supergravity treatment is 35000 pm; the flow rate of the concentrate is 80 mL/min;
(2) adding hexamethylenetetramine into the organic silicon phenolic resin, stirring for 25 minutes at 140 ℃, then adding glyceryl monostearate, and stirring for 10 minutes at 90 ℃; adding a phenanthroline derivative and 1, 8-octanedithiol, stirring for 30 minutes, and adding 4,4' -diphenylmethane bismaleimide and lanthanum cobalt oxide (LnCoO)3) Continuously stirring for 1 hour, then adding triethanolamine at 115 ℃, and stirring for 35 minutes to obtain a polymer matrix; adding graphene oxide into bisphenol A epoxy resin, stirring for 1 hour at 160 ℃, adding diphenylphosphine oxide and fatty amine polyoxyethylene ether, stirring for 2 hours at 120 ℃, then adding paraffin, stirring for 1 hour, adding a polymer matrix, and stirring for 10 minutes to obtain a heat-resistant resin system;
(3) uniformly dry-grinding polyester resin, molybdenum disulfide, nano powder, a heat-resistant resin system, polystyrene, polyphenylene sulfide, zinc dimethyldithiocarbamate and an ethylene-vinyl acetate copolymer, adding the mixture into an extruder, and extruding the mixture at 175 ℃ to obtain electric brush composition particles; the brush composition particles are hot-pressed, cut and polished to obtain the heat-resistant brush.
The hot pressing condition is 1MPa/150 ℃ curing for 2.5 hours, 2MPa/190 ℃ curing for 2.0 hours and 1.5MPa/220 ℃ curing for 4.5 hours.
Example two
A method of making a heat resistant brush comprising the steps of:
(1) under the protection of nitrogen, mixing ammonium hexachloroiridate, dioctyltin, zinc acetate, ethanol and cyclohexane; then refluxing and stirring for 1 hour, then adding a potassium hydroxide methanol solution, stirring for 30 minutes, and then adding tert-butyl hydroperoxide; reacting for 2 hours, naturally cooling to room temperature, adding ethyl acetate for coagulation and centrifugation; washing the centrifugal precipitate with water, and dispersing in ethanol to obtain a dispersion system; adding polyvinyl alcohol and ammonia water into a dispersion system, stirring for 1 hour at 50 ℃, then adding 3, 5-dimethylpyrazole and iron tetraphenylporphyrin, stirring for 3 hours at 60 ℃, then adding carbon nanotubes, stirring for 3 hours under reflux, and then concentrating to obtain a concentrate with the solid content of 80%; carrying out hypergravity treatment on the concentrate; then freeze-drying to obtain nanometer powder; the rotating speed of the hypergravity treatment is 35000 rpm; the flow rate of the concentrate is 90 mL/min;
(2) adding hexamethylenetetramine into the organic silicon phenolic resin, stirring for 25 minutes at 140 ℃, then adding glyceryl monostearate, and stirring for 10 minutes at 90 ℃; adding a phenanthroline derivative and 1, 8-octanedithiol, stirring for 30 minutes, and adding 4,4' -diphenylmethane bismaleimide and lanthanum cobalt oxide (LnCoO)3) Continuously stirring for 1 hour, then adding triethanolamine at 115 ℃, and stirring for 35 minutes to obtain a polymer matrix; adding graphene oxide into p-aminophenol triglycidyl epoxy resin, stirring for 1 hour at 160 ℃, adding diphenylphosphine oxide and fatty amine polyoxyethylene ether, stirring for 2 hours at 120 ℃, then adding paraffin, stirring for 1 hour, adding a polymer matrix, and stirring for 10 minutes to obtain a heat-resistant resin system;
(3) uniformly dry-grinding polyester resin, molybdenum disulfide, nano powder, a heat-resistant resin system, polystyrene, polyphenylene sulfide, zinc dimethyldithiocarbamate and an ethylene-vinyl acetate copolymer, adding the mixture into an extruder, and extruding the mixture at 175 ℃ to obtain electric brush composition particles; the brush composition particles are hot-pressed, cut and polished to obtain the heat-resistant brush.
The hot pressing condition is 1MPa/150 ℃ curing for 2.5 hours, 2MPa/190 ℃ curing for 1.5 hours and 1.5MPa/220 ℃ curing for 4.5 hours.
EXAMPLE III
A method of making a heat resistant brush comprising the steps of:
(1) under the protection of nitrogen, mixing ammonium hexachloroiridate, dioctyltin, zinc acetate, ethanol and cyclohexane; then refluxing and stirring for 1 hour, then adding a potassium hydroxide methanol solution, stirring for 30 minutes, and then adding tert-butyl hydroperoxide; reacting for 2 hours, naturally cooling to room temperature, adding ethyl acetate for coagulation and centrifugation; washing the centrifugal precipitate with water, and dispersing in ethanol to obtain a dispersion system; adding polyvinyl alcohol and ammonia water into a dispersion system, stirring for 1 hour at 50 ℃, then adding 3, 5-dimethylpyrazole and iron tetraphenylporphyrin, stirring for 3 hours at 60 ℃, then adding carbon nanotubes, stirring for 3 hours under reflux, and then concentrating to obtain a concentrate with the solid content of 80%; carrying out hypergravity treatment on the concentrate; then freeze-drying to obtain nanometer powder; the rotating speed of the supergravity treatment is 40000 rpm; the flow rate of the concentrate is 80 mL/min;
(2) adding hexamethylenetetramine into the organic silicon phenolic resin, stirring for 25 minutes at 140 ℃, then adding glyceryl monostearate, and stirring for 10 minutes at 90 ℃; adding a phenanthroline derivative and 1, 8-octanedithiol, stirring for 30 minutes, and adding 4,4' -diphenylmethane bismaleimide and lanthanum cobalt oxide (LnCoO)3) Continuously stirring for 1 hour, then adding triethanolamine at 115 ℃, and stirring for 35 minutes to obtain a polymer matrix; adding graphene oxide into bisphenol E epoxy resin, stirring for 1 hour at 160 ℃, adding diphenylphosphine oxide and fatty amine polyoxyethylene ether, stirring for 2 hours at 120 ℃, then adding paraffin, stirring for 1 hour, adding a polymer matrix, and stirring for 10 minutes to obtain a heat-resistant resin system;
(3) uniformly dry-grinding polyester resin, molybdenum disulfide, nano powder, a heat-resistant resin system, polystyrene, polyphenylene sulfide, zinc dimethyldithiocarbamate and an ethylene-vinyl acetate copolymer, adding the mixture into an extruder, and extruding the mixture at 175 ℃ to obtain electric brush composition particles; the brush composition particles are hot-pressed, cut and polished to obtain the heat-resistant brush.
The hot pressing condition is 1MPa/150 ℃ curing for 2.5 hours, 2MPa/190 ℃ curing for 2.0 hours and 1.5MPa/220 ℃ curing for 3.5 hours.
Example four
A method of making a heat resistant brush comprising the steps of:
(1) under the protection of nitrogen, mixing ammonium hexachloroiridate, dioctyltin, zinc acetate, ethanol and cyclohexane; then refluxing and stirring for 1 hour, then adding a potassium hydroxide methanol solution, stirring for 30 minutes, and then adding tert-butyl hydroperoxide; reacting for 2 hours, naturally cooling to room temperature, adding ethyl acetate for coagulation and centrifugation; washing the centrifugal precipitate with water, and dispersing in ethanol to obtain a dispersion system; adding polyvinyl alcohol and ammonia water into a dispersion system, stirring for 1 hour at 50 ℃, then adding 3, 5-dimethylpyrazole and iron tetraphenylporphyrin, stirring for 3 hours at 60 ℃, then adding carbon nanotubes, stirring for 3 hours under reflux, and then concentrating to obtain a concentrate with the solid content of 80%; carrying out hypergravity treatment on the concentrate; then freeze-drying to obtain nanometer powder; the rotating speed of the supergravity treatment is 40000 rpm; the flow rate of the concentrate is 90 mL/min;
(2) adding hexamethylenetetramine into the organic silicon phenolic resin, stirring for 25 minutes at 140 ℃, then adding glyceryl monostearate, and stirring for 10 minutes at 90 ℃; adding a phenanthroline derivative and 1, 8-octanedithiol, stirring for 30 minutes, and adding 4,4' -diphenyl ether bismaleimide and lanthanum cobalt oxide (LnCoO)3) Continuously stirring for 1 hour, then adding triethanolamine at 115 ℃, and stirring for 35 minutes to obtain a polymer matrix; adding graphene oxide into p-aminophenol triglycidyl epoxy resin, stirring for 1 hour at 160 ℃, adding diphenylphosphine oxide and fatty amine polyoxyethylene ether, stirring for 2 hours at 120 ℃, then adding paraffin, stirring for 1 hour, adding a polymer matrix, and stirring for 10 minutes to obtain a heat-resistant resin system;
(3) uniformly dry-grinding polyester resin, molybdenum disulfide, nano powder, a heat-resistant resin system, polystyrene, polyphenylene sulfide, zinc dimethyldithiocarbamate and an ethylene-vinyl acetate copolymer, adding the mixture into an extruder, and extruding the mixture at 175 ℃ to obtain electric brush composition particles; the brush composition particles are hot-pressed, cut and polished to obtain the heat-resistant brush.
The hot pressing condition is 1MPa/150 ℃ curing for 3.0 hours, 2MPa/190 ℃ curing for 2.0 hours and 1.5MPa/220 ℃ curing for 4.5 hours.
EXAMPLE five
A method of making a heat resistant brush comprising the steps of:
(1) under the protection of nitrogen, mixing ammonium hexachloroiridate, dioctyltin, zinc acetate, ethanol and cyclohexane; then refluxing and stirring for 1 hour, then adding a potassium hydroxide methanol solution, stirring for 30 minutes, and then adding tert-butyl hydroperoxide; reacting for 2 hours, naturally cooling to room temperature, adding ethyl acetate for coagulation and centrifugation; washing the centrifugal precipitate with water, and dispersing in ethanol to obtain a dispersion system; adding polyvinyl alcohol and ammonia water into a dispersion system, stirring for 1 hour at 50 ℃, then adding 3, 5-dimethylpyrazole and iron tetraphenylporphyrin, stirring for 3 hours at 60 ℃, then adding carbon nanotubes, stirring for 3 hours under reflux, and then concentrating to obtain a concentrate with the solid content of 80%; carrying out hypergravity treatment on the concentrate; then freeze-drying to obtain nanometer powder; the rotating speed of the hypergravity treatment is 35000 rpm; the flow rate of the concentrate is 80 mL/min;
(2) adding hexamethylenetetramine into the organic silicon phenolic resin, stirring for 25 minutes at 140 ℃, then adding glyceryl monostearate, and stirring for 10 minutes at 90 ℃; adding a phenanthroline derivative and 1, 8-octanedithiol, stirring for 30 minutes, and adding 4,4' -diphenyl ether bismaleimide and lanthanum cobalt oxide (LnCoO)3) Continuously stirring for 1 hour, then adding triethanolamine at 115 ℃, and stirring for 35 minutes to obtain a polymer matrix; adding graphene oxide into bisphenol A epoxy resin, stirring for 1 hour at 160 ℃, adding diphenylphosphine oxide and fatty amine polyoxyethylene ether, stirring for 2 hours at 120 ℃, then adding paraffin, stirring for 1 hour, adding a polymer matrix, and stirring for 10 minutes to obtain a heat-resistant resin system;
(3) uniformly dry-grinding polyester resin, molybdenum disulfide, nano powder, a heat-resistant resin system, polystyrene, polyphenylene sulfide, zinc dimethyldithiocarbamate and an ethylene-vinyl acetate copolymer, adding the mixture into an extruder, and extruding the mixture at 175 ℃ to obtain electric brush composition particles; the brush composition particles are hot-pressed, cut and polished to obtain the heat-resistant brush.
The hot pressing condition is 1MPa/150 ℃ curing for 3.0 hours, 2MPa/190 ℃ curing for 2.0 hours and 1.5MPa/220 ℃ curing for 3.5 hours.
EXAMPLE six
A method of making a heat resistant brush comprising the steps of:
(1) under the protection of nitrogen, mixing ammonium hexachloroiridate, dioctyltin, zinc acetate, ethanol and cyclohexane; then refluxing and stirring for 1 hour, then adding a potassium hydroxide methanol solution, stirring for 30 minutes, and then adding tert-butyl hydroperoxide; reacting for 2 hours, naturally cooling to room temperature, adding ethyl acetate for coagulation and centrifugation; washing the centrifugal precipitate with water, and dispersing in ethanol to obtain a dispersion system; adding polyvinyl alcohol and ammonia water into a dispersion system, stirring for 1 hour at 50 ℃, then adding 3, 5-dimethylpyrazole and iron tetraphenylporphyrin, stirring for 3 hours at 60 ℃, then adding carbon nanotubes, stirring for 3 hours under reflux, and then concentrating to obtain a concentrate with the solid content of 80%; carrying out hypergravity treatment on the concentrate; then freeze-drying to obtain nanometer powder; the rotating speed of the supergravity treatment is 40000 rpm; the flow rate of the concentrate is 90 mL/min;
(2) adding hexamethylenetetramine into the organic silicon phenolic resin, stirring for 25 minutes at 140 ℃, then adding glyceryl monostearate, and stirring for 10 minutes at 90 ℃; adding a phenanthroline derivative and 1, 8-octanedithiol, stirring for 30 minutes, and adding 4,4' -diphenyl sulfone bismaleimide and lanthanum cobalt oxide (LnCoO)3) Continuously stirring for 1 hour, then adding triethanolamine at 115 ℃, and stirring for 35 minutes to obtain a polymer matrix; adding graphene oxide into bisphenol A epoxy resin, stirring for 1 hour at 160 ℃, adding diphenylphosphine oxide and fatty amine polyoxyethylene ether, stirring for 2 hours at 120 ℃, then adding paraffin, stirring for 1 hour, adding a polymer matrix, and stirring for 10 minutes to obtain a heat-resistant resin system;
(3) uniformly dry-grinding polyester resin, molybdenum disulfide, nano powder, a heat-resistant resin system, polystyrene, polyphenylene sulfide, zinc dimethyldithiocarbamate and an ethylene-vinyl acetate copolymer, adding the mixture into an extruder, and extruding the mixture at 175 ℃ to obtain electric brush composition particles; the brush composition particles are hot-pressed, cut and polished to obtain the heat-resistant brush.
The hot pressing condition is 1MPa/150 ℃ curing for 3.0 hours, 2MPa/190 ℃ curing for 1.5 hours and 1.5MPa/220 ℃ curing for 4.5 hours.
In the invention, the chemical structural formula of the phenanthroline derivative is as follows:
Figure 237129DEST_PATH_IMAGE001
ammonium hexachloroiridate, dioctyltin, zinc acetate, ethanol, cyclohexane, potassium hydroxide methanol solution, tert-butyl hydroperoxide, polyvinyl alcohol, ammonia water, 3, 5-dimethylpyrazole, tetraphenylporphyrin iron and carbon nano tube in the mass ratio of 15: 30: 55: 200: 150: 20: 15: 20: 10: 8: 5: 3; the mass ratio of hexamethylene tetramine, organic silicon phenolic resin, glyceryl monostearate, a phenanthroline derivative, 1, 8-octanedithiol, bismaleimide, lanthanum cobalt trioxide, triethanolamine, graphene oxide, epoxy resin, diphenylphosphine, fatty amine polyoxyethylene ether and paraffin is 11: 20: 6: 5: 8: 100: 0.5: 10: 3: 30: 12: 8: 6; the mass ratio of the terylene resin, the molybdenum disulfide, the nano powder, the heat-resistant resin system, the polystyrene, the polyphenylene sulfide, the zinc dimethyldithiocarbamate and the ethylene-vinyl acetate copolymer is 12: 3: 28: 100: 5: 6: 2: 12.
The mass concentration of potassium hydroxide in the potassium hydroxide methanol solution is 4.5 percent; the molecular weight of the fatty amine polyoxyethylene ether is 2500-3500; the molecular weight of the polyvinyl alcohol is 1500-2000.
The electric brush and the existing electric brush base are combined to obtain a motor electric brush structure, and the motor electric brush structure is actually verified by utilizing a 24V speed reducer, and the motor electric brush still normally operates after being started for fifty thousand times; the abrasion of the electric brush is 3.7-3.8 mm, and the abrasion of the commutator is 1.03 mm.
Comparative example 1
A method for preparing a heat-resistant brush, which is similar to that of the example, except that the centrifugal precipitate (i.e., metal oxide) in the step (1) is replaced by graphite powder.
Comparative example No. two
A method for manufacturing a heat-resistant brush, which is similar to that of the example, except that ammonium hexachloroiridate is not added in the step (1).
Comparative example No. three
A method for preparing a heat-resistant electric brush is as follows from the examples, wherein the difference is that no ammonia water or tetraphenylporphyrin iron is added in the step (1).
Comparative example No. four
A method for preparing a heat-resistant brush, which is similar to that of the example, except that in the step (2), a phenanthroline derivative and 1, 8-octanedithiol are replaced by octanediamine.
Comparative example five
A method for preparing a heat-resistant brush is similar to that of the embodiment except that lanthanum cobalt oxide is not added in the step (2).
Comparative example six
The preparation method of the heat-resistant electric brush is consistent with the embodiment, wherein the difference is that no diphenylphosphine oxide, fatty amine polyoxyethylene ether and paraffin are added in the step (2).
Comparative example seven
A heat-resistant brush is prepared in a manner consistent with the examples, except that polystyrene and polyphenylene sulfide are not added in step (3).
Comparative example eight
A method for preparing a heat-resistant electric brush is consistent with the embodiment, wherein the difference is that no carbon nano tube or graphene oxide is added.
Tg test instrument and conditions: DMA and the heating rate is 5 ℃/min; flame retardancy: judging according to UL94 vertical burning test standard; CT test instruments and conditions: TMA, the temperature of which is raised from room temperature 25 ℃ to 300 ℃ at a temperature raising rate of 10 ℃/min, and the coefficient of thermal expansion in the plane direction at 50 ℃ to 130 ℃ is measured; boiling in water for 96 hours to test the water absorption; testing the electrical property according to the physical and chemical property test method of the electric carbon brush; testing the mechanical property by a universal testing machine; testing the maximum number of processed pieces in a finishing period by using the conventional grinding wheel; the friction was carried out for 500 hours, and the wear rate was measured.
TABLE 1 Brush characterization
Tg Td Coefficient of smoothing Resistivity of CTE Oxygen index Flame retardant rating Compressive strength Number of processed pieces
Example one 332℃ 459℃ 2Ω 3μΩm 5.9ppm/℃ 32 V0 >180N >3500
Example two 331℃ 457℃ 2Ω 3μΩm 5.9ppm/℃ 32 V0 >180N >3500
EXAMPLE III 331℃ 455℃ 2Ω 3μΩm 6.3ppm/℃ 31 V0 >180N >3500
Example four 329℃ 457℃ 2Ω 4μΩm 6.2ppm/℃ 32 V0 >180N >3500
EXAMPLE five 327℃ 459℃ 2Ω 4μΩm 6.3ppm/℃ 32 V0 >180N >3500
EXAMPLE six 328℃ 457℃ 2Ω 3μΩm 6.5ppm/℃ 32 V0 >180N >3500
Comparative example 1 293℃ 411℃ 10Ω 26μΩm 7.7ppm/℃ 30 V0 >180N >3500
Comparative example No. two 292℃ 402℃ 7Ω 17μΩm 7.6ppm/℃ 30 V0 165N 3200
Comparative example No. three 299℃ 415℃ 6Ω 11μΩm 7.5ppm/℃ 30 V0 >180N 3500
Comparative example No. four 294℃ 412℃ 5Ω 6μΩm 8.1ppm/℃ 30 V0 155N 3300
Comparative example five 297℃ 409℃ 4Ω 6μΩm 8.0ppm/℃ 29 V0 >180N >3500
Comparative example six 288℃ 391℃ 5Ω 8μΩm 8.1ppm/℃ 28 V1 160N >3500
Comparative example seven 291℃ 407℃ 4Ω 6μΩm 8.0ppm/℃ 30 V0 >180N 3400
Comparative example eight 292℃ 413℃ 3Ω 5μΩm 8.1ppm/℃ 31 V0 >180N >3500
TABLE 2 characterization of properties
Bending strength Water absorption rate Coefficient of friction Impact strength Rate of wear Flexural modulus
Example one 236MPa 0.61% 0.07 30.5KJ/m2 0.85mg/h 4.66Gpa
Example two 234MPa 0.65% 0.07 30.1KJ/m2 0.92mg/h 4.65Gpa
EXAMPLE III 232MPa 0.62% 0.08 29.9KJ/m2 0.88mg/h 4.68Gpa
Example four 231MPa 0.65% 0.07 30.5KJ/m2 0.88mg/h 4.60Gpa
EXAMPLE five 233MPa 0.62% 0.07 29.9KJ/m2 0.89mg/h 4.61Gpa
EXAMPLE six 232MPa 0.63% 0.08 30.1KJ/m2 0.87mg/h 4.61Gpa
Comparative example 1 211MPa 0.75% 0.13 28.1KJ/m2 1.09mg/h 3.23Gpa
Comparative example No. two 214MPa 0.76% 0.12 28.5KJ/m2 1.09mg/h 3.35Gpa
Comparative example No. three 202MPa 0.81% 0.15 28.0KJ/m2 1.05mg/h 3.47Gpa
Comparative example No. four 197MPa 0.81% 0.11 28.7KJ/m2 1.06mg/h 3.36Gpa
Comparative example five 208MPa 0.75% 0.12 27.3KJ/m2 1.05mg/h 3.19Gpa
Comparative example six 207MPa 0.82% 0.12 28.8KJ/m2 1.07mg/h 3.55Gpa
Comparative example seven 211MPa 0.7% 0.12 28.1KJ/m2 1.04mg/h 3.61Gpa
Comparative example eight 227MPa 0.66% 0.10 29.9KJ/m2 0.90mg/h 4.59Gpa

Claims (3)

1. A method for preparing a heat-resistant electric brush is characterized by comprising the following steps:
(1) under the protection of nitrogen, mixing ammonium hexachloroiridate, dioctyltin, zinc acetate, ethanol and cyclohexane; then refluxing and stirring for 1 hour, then adding a potassium hydroxide methanol solution, stirring for 30 minutes, and then adding tert-butyl hydroperoxide; reacting for 2 hours, naturally cooling to room temperature, adding ethyl acetate for coagulation and centrifugation; washing the centrifugal precipitate with water, and dispersing in ethanol to obtain a dispersion system; adding polyvinyl alcohol and ammonia water into a dispersion system, stirring for 1 hour at 50 ℃, then adding 3, 5-dimethylpyrazole and iron tetraphenylporphyrin, stirring for 3 hours at 60 ℃, then adding carbon nanotubes, stirring for 3 hours under reflux, and then concentrating to obtain a concentrate with the solid content of 80%; carrying out hypergravity treatment on the concentrate; then freeze-drying to obtain nanometer powder; the rotating speed of the supergravity treatment is 35000-40000 rpm; the flow rate of the concentrate is 80-90 mL/min;
(2) adding hexamethylenetetramine into the organic silicon phenolic resin, stirring for 25 minutes at 140 ℃, then adding glyceryl monostearate, and stirring for 10 minutes at 90 ℃; adding a phenanthroline derivative and 1, 8-octanedithiol, stirring for 30 minutes, and adding bismaleimide and lanthanum cobalt oxide (LnCoO)3) Continuously stirring for 1 hour, then adding triethanolamine at 115 ℃, and stirring for 35 minutes to obtain a polymer matrix; adding graphene oxide into epoxy resin, stirring for 1 hour at 160 ℃, adding diphenylphosphine oxide and fatty amine polyoxyethylene ether, stirring for 2 hours at 120 ℃, then adding paraffin, stirring for 1 hour, adding a polymer matrix, and stirring for 10 minutes to obtain a heat-resistant resin system;
the chemical structural formula of the phenanthroline derivative is as follows:
Figure DEST_PATH_IMAGE001
(3) uniformly dry-grinding polyester resin, molybdenum disulfide, nano powder, a heat-resistant resin system, polystyrene, polyphenylene sulfide, zinc dimethyldithiocarbamate and an ethylene-vinyl acetate copolymer, adding the mixture into an extruder, and extruding the mixture at 175 ℃ to obtain electric brush composition particles; carrying out hot pressing, cutting and polishing on the electric brush composition particles to obtain a heat-resistant electric brush;
ammonium hexachloroiridate, dioctyltin, zinc acetate, ethanol, cyclohexane, potassium hydroxide methanol solution, tert-butyl hydroperoxide, polyvinyl alcohol, ammonia water, 3, 5-dimethylpyrazole, tetraphenylporphyrin iron and carbon nano tube in the mass ratio of 15: 30: 55: 200: 150: 20: 15: 20: 10: 8: 5: 3; the mass ratio of hexamethylene tetramine, organic silicon phenolic resin, glyceryl monostearate, a phenanthroline derivative, 1, 8-octanedithiol, bismaleimide, lanthanum cobalt trioxide, triethanolamine, graphene oxide, epoxy resin, diphenylphosphine, fatty amine polyoxyethylene ether and paraffin is 11: 20: 6: 5: 8: 100: 0.5: 10: 3: 30: 12: 8: 6; the mass ratio of the terylene resin, the molybdenum disulfide, the nano powder, the heat-resistant resin system, the polystyrene, the polyphenylene sulfide, the zinc dimethyldithiocarbamate and the ethylene-vinyl acetate copolymer is 12: 3: 28: 100: 5: 6: 2: 12;
the hot pressing conditions are 1MPa/150 ℃ curing for 2.5-3.0 hours, 2MPa/190 ℃ curing for 1.5-2.0 hours, and 1.5MPa/220 ℃ curing for 3.5-4.5 hours.
2. An electric brush composition and a preparation method thereof are characterized by comprising the following steps:
(1) under the protection of nitrogen, mixing ammonium hexachloroiridate, dioctyltin, zinc acetate, ethanol and cyclohexane; then refluxing and stirring for 1 hour, then adding a potassium hydroxide methanol solution, stirring for 30 minutes, and then adding tert-butyl hydroperoxide; reacting for 2 hours, naturally cooling to room temperature, adding ethyl acetate for coagulation and centrifugation; washing the centrifugal precipitate with water, and dispersing in ethanol to obtain a dispersion system; adding polyvinyl alcohol and ammonia water into a dispersion system, stirring for 1 hour at 50 ℃, then adding 3, 5-dimethylpyrazole and iron tetraphenylporphyrin, stirring for 3 hours at 60 ℃, then adding carbon nanotubes, stirring for 3 hours under reflux, and then concentrating to obtain a concentrate with the solid content of 80%; carrying out hypergravity treatment on the concentrate; then freeze-drying to obtain nanometer powder; the rotating speed of the supergravity treatment is 35000-40000 rpm; the flow rate of the concentrate is 80-90 mL/min;
(2) adding hexamethylenetetramine into the organic silicon phenolic resin, stirring for 25 minutes at 140 ℃, then adding glyceryl monostearate, and stirring for 10 minutes at 90 ℃; adding a phenanthroline derivative and 1, 8-octanedithiol, stirring for 30 minutes, and adding bismaleimide and lanthanum cobalt oxide (LnCoO)3) Continuously stirring for 1 hour, then adding triethanolamine at 115 ℃, and stirring for 35 minutes to obtain a polymer matrix; adding graphene oxide into epoxy resin, stirring for 1 hour at 160 ℃, adding diphenylphosphine oxide and fatty amine polyoxyethylene ether, stirring for 2 hours at 120 ℃, then adding paraffin, stirring for 1 hour, adding a polymer matrix, and stirring for 10 minutes to obtain a heat-resistant resin system;
the chemical structural formula of the phenanthroline derivative is as follows:
Figure 76315DEST_PATH_IMAGE001
(3) the preparation method comprises the following steps of (1) uniformly dry-grinding polyester resin, molybdenum disulfide, nano powder, a heat-resistant resin system, polystyrene, polyphenylene sulfide, zinc dimethyldithiocarbamate and an ethylene-vinyl acetate copolymer, adding the mixture into an extruder, and extruding the mixture at 175 ℃ to obtain an electric brush composition;
ammonium hexachloroiridate, dioctyltin, zinc acetate, ethanol, cyclohexane, potassium hydroxide methanol solution, tert-butyl hydroperoxide, polyvinyl alcohol, ammonia water, 3, 5-dimethylpyrazole, tetraphenylporphyrin iron and carbon nano tube in the mass ratio of 15: 30: 55: 200: 150: 20: 15: 20: 10: 8: 5: 3; the mass ratio of hexamethylene tetramine, organic silicon phenolic resin, glyceryl monostearate, a phenanthroline derivative, 1, 8-octanedithiol, bismaleimide, lanthanum cobalt trioxide, triethanolamine, graphene oxide, epoxy resin, diphenylphosphine, fatty amine polyoxyethylene ether and paraffin is 11: 20: 6: 5: 8: 100: 0.5: 10: 3: 30: 12: 8: 6; the mass ratio of the terylene resin, the molybdenum disulfide, the nano powder, the heat-resistant resin system, the polystyrene, the polyphenylene sulfide, the zinc dimethyldithiocarbamate and the ethylene-vinyl acetate copolymer is 12: 3: 28: 100: 5: 6: 2: 12.
3. The method according to claim 1, wherein the mass concentration of potassium hydroxide in the potassium hydroxide methanol solution is 4.5%; the molecular weight of the fatty amine polyoxyethylene ether is 2500-3500; the molecular weight of the polyvinyl alcohol is 1500-2000.
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