CN107254169A

CN107254169A - A kind of heat-resisting brush and preparation method thereof

Info

Publication number: CN107254169A
Application number: CN201710471313.9A
Authority: CN
Inventors: 梁国正
Original assignee: Suzhou University
Current assignee: Suzhou University
Priority date: 2017-06-20
Filing date: 2017-06-20
Publication date: 2017-10-17
Anticipated expiration: 2037-06-20
Also published as: CN107254169B

Abstract

The invention provides a kind of heat-resisting brush and preparation method thereof, based on phenolic resin, bimaleimide resin, with reference to epoxy resin, pass through the selection compatibility of resin matrix, with reference to rational preparation technology, the brush that extruding pelletization is molded preparation again possesses excellent heat resistance, anti-wear performance, while having good electrical property；Available for high-quality, high request motor, engine.

Description

A kind of heat-resisting brush and preparation method thereof

Technical field

The invention belongs to power tool accessory technical field, and in particular to a kind of heat-resisting brush and preparation method thereof.

Background technology

Current potentiometer product, more particularly to Aero-Space, weaponry etc. are to special organic solid potentiometer, glass Glaze potentiometer has very strict technical requirements, and the output voltage signal of adjustment potentiometer must very accurately and reliably, its skill Art requirement and the brush of potentiometer are closely related, thus requirement of the potentiometer to brush must simultaneously meet apparent size, resistance, The requirement of many indexs such as wear-resistant coefficient, compression strength, smoothing factor, collision and vibrations.

Existing brush performance is poor, and stability is bad, and brush unit pressure is too high, and resistance is big, hardness is high, causes electricity The abrasion aggravation of machine brush, unit pressure is too small, contacts unstable, commutation ability is poor, mechanical spark easily occurs；Particularly Wear no resistance, commutation ability is poor, poor anti jamming capability, heat resistance not enough, it is impossible to meet high performance motor to the various of brush It is required that.

Brush is divided into soft brush, middle hard brush and hard brush by the soft or hard of material；It is divided into by the color of brush Black electrical brush (being made of pure carbon graphite material) and color brush (being made of the metal materials such as copper and graphite)；By brush material Difference, can be divided into：(1) electrographite brush, (2) electrographite brush, (3) metal-graphite brush.In the prior art, it is general to use Carbon, graphite composite powder are base-material, and using resin as adhesives, brush is manufactured through kneading, milling, shaping and solidification.

The content of the invention

The invention provides a kind of heat-resisting brush and preparation method thereof, using phenolic resin, bimaleimide resin as base Plinth, with reference to epoxy resin, by the selection compatibility of resin matrix, with reference to rational preparation technology, extruding pelletization is molded preparation again Brush possess excellent heat resistance, anti-wear performance, while having good electrical property；It is electric available for high-quality, high request Machine, engine.

To achieve the above object of the invention, the present invention is adopted the following technical scheme that：A kind of preparation method of heat-resisting brush, including Following steps：

（1）Under nitrogen protection, six ammonium chloroiridates of mixing, dioctyl tin, zinc acetate, ethanol and hexamethylene；It is then refluxed for stirring 1 Hour, potassium hydroxide methanol solution is then added, stirring adds TBHP after 30 minutes；It is natural after reacting 2 hours Room temperature is cooled to, the centrifugation of ethyl acetate coagulation is added；Resulting dispersion system in ethanol is scattered in after centrifugal sediment is washed；Dividing Polyvinyl alcohol, ammoniacal liquor are added in granular media system, 50 DEG C are stirred 1 hour, then add 3,5- dimethyl pyrazoles, tetraphenylporphyrin iron, 60 DEG C are stirred 3 hours, then add CNT, then return stirring 3 hours is concentrated to give the concentrate of solid content 80%；Will Concentrate carries out hypergravity processing；Then it is freeze-dried, obtains nano powder；The rotating speed of hypergravity processing for 35000~ 40000rpm；The flow of concentrate is 80~90mL/min；

（2）Hexa is added in organosilicon phenolic resin, 140 DEG C are stirred 25 minutes, then add monostearate sweet Grease, 90 DEG C are stirred 10 minutes；Hello quinoline derivant, pungent two mercaptan of 1,8- are added, after stirring 30 minutes, bismaleimide is added Amine, three cobalt oxide lanthanums（LnCoO₃）, continue to stir 1 hour, triethanolamine then added in 115 DEG C, stirring is obtained after 35 minutes Polymeric matrix；Add graphene oxide into epoxy resin, 160 DEG C of stirrings add diphenyl phosphine oxide and fatty amine after 1 hour and gathered Oxygen vinethene, 120 DEG C are stirred 2 hours, then add paraffin, are stirred 1 hour, add polymeric matrix, are stirred 10 minutes, are obtained Heat stable resin system；

The chemical structural formula of the hello quinoline derivant is as follows：

（3）By polyester resin, molybdenum disulfide, nano powder, heat stable resin system, polystyrene, polyphenylene sulfide, DMDS generation Added after carbaminate, the dry grinding of ethylene vinyl acetate copolymer are uniform in extruder, brush is obtained in 175 DEG C of extrusions Composition particle；Brush composition particle obtains heat-resisting brush by hot pressing, cutting, polishing.

The invention also discloses a kind of nanometer conductive powder and preparation method thereof, comprise the following steps, under nitrogen protection, mix Close six ammonium chloroiridates, dioctyl tin, zinc acetate, ethanol and hexamethylene；Stirring 1 hour is then refluxed for, potassium hydroxide is then added Methanol solution, stirring adds TBHP after 30 minutes；Reaction naturally cools to room temperature after 2 hours, add acetic acid second Ester coagulation is centrifuged；Resulting dispersion system in ethanol is scattered in after centrifugal sediment is washed；In dispersion add polyvinyl alcohol, Ammoniacal liquor, 50 DEG C are stirred 1 hour, then add 3,5- dimethyl pyrazoles, tetraphenylporphyrin iron, and 60 DEG C are stirred 3 hours, are then added CNT, return stirring 3 hours, is then concentrated to give the concentrate of solid content 80%；Concentrate is subjected to hypergravity processing； Then it is freeze-dried, obtains nano powder；The rotating speed of the hypergravity processing is 35000~40000rpm；The flow of concentrate is 80~90mL/min.

The invention also discloses a kind of polymeric matrix and preparation method thereof, comprise the following steps, by hexa Add in organosilicon phenolic resin, 140 DEG C are stirred 25 minutes, then add glycerin monostearate, 90 DEG C are stirred 10 minutes；Plus Enter pungent two mercaptan of hello quinoline derivant, 1,8-, after stirring 30 minutes, add BMI, three cobalt oxide lanthanums（LnCoO₃）, after Continuous stirring 1 hour, then adds triethanolamine in 115 DEG C, and stirring obtains polymeric matrix after 35 minutes.

The invention also discloses a kind of brush composition and preparation method thereof, comprise the following steps：

（3）By polyester resin, molybdenum disulfide, nano powder, heat stable resin system, polystyrene, polyphenylene sulfide, DMDS generation Added after carbaminate, the dry grinding of ethylene vinyl acetate copolymer are uniform in extruder, brush is obtained in 175 DEG C of extrusions Composition.

The invention also discloses a kind of heat stable resin system and preparation method thereof, comprise the following steps, by hexa-methylene four Amine is added in organosilicon phenolic resin, and 140 DEG C are stirred 25 minutes, then adds glycerin monostearate, and 90 DEG C are stirred 10 minutes； Hello quinoline derivant, pungent two mercaptan of 1,8- are added, after stirring 30 minutes, BMI, three cobalt oxide lanthanums are added（LnCoO₃）, Continue to stir 1 hour, triethanolamine is then added in 115 DEG C, stirring obtains polymeric matrix after 35 minutes；By graphene oxide Add in epoxy resin, 160 DEG C of stirrings add diphenyl phosphine oxide and aliphatic amine polyoxyethylene ether after 1 hour, and 120 DEG C are stirred 2 hours, Then paraffin is added, is stirred 1 hour, polymeric matrix is added, stirs 10 minutes, obtains heat stable resin system.

In above-mentioned technical proposal, six ammonium chloroiridates, dioctyl tin, zinc acetate, ethanol, hexamethylene, methanolic potassium hydroxide are molten Liquid, TBHP, polyvinyl alcohol, ammoniacal liquor, 3,5- dimethyl pyrazoles, tetraphenylporphyrin iron, the mass ratio of CNT For 15: 30: 55: 200: 150: 20: 15: 20: 10: 8: 5: 3；Hexa, organosilicon phenolic resin, glycerol monostearate Pungent two mercaptan of ester, hello quinoline derivant, 1,8-, BMI, three cobalt oxide lanthanums, triethanolamine, graphene oxide, asphalt mixtures modified by epoxy resin Fat, diphenyl phosphine oxide, aliphatic amine polyoxyethylene ether, the mass ratio of paraffin are 11: 20: 6: 5: 8: 100: 0.5: 10: 3: 30: 12: 8: 6；Polyester resin, molybdenum disulfide, nano powder, heat stable resin system, polystyrene, polyphenylene sulfide, DMDS are for amino first Sour zinc, the mass ratio of ethylene vinyl acetate copolymer are 12: 3: 28: 100: 5: 6: 2: 12.

In the present invention, the mass concentration of potassium hydroxide is 4.5% in the potassium hydroxide methanol solution；The fatty amine gathers The molecular weight of oxygen vinethene is 2500~3500；The molecular weight of the polyvinyl alcohol is 1500~2000.The present invention is by adding Ammoniacal liquor is added while polyvinyl alcohol, tetraphenylporphyrin iron is added after mixing, in addition to increasing conductive powder body surface-active, more It is important that the molecular weight of polyvinyl alcohol has been reduced has certain degradation to the strand of polyvinyl alcohol, this is to rear Continuous electrical-conductive nanometer powder is helped with after mixed with resin, improving the relevant key of dispersive property and continuous performance of metal oxide, especially It is the influence for avoiding hot property, the polyvinyl alcohol of anti-wear performance difference to overall performance, has given full play to polyvinyl alcohol in conducting powder Body surface face combines other compounds and improves activity and increase compatibility to embody the advantage of good electrical properties, it is thus also avoided that its Participate in resin body and cause the problem of heat resistance, wearability decline.

The hot pressing condition of the present invention is small for 1MPa/150 DEG C of solidification+2MPa/190 DEG C of solidifications 1.5~2.0 in 2.5~3.0 hours When+1.5MPa/220 DEG C solidify 3.5~4.5 hours, with temperature rise, points three sections progressively solidify, the excellent modification of availability Resin；Unmodified resin elongation percentage is low, fragility is big, the brush of preparation not endurance, therefore should not use, two allyls of existing addition Based compound, diamine, epoxy resin can cause the reduction of heat resistance or humidity resistance.The modified Epoxy Resin/Phenol aldehyde of the present invention/bis- Maleimide resin is on the premise of its heat resistance and bending modulus are unaffected, and its toughness is improved significantly, especially Reduce brush friction cracking risk.

The invention also discloses the product according to above-mentioned preparation method preparation and a kind of motor brush structure, the electricity Brush configuration includes brush prepared by above-mentioned preparation method, in addition to brushgear housing.

The present invention devises several micromolecular compounds in addition to high performance resin, with reference to polymerization technology, poly- During closing Polymerization induced phase separation, system can form two-arch tunnel structure, and can occur under certain condition opposite The phenomenon turned, i.e., turn into the auxiliary continuous phase of system as a small amount of component reaction formation thermoplastic unit.Because reversion phase structure is Netted continuous phase is constituted by a small amount of thermoplastic unit and is constituted, and the mechanical property of system and heat, electrical property are often with master Based on continuous phase, a small amount of thermoplastic unit is controlled by parameter designing, this structure is conducive to increasing substantially for system performance.

Existing toughener has certain toughness reinforcing, plasticization effect, but due to the limitation of structure so that aathermoset resin system is added System crosslink density, mechanical property and heat resistance have declined afterwards, have run counter to the use original intention of high performance heat resistant polymer；Root According to technical scheme, there is stronger activity using glycerin monostearate, pungent two mercaptan of 1,8-, first can be sent out with phenolic aldehyde Raw reaction, then occur graft reaction with epoxy resin, inside introduce toughness and heat resistance（Breaking phenol ring needs higher heat Energy）Good long-chain and benzene ring structure, hardness can also be reduced by playing intrinsic toughening effect, so that reach has to matrix resin Put the modified purpose of arrow, and the combination of hexa, diphenyl phosphine oxide then avoids excessive flexibility, has solidfied material high resistance to Hot and mechanical strength, to meet the technical requirements of brush material heat resistance, workability, rub resistance, water resistance.

The present invention is modified with metal iridium obtains complex conductive fillerses first, and brush material is manufactured then in conjunction with resin matrix, The powder of different properties and organic molecule and polymer is caused to form uniform network structure by the chemism of iridium, profit In each constituent element in the interaction of interface and mutually wetting, whole material system is set to be in the most steady state of thermodynamics, in brush The carbide and small molecule material matter produced under material at high temperature operating mode is few, so the heat fading of coefficient of friction is small, particularly, in tree Modified RE metal is added in resin system, it is to avoid the influence polymerizeing to resin matrix, the conductivity level of system can also be improved；Make Obtain product coefficient of friction height of the invention and electric performance stablity.

The indices of brush practical application influence each other very greatly, and many index will reach that requirement is extremely difficult simultaneously, than Such as say that brush resistance itself is the smaller the better, but resistance is small, intensity is with regard to impacted step-down.The kind of brush material, proportioning, Method in dispersing uniformity and process in granularity size, process etc. has influence to technical indicator, solution Certainly the key of problem is exactly that can solve the problem that while meet the scheme of all technical requirement, pass through formula with of both technique With reference to can just reach technique effect.

The present invention adds double bond and organosilicon phenolic aldehyde tree in organosilicon phenolic resin, solidification process in BMI Addition reaction occurs for the methylol of fat, improves the heat resistance and adhesive strength of organosilicon phenolic resin, and keep its toughness； Avoid the storage at normal temperature phase from declining by the addition of epoxy resin, solve under a small amount of carboxyl and amido normal temperature of presence with having The problem of condensation is caused occurs for machine silicon phenolic resin methylol.

With the implementation of the disabling anti-preparation method of harmful substance (RoHS), ep-type material has not been a demand, but is become Into a kind of requirement of fundamental property, although the regulation of country variant is not quite similar, but be generally uniform.In existing environmental protection In type halogen-free material formula composition, it is typically chosen phosphide and makees flame retardant substitution halogen compounds, but use phosphorous flame-retardant material During material, the inorganic particle that need to generally arrange in pairs or groups just has method by UL-94 test specifications, the inorganic particle arranged in pairs or groups usually hydroxide Thing, the hydroxide more often used is silica and aluminium hydroxide respectively, there is distinct disadvantage during for brush, except shadow Ring outside electrical property, can more influence wear-resisting, heat resistance；The present invention by the cooperation between organic matter, such as P-Si-N elements Synergy, limits the usage ratio of several compounds, realizes the halogen-free flameproof of brush, reach V0 grades.

In the case of volume is less and less, the speed of service is more and more faster, the heat that brush is produced is also increasing, these If heat can not be expelled to external environment in good time, by make brush assembly of electric because temperature is too high have influence on product reliability and caused by Service life lowers.Therefore, how to radiate while improving the heat-resisting stable running to maintain system will become more and more important, because For in the reason for brushgear is damaged, because high temperature causes the ratio of damage or loss of function for example to vibrate, rub far above other Influence caused by the factors such as wiping；Therefore, the exploitation of the high heat resistant substrate material of various demand characteristics is provided simultaneously with, is also brush Industry one of continual Research Emphasis for a long time.

Phenolic aldehyde is heat-resist with bismaleimide resin, but fragility and water imbibition are not enough, typically by epoxide modified, but ring It is obvious that oxygen can cause hot property to decline, and prior art has many modified schemes, substantially only for toughness and heat resistance, does not have Refer to wearability and electric conductivity, report more not on brush base resin.The present invention by hello quinoline derivant with The use of polyphenylene sulfide, increases the hydrophobic property of modified heat convertible resin composition, also passes through reactive mercapto, ammonia in addition Base, pyrazoles, being introduced into system can make the crosslink density of resin combination decrease, and coordinate polystyrene, ethyl vinyl acetate second Alkenyl ester copolymer, toughness can increased, so that gained modified resin composition has higher mechanical strength and processing Stability；In addition, not interfering with the last crosslinking curing of modified resin as netted knot with a certain proportion of micromolecular compound Structure, can avoid the generation of low molecule amount condensation polymer on the contrary；Therefore, by several compounds to bimaleimide resin, epoxy Resin and phenolic resin are modified, and while the heat resistance and intensity of resin is kept, are effectively improved humidity resistance And toughness, while small molecule reduces the generation of low-molecular-weight polycondensate in thermosetting resin curing process, reduce friction and lack Fall into and stress defect, anti-wear performance is improved to a certain degree.

Passing ratio of the present invention, which is limited, in the molecular structure controls the content of the rigid radicals such as phenyl ring within the specific limits, so that The melt viscosity of resin is reduced, technique processability is improved；And kept due to the rigid structure of resin matrix Good heat resistance, and with good moisture-proof, anti-flammability and reliability, low in-plane thermal coefficient of expansion.It is existing There is technology epoxy to play certain catalytic action to curing reaction of span etc., be conducive to improving monomer in solidification process Conversion ratio, promotes the completion of curing reaction；However, existing modified resin system is existed, reactivity is larger, and the work phase is short Manufacturability issues, this mechanical property, electrical property, practical application to resin system can have adverse effect on.The present invention by 1, Pungent two mercaptan of 8-, PZ and paraffin are incorporated into BMI/phenolic aldehyde/epoxy modified resin In, the processing performance of uncured resin can not only be improved, additionally it is possible to improve the mechanics of solidified resin, the performance such as heat-resisting；Hello quinoline Pungent two mercaptan of derivative, 1,8- can be with resin monomer polymerisation, so as to introduce thermosetting beneficial to by certain flexible unit In curing network structure.The chemical chain structure of the present invention, is conducive to, in the case where heat resistance loss is small, improving resin material Toughness, electricity, the performance, such as boiling water boiling 96 hours such as wear-resisting, water-fast, water absorption rate is less than 0.8%.

The use metal composite oxide iridium-tin-zinc oxide nano-particles of the invention are as conductive material, both There is provided brush excellent electric conductivity, again resin matrix can be promoted to form good network structure, so that comprehensive beneficial to brush The rare earth metal added during the raising, especially binding resin pre-polymerization of energy avoids point that existing carbon material exists as conductive agent Dissipate uneven, it is bad with resin system compatibility so that the problem of brush preferably can not reach excellent combination property.Add simultaneously A small amount of carbon material can increase stabilization, the patency of conductive network in favor of the special construction of carbon material, further improve brush electricity Performance.

The present invention carry out resin modified under low temperature in extrusion first, both solved fusion method presence polymerization it is uneven, Easily there is the defect of oligomer, especially by the effect of adding technology and small molecule, solve the reaction of extrusion molding presence Property is weak and the problem of be not used to a variety of properties different compound high polymer melting mixing；By in thermosetting resin main body Add the good thermoplastic resin of hot property not only to have improved performed polymer processability but also avoided polymerization excessive, especially thermoplastic resin The brush that the addition of fat is obtained is easy to polishing processing, and mechanical property is good, and electrical property, hot property are still good；By the present invention The modified resin of preparation is used for after brush preparation, be able to can be obtained with the mixing of conductive powder body well and with reference to curing process The good brush product of homogeneous stabilization, performance especially electrical property, hot property, anti-wear performance, fire resistance.

Because particle diameter is small, specific surface area big, surface energy is high, it is easy to reunite, therefore be difficult to evenly spread to In high polymer material, the method such as existing machinery stirring, banburying, ultrasonic disperse, but dispersion effect is not satisfactory.The present invention is first The activity that metal iridium improves combined oxidation metal is added, conductive powder body and resin matrix are unfavorable on the contrary if do not handled further Mixing, recycle polyvinyl alcohol to handle the surface of particle, while adding 3,5- dimethyl pyrazoles and tetraphenyl porphin Quinoline iron, different to inorganic filler progress processing from other coupling agents, a small amount of drop occurs under certain condition of the present invention for polyvinyl alcohol Solution, has two benefits, one is to avoid macromolecular chain structure that influence electric conductivity is completely covered on particle, and two be that can increase by 3, The reactivity of 5- dimethyl pyrazoles, CNT so that particle surface carries acitve organic matter, especially in the presence of ammoniacal liquor, The exposure level and effect of metal oxide and micromolecular compound can be improved；Handle, thoroughly solve finally by hypergravity The problem of particle aggregation, while retaining particle surface active group.Therefore, the electrical-conductive nanometer powder that the present invention is obtained can be effective Receive the agglomeration of particulate, can same epoxy resin, phenolic resin, span moreover, receiving the functional group on particulate surface The polymer such as resin carry out co-polymeric, substantially increase and receive the dispersiveness and stability of particulate in the polymer, from electrical Can, heat resistance and anti-wear performance this it appears that.

Embodiment

Embodiment one

A kind of preparation method of heat-resisting brush, comprises the following steps：

（1）Under nitrogen protection, six ammonium chloroiridates of mixing, dioctyl tin, zinc acetate, ethanol and hexamethylene；It is then refluxed for stirring 1 Hour, potassium hydroxide methanol solution is then added, stirring adds TBHP after 30 minutes；It is natural after reacting 2 hours Room temperature is cooled to, the centrifugation of ethyl acetate coagulation is added；Resulting dispersion system in ethanol is scattered in after centrifugal sediment is washed；Dividing Polyvinyl alcohol, ammoniacal liquor are added in granular media system, 50 DEG C are stirred 1 hour, then add 3,5- dimethyl pyrazoles, tetraphenylporphyrin iron, 60 DEG C are stirred 3 hours, then add CNT, then return stirring 3 hours is concentrated to give the concentrate of solid content 80%；Will Concentrate carries out hypergravity processing；Then it is freeze-dried, obtains nano powder；The rotating speed of the hypergravity processing is 35000pm；It is dense The flow of contracting thing is 80mL/min；

（2）Hexa is added in organosilicon phenolic resin, 140 DEG C are stirred 25 minutes, then add monostearate sweet Grease, 90 DEG C are stirred 10 minutes；Hello quinoline derivant, pungent two mercaptan of 1,8- are added, after stirring 30 minutes, 4,4'- hexichol first is added Alkane BMI, three cobalt oxide lanthanums（LnCoO₃）, continue to stir 1 hour, triethanolamine, stirring then added in 115 DEG C Polymeric matrix is obtained after 35 minutes；Add graphene oxide into bisphenol A epoxide resin, 160 DEG C stirring 1 hour after add two Benzene phosphine oxide and aliphatic amine polyoxyethylene ether, 120 DEG C are stirred 2 hours, then add paraffin, are stirred 1 hour, add polymer matrix Body, stirs 10 minutes, obtains heat stable resin system；

Hot pressing condition is that+1.5MPa/220 DEG C of 1MPa/150 DEG C of solidification+2MPa/190 DEG C of solidifications in 2.5 hours 2.0 hours are solid Change 4.5 hours.

Embodiment two

（1）Under nitrogen protection, six ammonium chloroiridates of mixing, dioctyl tin, zinc acetate, ethanol and hexamethylene；It is then refluxed for stirring 1 Hour, potassium hydroxide methanol solution is then added, stirring adds TBHP after 30 minutes；It is natural after reacting 2 hours Room temperature is cooled to, the centrifugation of ethyl acetate coagulation is added；Resulting dispersion system in ethanol is scattered in after centrifugal sediment is washed；Dividing Polyvinyl alcohol, ammoniacal liquor are added in granular media system, 50 DEG C are stirred 1 hour, then add 3,5- dimethyl pyrazoles, tetraphenylporphyrin iron, 60 DEG C are stirred 3 hours, then add CNT, then return stirring 3 hours is concentrated to give the concentrate of solid content 80%；Will Concentrate carries out hypergravity processing；Then it is freeze-dried, obtains nano powder；The rotating speed of the hypergravity processing is 35000rpm； The flow of concentrate is 90mL/min；

（2）Hexa is added in organosilicon phenolic resin, 140 DEG C are stirred 25 minutes, then add monostearate sweet Grease, 90 DEG C are stirred 10 minutes；Hello quinoline derivant, pungent two mercaptan of 1,8- are added, after stirring 30 minutes, 4,4'- hexichol first is added Alkane BMI, three cobalt oxide lanthanums（LnCoO₃）, continue to stir 1 hour, triethanolamine, stirring then added in 115 DEG C Polymeric matrix is obtained after 35 minutes；Add graphene oxide into para aminophenol three glycidyl epoxy resin, 160 DEG C Stirring adds diphenyl phosphine oxide and aliphatic amine polyoxyethylene ether after 1 hour, 120 DEG C are stirred 2 hours, then adds paraffin, and stirring 1 is small When, polymeric matrix is added, stirs 10 minutes, obtains heat stable resin system；

Hot pressing condition is that+1.5MPa/220 DEG C of 1MPa/150 DEG C of solidification+2MPa/190 DEG C of solidifications in 2.5 hours 1.5 hours are solid Change 4.5 hours.

Embodiment three

（1）Under nitrogen protection, six ammonium chloroiridates of mixing, dioctyl tin, zinc acetate, ethanol and hexamethylene；It is then refluxed for stirring 1 Hour, potassium hydroxide methanol solution is then added, stirring adds TBHP after 30 minutes；It is natural after reacting 2 hours Room temperature is cooled to, the centrifugation of ethyl acetate coagulation is added；Resulting dispersion system in ethanol is scattered in after centrifugal sediment is washed；Dividing Polyvinyl alcohol, ammoniacal liquor are added in granular media system, 50 DEG C are stirred 1 hour, then add 3,5- dimethyl pyrazoles, tetraphenylporphyrin iron, 60 DEG C are stirred 3 hours, then add CNT, then return stirring 3 hours is concentrated to give the concentrate of solid content 80%；Will Concentrate carries out hypergravity processing；Then it is freeze-dried, obtains nano powder；The rotating speed of the hypergravity processing is 40000rpm； The flow of concentrate is 80mL/min；

（2）Hexa is added in organosilicon phenolic resin, 140 DEG C are stirred 25 minutes, then add monostearate sweet Grease, 90 DEG C are stirred 10 minutes；Hello quinoline derivant, pungent two mercaptan of 1,8- are added, after stirring 30 minutes, 4,4'- hexichol first is added Alkane BMI, three cobalt oxide lanthanums（LnCoO₃）, continue to stir 1 hour, triethanolamine, stirring then added in 115 DEG C Polymeric matrix is obtained after 35 minutes；Add graphene oxide into bis-phenol E epoxy resin, 160 DEG C stirring 1 hour after add two Benzene phosphine oxide and aliphatic amine polyoxyethylene ether, 120 DEG C are stirred 2 hours, then add paraffin, are stirred 1 hour, add polymer matrix Body, stirs 10 minutes, obtains heat stable resin system；

Hot pressing condition is that+1.5MPa/220 DEG C of 1MPa/150 DEG C of solidification+2MPa/190 DEG C of solidifications in 2.5 hours 2.0 hours are solid Change 3.5 hours.

Example IV

（1）Under nitrogen protection, six ammonium chloroiridates of mixing, dioctyl tin, zinc acetate, ethanol and hexamethylene；It is then refluxed for stirring 1 Hour, potassium hydroxide methanol solution is then added, stirring adds TBHP after 30 minutes；It is natural after reacting 2 hours Room temperature is cooled to, the centrifugation of ethyl acetate coagulation is added；Resulting dispersion system in ethanol is scattered in after centrifugal sediment is washed；Dividing Polyvinyl alcohol, ammoniacal liquor are added in granular media system, 50 DEG C are stirred 1 hour, then add 3,5- dimethyl pyrazoles, tetraphenylporphyrin iron, 60 DEG C are stirred 3 hours, then add CNT, then return stirring 3 hours is concentrated to give the concentrate of solid content 80%；Will Concentrate carries out hypergravity processing；Then it is freeze-dried, obtains nano powder；The rotating speed of the hypergravity processing is 40000rpm； The flow of concentrate is 90mL/min；

（2）Hexa is added in organosilicon phenolic resin, 140 DEG C are stirred 25 minutes, then add monostearate sweet Grease, 90 DEG C are stirred 10 minutes；Hello quinoline derivant, pungent two mercaptan of 1,8- are added, after stirring 30 minutes, 4,4'- diphenyl ether is added BMI, three cobalt oxide lanthanums（LnCoO₃）, continue to stir 1 hour, triethanolamine, stirring 35 then added in 115 DEG C Polymeric matrix is obtained after minute；Add graphene oxide into para aminophenol three glycidyl epoxy resin, 160 DEG C are stirred Mix and diphenyl phosphine oxide and aliphatic amine polyoxyethylene ether are added after 1 hour, 120 DEG C are stirred 2 hours, then add paraffin, stirring 1 is small When, polymeric matrix is added, stirs 10 minutes, obtains heat stable resin system；

Hot pressing condition is that+1.5MPa/220 DEG C of 1MPa/150 DEG C of solidification+2MPa/190 DEG C of solidifications in 3.0 hours 2.0 hours are solid Change 4.5 hours.

Embodiment five

（1）Under nitrogen protection, six ammonium chloroiridates of mixing, dioctyl tin, zinc acetate, ethanol and hexamethylene；It is then refluxed for stirring 1 Hour, potassium hydroxide methanol solution is then added, stirring adds TBHP after 30 minutes；It is natural after reacting 2 hours Room temperature is cooled to, the centrifugation of ethyl acetate coagulation is added；Resulting dispersion system in ethanol is scattered in after centrifugal sediment is washed；Dividing Polyvinyl alcohol, ammoniacal liquor are added in granular media system, 50 DEG C are stirred 1 hour, then add 3,5- dimethyl pyrazoles, tetraphenylporphyrin iron, 60 DEG C are stirred 3 hours, then add CNT, then return stirring 3 hours is concentrated to give the concentrate of solid content 80%；Will Concentrate carries out hypergravity processing；Then it is freeze-dried, obtains nano powder；The rotating speed of the hypergravity processing is 35000rpm； The flow of concentrate is 80mL/min；

（2）Hexa is added in organosilicon phenolic resin, 140 DEG C are stirred 25 minutes, then add monostearate sweet Grease, 90 DEG C are stirred 10 minutes；Hello quinoline derivant, pungent two mercaptan of 1,8- are added, after stirring 30 minutes, 4,4'- diphenyl ether is added BMI, three cobalt oxide lanthanums（LnCoO₃）, continue to stir 1 hour, triethanolamine, stirring 35 then added in 115 DEG C Polymeric matrix is obtained after minute；Add graphene oxide into bisphenol A epoxide resin, 160 DEG C stirring 1 hour after add hexichol Phosphine oxide and aliphatic amine polyoxyethylene ether, 120 DEG C are stirred 2 hours, then add paraffin, are stirred 1 hour, add polymeric matrix, Stirring 10 minutes, obtains heat stable resin system；

Hot pressing condition is that+1.5MPa/220 DEG C of 1MPa/150 DEG C of solidification+2MPa/190 DEG C of solidifications in 3.0 hours 2.0 hours are solid Change 3.5 hours.

Embodiment six

（2）Hexa is added in organosilicon phenolic resin, 140 DEG C are stirred 25 minutes, then add monostearate sweet Grease, 90 DEG C are stirred 10 minutes；Hello quinoline derivant, pungent two mercaptan of 1,8- are added, after stirring 30 minutes, 4,4'- diphenyl sulphone (DPS)s are added BMI, three cobalt oxide lanthanums（LnCoO₃）, continue to stir 1 hour, triethanolamine, stirring 35 then added in 115 DEG C Polymeric matrix is obtained after minute；Add graphene oxide into bisphenol A epoxide resin, 160 DEG C stirring 1 hour after add hexichol Phosphine oxide and aliphatic amine polyoxyethylene ether, 120 DEG C are stirred 2 hours, then add paraffin, are stirred 1 hour, add polymeric matrix, Stirring 10 minutes, obtains heat stable resin system；

Hot pressing condition is that+1.5MPa/220 DEG C of 1MPa/150 DEG C of solidification+2MPa/190 DEG C of solidifications in 3.0 hours 1.5 hours are solid Change 4.5 hours.

In the present invention, the chemical structural formula of the hello quinoline derivant is as follows：

It is six ammonium chloroiridates, dioctyl tin, zinc acetate, ethanol, hexamethylene, potassium hydroxide methanol solution, TBHP, poly- Vinyl alcohol, ammoniacal liquor, 3,5- dimethyl pyrazoles, tetraphenylporphyrin iron, the mass ratio of CNT are 15: 30: 55: 200: 150: 20 ∶15∶20∶10∶8∶5∶3；Hexa, organosilicon phenolic resin, glycerin monostearate, hello quinoline derivant, 1,8- are pungent Two mercaptan, BMI, three cobalt oxide lanthanums, triethanolamine, graphene oxide, epoxy resin, diphenyl phosphine oxide, fatty amine gather Oxygen vinethene, the mass ratio of paraffin are 11: 20: 6: 5: 8: 100: 0.5: 10: 3: 30: 12: 8: 6；Polyester resin, molybdenum disulfide, Nano powder, heat stable resin system, polystyrene, polyphenylene sulfide, PZ, ethene-vinyl acetate base The mass ratio of ester copolymer is 12: 3: 28: 100: 5: 6: 2: 12.

The mass concentration of potassium hydroxide is 4.5% in potassium hydroxide methanol solution；The molecule of the aliphatic amine polyoxyethylene ether Measure as 2500~3500；The molecular weight of the polyvinyl alcohol is 1500~2000.

Above-mentioned brush is combined with existing brushgear housing and obtains motor brush structure, using 24V reductor actual verifications, is started After 50000 times, electricity still runs well；3.7~3.8 millimeters of brush wear, 1.03 millimeters of commutator wear.

Comparative example one

A kind of preparation method of heat-resisting brush, consistent with embodiment one, wherein difference is, step（1）Middle centrifugation Thing（That is metal oxide）Change graphite powder into.

Comparative example two

A kind of preparation method of heat-resisting brush, consistent with embodiment one, wherein difference is, step（1）In be added without six Ammonium chloroiridate.

Comparative example three

A kind of preparation method of heat-resisting brush, consistent with embodiment one, wherein difference is, step（1）In be added without ammonia Water, tetraphenylporphyrin iron.

Comparative example four

A kind of preparation method of heat-resisting brush, consistent with embodiment one, wherein difference is, step（2）It is middle that hello quinoline spreads out Biological, pungent two mercaptan of 1,8- replaces with octamethylenediamine.

Comparative example five

A kind of preparation method of heat-resisting brush, consistent with embodiment one, wherein difference is, step（2）In be added without three Cobalt oxide lanthanum.

Comparative example six

A kind of preparation method of heat-resisting brush, consistent with embodiment one, wherein difference is, step（2）In be added without two Benzene phosphine oxide, aliphatic amine polyoxyethylene ether, paraffin.

Comparative example seven

A kind of preparation method of heat-resisting brush, consistent with embodiment one, wherein difference is, step（3）In be added without it is poly- Styrene, polyphenylene sulfide.

Comparative example eight

A kind of preparation method of heat-resisting brush, consistent with embodiment one, wherein difference is, is added without CNT, oxygen Graphite alkene.

Tg testers and condition：DMA, 5 DEG C/min of heating rate；Anti-flammability：According to UL94 testing vertical flammability standards Judged；CT testers and condition：TMA, 300 DEG C, measure are warming up to for 25 DEG C with 10 DEG C/min heating rate from room temperature In-plane thermal coefficient of expansion at from 50 DEG C to 130 DEG C；Water boils 96 hours test water absorption rates；According to electrical carbon brush physical chemistry Can method of testing test electrical property；Universal testing machine tests mechanical property；Tested using existing emery wheel in a finishing phase most greatly Workpiece number；Friction 500 hours, test wear rate.

The brush of table 1 characterizes one

Tg

Td

Smoothing factor

Resistivity

CTE

Oxygen index (OI)

Flame retardant rating

Compression strength

Process number of packages

Embodiment one

332℃

459℃

2Ω

3μΩm

5.9ppm/℃

32

V0

>180N

>3500

Embodiment two

331℃

457℃

2Ω

3μΩm

5.9ppm/℃

32

V0

>180N

>3500

Embodiment three

331℃

455℃

2Ω

3μΩm

6.3ppm/℃

31

V0

>180N

>3500

Example IV

329℃

457℃

2Ω

4μΩm

6.2ppm/℃

32

V0

>180N

>3500

Embodiment five

327℃

459℃

2Ω

4μΩm

6.3ppm/℃

32

V0

>180N

>3500

Embodiment six

328℃

457℃

2Ω

3μΩm

6.5ppm/℃

32

V0

>180N

>3500

Comparative example one

293℃

411℃

10Ω

26μΩm

7.7ppm/℃

30

V0

>180N

>3500

Comparative example two

292℃

402℃

7Ω

17μΩm

7.6ppm/℃

30

V0

165N

3200

Comparative example three

299℃

415℃

6Ω

11μΩm

7.5ppm/℃

30

V0

>180N

3500

Comparative example 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

The performance characterization two of table 2

Bending strength

Water absorption rate

Coefficient of friction

Impact strength

Wear rate

Bending modulus

Embodiment one

236MPa

0.61%

0.07

30.5KJ/m²

0.85mg/h

4.66Gpa

Embodiment two

234MPa

0.65%

0.07

30.1KJ/m²

0.92mg/h

4.65Gpa

Embodiment three

232MPa

0.62%

0.08

29.9KJ/m²

0.88mg/h

4.68Gpa

Example IV

231MPa

0.65%

0.07

30.5KJ/m²

0.88mg/h

4.60Gpa

Embodiment five

233MPa

0.62%

0.07

29.9KJ/m²

0.89mg/h

4.61Gpa

Embodiment six

232MPa

0.63%

0.08

30.1KJ/m²

0.87mg/h

4.61Gpa

Comparative example one

211MPa

0.75%

0.13

28.1KJ/m²

1.09mg/h

3.23Gpa

Comparative example two

214MPa

0.76%

0.12

28.5KJ/m²

1.09mg/h

3.35Gpa

Comparative example three

202MPa

0.81%

0.15

28.0KJ/m²

1.05mg/h

3.47Gpa

Comparative example 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

1. a kind of preparation method of heat-resisting brush, it is characterised in that comprise the following steps：

2. a kind of preparation method of nanometer conductive powder, it is characterised in that comprise the following steps, under nitrogen protection, mixes chlordene Iridium acid ammonium, dioctyl tin, zinc acetate, ethanol and hexamethylene；Stirring 1 hour is then refluxed for, methanolic potassium hydroxide is then added molten Liquid, stirring adds TBHP after 30 minutes；Reaction naturally cools to room temperature after 2 hours, add ethyl acetate coagulation Centrifugation；Resulting dispersion system in ethanol is scattered in after centrifugal sediment is washed；Polyvinyl alcohol, ammoniacal liquor are added in dispersion, 50 DEG C are stirred 1 hour, then add 3,5- dimethyl pyrazoles, tetraphenylporphyrin iron, and 60 DEG C are stirred 3 hours, are then added carbon and are received Mitron, return stirring 3 hours, is then concentrated to give the concentrate of solid content 80%；Concentrate is subjected to hypergravity processing；Then Freeze-drying, obtains nano powder；The rotating speed of the hypergravity processing is 35000~40000rpm；The flow of concentrate be 80~ 90mL/min。

3. a kind of preparation method of polymeric matrix, it is characterised in that comprise the following steps, hexa is added organic In silicon phenolic resin, 140 DEG C are stirred 25 minutes, then add glycerin monostearate, and 90 DEG C are stirred 10 minutes；Hello quinoline is added to spread out Biological, pungent two mercaptan of 1,8-, after stirring 30 minutes, adds BMI, three cobalt oxide lanthanums（LnCoO₃）, continue to stir 1 Hour, triethanolamine is then added in 115 DEG C, stirring obtains polymeric matrix after 35 minutes.

4. a kind of preparation method of brush composition, it is characterised in that comprise the following steps：

5. a kind of preparation method of heat stable resin system, it is characterised in that comprise the following steps, hexa, which is added, to be had In machine silicon phenolic resin, 140 DEG C are stirred 25 minutes, then add glycerin monostearate, and 90 DEG C are stirred 10 minutes；Add hello quinoline Pungent two mercaptan of derivative, 1,8-, after stirring 30 minutes, adds BMI, three cobalt oxide lanthanums（LnCoO₃）, continue to stir 1 hour, triethanolamine is then added in 115 DEG C, stirring obtains polymeric matrix after 35 minutes；Add graphene oxide into epoxy In resin, 160 DEG C of stirrings add diphenyl phosphine oxide and aliphatic amine polyoxyethylene ether after 1 hour, and 120 DEG C are stirred 2 hours, are then added Paraffin, is stirred 1 hour, adds polymeric matrix, is stirred 10 minutes, is obtained heat stable resin system.

6. preparation method according to claim 1, it is characterised in that six ammonium chloroiridates, dioctyl tin, zinc acetate, ethanol, Hexamethylene, potassium hydroxide methanol solution, TBHP, polyvinyl alcohol, ammoniacal liquor, 3,5- dimethyl pyrazoles, tetraphenyl porphin Quinoline iron, the mass ratio of CNT are 15: 30: 55: 200: 150: 20: 15: 20: 10: 8: 5: 3；Hexa, organosilicon Pungent two mercaptan of phenolic resin, glycerin monostearate, hello quinoline derivant, 1,8-, BMI, three cobalt oxide lanthanums, three second Hydramine, graphene oxide, epoxy resin, diphenyl phosphine oxide, aliphatic amine polyoxyethylene ether, the mass ratio of paraffin are 11: 20: 6: 5: 8: 100∶0.5∶10∶3∶30∶12∶8∶6；Polyester resin, molybdenum disulfide, nano powder, heat stable resin system, polystyrene, polyphenylene sulfide Ether, PZ, the mass ratio of ethylene vinyl acetate copolymer are 12: 3: 28: 100: 5: 6: 2: 12。

7. preparation method according to claim 1, it is characterised in that potassium hydroxide in the potassium hydroxide methanol solution Mass concentration is 4.5%；The molecular weight of the aliphatic amine polyoxyethylene ether is 2500~3500；The molecular weight of the polyvinyl alcohol For 1500~2000.

8. preparation method according to claim 1, it is characterised in that the condition of hot pressing be 1MPa/150 DEG C of solidification 2.5~ + 1.5MPa/220 DEG C of solidifications in 1.5~2.0 hours of+2MPa/190 DEG C of solidifications in 3.0 hours 3.5~4.5 hours.

9. product prepared by any one preparation method according to claims 1 to 5.

10. a kind of motor brush structure, it is characterised in that the brush structure includes preparation method described in claim 1 and prepared Brush, in addition to brushgear housing.