CN1170910C - Cold pressing process of preparing friction material by using phenolic resin as adhesive - Google Patents
Cold pressing process of preparing friction material by using phenolic resin as adhesive Download PDFInfo
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Abstract
The present invention discloses a production method for a friction material by adopting bicomponent liquid resins of a first component resin and a second component resin as adhesives through cold press moulding, wherein the adopted first component resin is a cashew nut shell oil resin or a modified cashew nut shell oil resin, and the second component resin is a phenolic resin or a modified phenolic resin. The bicomponent resin adopted by the present invention has the advantages of higher reactivity and no necessity for clamping devices during the process of heat treatment, and can ensure the uniformity and the compactness of the structure of moulding materials after treated by the heat treatment and no occurrence of shape changes. In addition, the method of the present invention has the advantages of greatly reduced production energy consumption and improved production efficiency, and the friction material produced by adopting the method of the present invention has favorable performance.
Description
The present invention relates to resol and prepare the method for friction materials as tackiness agent, specifically adopt two component resol as tackiness agent, coldmoulding prepares the method for friction materials.
Friction materials among the present invention refers to braking automobile liner, car clutch face sheet, train braking sheet, subway brake facing, engineering machinery brake and engineering machinery clutch surface.Friction materials of the present invention can be an asbestos friction material, also can be asbestos-free friction material.Used no fibrous magnesium silicate refers to steel fiber, copper fiber, aluminum fiber, glass fibre, organic fibre and non-asbestos mineral wool in the no asbestos abrasives.Be widely adopted with the have asbestos and the asbestos-free friction material of resol as the tackiness agent preparation.Generally adopt pressure sintering to prepare friction materials at present both at home and abroad, promptly friction materials need be done further processing then 150 ℃～180 ℃ mould inner pressure typing.The time that material stops in press also will be between 10-20 minute.The shortcoming of pressure sintering is the energy consumption height, and production efficiency is low, and environmental pollution is comparatively serious.It is a kind of developing new technology that cold press process prepares abrasives.So-called cold press process is exactly under normal temperature condition, and blended friction materials raw material is finalized the design at mould inner pressure, becomes molding mass, molding mass is directly heat-treated, thereby avoided the technological process of friction materials 150 ℃～180 ℃ mould inner pressure typing.The cold press process of being reported at present prepares abrasives technology, for example, publication number is in two Chinese patent application of CN1143662A, CN1211604A, the tackiness agent that adopts is universal resol, this resin activity is low, molding mass is in heat treatment process, and not only distortion is big, and loosely organized.In order to overcome this shortcoming, have to use anchor clamps to be fixed into moulding mixture, consequently need a large amount of anchor clamps, and in production process anchor clamps mounting or dismounting trouble.Remove in addition, present cold-press process also has some other harsh requirements, for example, publication number is that to require the thermal treatment temp of molding mass in the Chinese patent application of CN1211604A be 315～325 ℃, and friction materials manufacturing enterprise generally is difficult to adopt so high thermal treatment temp.In addition, so high thermal treatment temp will make friction materials hardness excessive, and this probability that produces noise in the time of can causing friction materials work increases greatly.Because cold-press process is not mature enough, therefore prepares in the industry at abrasives at present and seldom adopt.
The object of the present invention is to provide and a kind ofly adopt two component resol to cold pressing to prepare the method for friction materials as tackiness agent, it not only can prepare high performance friction materials, and production energy consumption can be reduced significantly, enhance productivity, thereby make technology industrialization, the through engineering approaches of the preparation friction materials of colding pressing.
For achieving the above object, the present invention adopts phenolic resin as adhesive to cold pressing to prepare the method for friction materials to be achieved in that to adopt the two components resin of first, second as tackiness agent, after tackiness agent, fiber, filler mixing, compression molding is directly heat-treated molding mass and is made abrasives; The first components resin that is adopted is a kind of in the two modification cashew nut shell oil liquid resins of cashew nut shell oil liquid resin, boride modification cashew nut shell oil liquid resin, phenol modification cashew nut shell oil liquid resin or boron and phenol, and the component B resin that is adopted is phenolic aldehyde liquid resin or aminated compounds modified phenolic liquid resin; The weight ratio of described first components resin and component B resin is in 5: 1～1: 2 scope, and when needing the good hardness of material snappiness to hang down, the first components resin can be used more; Otherwise when needing hardness high, then the component B resin can be used more.
Above-mentioned employing phenolic resin as adhesive is colded pressing and is prepared the method for friction materials, the temperature range of described compression molding is 0～60 ℃, its die temperature is in 0～60 ℃ of scope, the temperature of molding compound is in 0～60 ℃ of scope, compression molding pressure is 10～200Mpa, is 5～30 seconds in the following time length of pressure; Molding mass does not use anchor clamps and directly heat-treats in 70～200 ℃ of temperature ranges, the treatment time is 8～20 hours.
Above-mentioned employing phenolic resin as adhesive is colded pressing and is prepared the method for friction materials, and described boride is boric acid or boron trioxide (B
2O
3), described phenol modification refers to phenol or cresol modified, and the two modifications of described boron and phenol refer to each a kind of while modification of using in boride and the phenol modification, and described aminated compounds refers to trimeric cyanamide or aniline.
Adopt phenolic resin as adhesive to cold pressing and prepare the method for friction materials, adopt following method preparation as the cashew nut shell oil resin of first components resin: with cashew nut shell oil and catalyzer at the reactor internal heating, the weight ratio of cashew nut shell oil and catalyzer is 100: (0.5～6), carry out heat polymerization under 180～280 ℃ temperature, the reaction times is 2～10 hours.Adopt viscosity measurement control cashew nut shell oil auto-polymerization reaction end.After reaching needed viscosity, resin temperature is cooled to 80～140 ℃, removes catalyzer, add an amount of solvent cut and be first component finished product.
Adopt phenolic resin as adhesive to cold pressing and prepare the method for friction materials, can be prepared as follows: one or both and catalyzer of cashew nut shell oil, boric acid or boron trioxide are added reactor simultaneously as the boron modification cashew nut shell oil resin of first components resin.One or both of cashew nut shell oil, boric acid or boron trioxide, catalyzer three's weight ratio is 100: (2～15): (0.5～6).Carry out polyreaction under 180～280 ℃ temperature, the reaction times is 2～10 hours.Adopt viscosity measurement control resin polymerization reaction end.After reaching needed viscosity resin is cooled to 80～140 ℃, removes catalyzer, add an amount of solvent cut and be first component finished product.
Adopt phenolic resin as adhesive to cold pressing and prepare the method for friction materials, adopt following method to prepare: one or both and catalyzer of cashew nut shell oil, phenol or cresols are added reactor simultaneously as the phenol modification cashew nut shell oil resin of first components resin.One or both of cashew nut shell oil, phenol or cresols, catalyzer three's weight ratio is 100: (5～50): (0.5～6).Carry out polyreaction under 180～280 ℃ temperature, the reaction times is 2～10 hours.Adopt viscosity measurement control resin polymerization reaction end.After reaching needed viscosity, 180～220 ℃ of underpressure distillation 0.5～1 hour, vacuum tightness was 5～70mm mercury column, to remove unreacted free phenol.Resin is cooled to 80～140 ℃, removes catalyzer, add an amount of solvent cut and be first component finished product.
Adopt phenolic resin as adhesive to cold pressing and prepare the method for friction materials, adopt following method preparation as the boron and the two component modification cashew nut shell oil resins of phenol of first components resin: with cashew nut shell oil, phenol or cresols one or both, boric acid or boron trioxide one or both, catalyzer adding simultaneously earlier.The weight ratio of one or both of one or both of cashew nut shell oil, boric acid or boron trioxide, phenol or cresols, catalyzer is 100: (2～25): (5～50): (0.5～6).Carry out polyreaction under 180～280 ℃ temperature, the reaction times is 2～10 hours.Adopt viscosity measurement control resin polymerization reaction end.After reaching needed viscosity, 180～220 ℃ of underpressure distillation 0.5～1 hour, to remove unreacted free phenol.Be cooled to 80～140 ℃, remove catalyzer, add an amount of solvent cut and be first component finished product.
Adopt phenolic resin as adhesive to cold pressing and prepare the method for friction materials, the synthetic used catalyzer of first components resin is a lewis acid catalyst, for example zinc chloride, tin tetrachloride, aluminum chloride, titanium tetrachloride, sulfuric acid, Vanadium Pentoxide in FLAKES and phosphoric acid etc., also can adopt organic sulfonic acid class catalyzer, for example tosic acid, Phenylsulfonic acid.Used cashew nut shell oil raw material comprises: the cashew nut shell oil that does not pass through any processing; Cashew nut shell oil through the decarboxylation processing; Through distillation purified cashew nut shell oil---cardanol.
Adopt phenolic resin as adhesive to cold pressing and prepare the method for friction materials, can add solvent cut in the first components resin, solvent can be ethanol, ethyl acetate, toluene, dimethylbenzene or gasoline; The solid content of resin is controlled at 75～85%.
Above-mentioned employing phenolic resin as adhesive is colded pressing and is prepared the method for friction materials, adopt a kind of in following two kinds of methods to remove catalyzer in the first components resin: (1) is cooled to 100～140 ℃ with the first components resin, add toluene or dimethylbenzene, be cooled to 90～95 ℃ again, hot water with 85～95 ℃, wash several times, after water precipitation is separated, distill out remaining moisture and solvent; (2) adopt in the alkaline conditioner and lewis acid catalyst or organic sulfonic acid, alkaline conditioner is sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, hydrated barta, sodium bicarbonate and organic amine (aliphatic amide or aromatic amine).Earlier the first components resin is cooled to 80～95 ℃ during operation, adds alkaline conditioner again and get final product.
Adopt phenolic resin as adhesive to cold pressing and prepare the method for friction materials, phenol as the phenolic aldehyde liquid resin of component B resin mainly refers to phenol and cresols, aldehyde refers to formaldehyde, it adopts the preparation of following method: a kind of of phenol or cresols or two kinds, formaldehyde, basic catalyst are added reactor simultaneously, the mol ratio of phenol or cresols and formaldehyde is 1: (1.05～1.5), the weight ratio of phenol or cresols and basic catalyst is 100: (0.2～4), carry out condensation reaction under 65～95 ℃ condition, the reaction times is 1～6 hour.The polymerization velocity of measuring reactant is with the control reaction end, and the polymerization velocity of resin on 150 ℃ of metal hot plates is 80～250 seconds reaction ends.After reaching desired reaction end, add corresponding acid regulator with in and basic catalyst, decompression dehydration to 80～95 ℃, vacuum tightness is 5～70mm mercury column, is second component finished product.
Adopt phenolic resin as adhesive to cold pressing and prepare the method for friction materials, adopt following method preparation as the aminated compounds modified phenolic liquid resin of component B resin: a kind of of phenol or cresols or two kinds, aminated compounds, formaldehyde, basic catalyst are added reactor simultaneously, phenol or cresols, aminated compounds, formaldehyde three's mol ratio is 1: (0.02～0.2): (1.05～1.6), the weight ratio of phenol or cresols and basic catalyst are 100: (0.2～4).Reacted under 65～95 ℃ condition 1～6 hour, the polymerization velocity of measuring reactant is with the control reaction end, and the polymerization velocity of resin on 150 ℃ of metal hot plates is 100～300 seconds reaction ends.Add corresponding acid regulator with in and basic catalyst, decompression dehydration to 80～95 ℃, vacuum tightness is 5～70mm mercury column, is second component finished product.
Among the present invention, acid regulator can be oxalic acid, MALEIC ANHYDRIDE or sulfuric acid.
Above-mentioned employing phenolic resin as adhesive is colded pressing and is prepared the method for friction materials, and the synthetic used catalyzer of component B resin is a basic catalyst, and described basic catalyst can be ammoniacal liquor, sodium hydroxide, calcium hydroxide, hydrated barta or magnesium hydroxide.
Above-mentioned employing phenolic resin as adhesive is colded pressing and is prepared the method for friction materials, can add solvent cut in the component B resin, and solvent can be methyl alcohol, ethanol, toluene, dimethylbenzene or gasoline.Yet solubilizing agent not, solubilizing agent is not water-based resin.The solid content of resin is controlled at 75～85%.
Adopt phenolic resin as adhesive to cold pressing and prepare the method for friction materials, can add an amount of hexamethylenetetramine in the two components resin of first, second, consumption is 0～6% of a first components resin weight, and when the component B resin demand was on the low side, the hexamethylenetetramine consumption can be limit on the upper side; Otherwise limit on the lower side.
Adopt phenolic resin as adhesive to cold pressing and prepare the method for friction materials, the weight content of each composition is as follows in the prescription of abrasives: in (1) asbestos abrasives: resin 15～30%, fiber 35～45%, rubber 0～8%, filler or friction conditioning agent 19～50%; (2) in the no asbestos abrasives: resin 15～30%, fiber 10～35%, rubber 0～8%, filler or friction conditioning agent 29～75%.
Adopt phenolic resin as adhesive to cold pressing and prepare the method for friction materials, the manufacturing processed of colding pressing that its staple fibre strengthens clutch surface (chenille article) or brake friction material is as follows: filler, fiber, resin, solidifying agent (hexamethylenetetramine) and rubber etc. are mixed in mixer, temperature in the mixer is controlled at 50～90 ℃, and mixing time is 0.5～3 hour.Mixer is kneader or the Banbury mixer that has chuck.With the temperature in steam and the chilled water modulation mixer.Vacuum extractor is housed on the mixer, after mixing 15～30 minutes, starts vacuum pump, vacuum tightness is 10～70mm mercury column, and solvent in the compound and moisture are removed.On the high side as resin demand, for example be 25～30% by weight percentage, then need adopt tablets press the blended molding compound to be caused the particle of tablet size; On the low side as resin demand, be 15～18% by weight percentage for example, then must not adopt granulation process.Molding compound after mixing back or the granulation is delivered to press go compacting.The temperature of mould cavity temperature and molding compound is 0～60 ℃, and the required pressure of colding pressing is 10～200Mpa, and the time that molding compound is kept under pressure is 5～30 seconds.Employed releasing agent is lubricating grease or Vaseline during mold pressing.The brake(-holder) block that suppresses delivered in the baking oven heat-treat, adopt staged to heat up during curing and solidify.Friction materials after heat treatment through ground, is the friction materials finished product.
Above-mentioned employing phenolic resin as adhesive is colded pressing and is prepared the method for friction materials, and the temperature of mould cavity temperature and molding compound is preferably in 15～25 ℃, and the required pressure of colding pressing is preferably 40～80Mpa, and the time that molding compound is kept under pressure is preferably 8～12 seconds.
Adopt phenolic resin as adhesive to cold pressing and prepare the method for friction materials, its macrofiber strengthens clutch surface (winding-type) to be adopted as next step pickling process technology manufacturing: the two components resin of first, second, solvent and filler are mixed, be mixed with the suitable slurry of viscosity, after macrofiber flooded in slurry, through the rubber roll extruding, send to drying again, drying temperature is 70～90 ℃, and the time of passing through in dry drying tunnel is 20～60 minutes.Fibrous bundle behind the dipping or cloth are sent into the wrapping machine winding through cutting out.In the one step pickling process, the part by weight of first component and component B is 1.5: 1～3: 1.Macrofiber can be a fibrous bundle, also can be woven cloth.
Adopt phenolic resin as adhesive to cold pressing and prepare the method for friction materials, its macrofiber strengthens clutch surface (winding-type) and adopts following two step pickling process technologies to make: dipping is with the two components resin of first, second for the first time, be mixed with the lower slurry of viscosity with solvent, fibrous bundle and cloth process are flooded for the first time.Suitably after the oven dry, carry out the dipping second time again.For the second time dipping is identical with impregnation steps in the single stage method.The resin solution viscosity of dipping preparation for the first time is lower, and the solid content of resin is 25～35%; Dipping solution viscosity can be high for the second time, and viscosity can be than the mixed serum height of single-steeping method.Two step pickling processes, twice used two components resin ratio can be different.Two steps in the pickling processes the first time steeping fluid first component and the ratio of component B be 2: 1～1: 2, the ratio of steeping fluid first component and component B is 2: 1～5: 1 for the second time.To send into the wrapping machine winding through dipping and exsiccant macrofiber bundle, and must send into the wrapping machine winding again through cutting out through dipping and exsiccant cloth.To send to through the molding compound that twines again and cold pressing and thermal treatment.Its process is identical with the process of brake friction material.Macrofiber can be a fibrous bundle, also can be woven cloth.
Adopt phenolic resin as adhesive to cold pressing and prepare the method for friction materials, adopt following processing step in formula system, to add styrene-butadiene rubber(SBR) or nitrile rubber: rubber through over-mastication, is dissolved it with solvent again, and add vulcanizing agent, promotor and anti-aging agent.When batch mixing, elastomer latex and first, the component B resin for preparing added mixer simultaneously.Because first components resin and elastomer latex have good consistency, also first components resin and elastomer latex directly can be mixed, physics is prepared into modified rubber cashew nut shell oil resin, in order to using, adds mixer with the component B resin again during batch mixing.
As everyone knows, macromolecule resin has this characteristics: during the temperature rising, viscosity can significantly reduce, promptly mobile meeting phenomenal growth; When state of cure (crosslinked) increased, viscosity can enlarge markedly, promptly mobile can significantly the reduction up to becoming insoluble infusible solid.The two components resin that adopt in the inventive method have following characteristics: the two components of first, second are deposited separately respectively, can not react; After the two components of first, second mixed, at room temperature (≤35 ℃) can be placed 3～90 days, can not take place more significantly to react; Two components were kept 1～4 hour at 70～90 ℃ after mixing, and significantly curing reaction can take place, and for example, on 80 ℃ metal hot plate, it is 30～120 minutes that two components mix the back gel time; Curing reaction faster then can take place at 120～160 ℃ after mixing in two components, and for example, on 150 ℃ metal hot plate, it was 20～100 seconds that two components mix the back gel time.Add two components resin of filler and filamentary material, after mixing and colding pressing, under 70～90 ℃ of conditions, can not flow immediately; Along with temperature is deeply inner by the top layer, a kind of trend is creep flow very slowly generation, and another kind of trend is that slower crosslinking curing takes place.Second kind of trend is faster than first kind of trend in the methods of the invention, so just can guarantee in the process of handling that is heating and curing, the creep flow material deformation that causes can not take place, thereby guarantees that being cold-pressed into moulding mixture has good guarantor's type (external form does not change) effect.The two-component adhesive that the inventive method adopts also has the following advantages: as long as follow suitable thermal treatment process, can guarantee the densification of material internal even structure, can not produce subsurface defects such as bubble, pore, layering, material can have favorable mechanical performance and friction and wear behavior.Simultaneously, can find out from technique scheme that the inventive method can make the cashew nut shell oil content in the tackiness agent regulate arbitrarily between 30～85%, this has substantially exceeded the content (10～30%) of cashew nut shell oil in the existing cashew nut oil modified alkyd resin.Therefore, adopt the friction materials of the inventive method preparation, its snappiness is good ,-hardness is low, stable friction factor, abrasion are low, noise is low advantage are more outstanding.Resin after the two components of the present invention solidify is actually boron modification or aminated compounds modified phenolic resins, and this resinoid has the good temperature resistance energy.For example, boron, the two modification cashew nut shell oil resol of trimeric cyanamide have very good resistance to elevated temperatures.Adopt the inventive method, working conditions that can be different according to friction materials, the content of preferred boride, aminated compounds, cashew nut shell oil and phenolic compound makes the over-all properties optimizing of friction materials.In addition, when preparing friction materials according to the inventive method, add an amount of hexamethylenetetramine, portion forms uniform nano level to micron-sized micropore within it, this is in heat treatment process, hexamethylenetetramine slowly discharges due to the ammonia equably, and the material with this structure is a kind of good suction noise material.Therefore, adopt the inventive method to prepare friction materials, can reduce the probability that noise produces significantly.The inventive method has been got rid of pressure sintering mould and molding compound has been carried out electrically heated processing step, can reduce production energy consumption significantly.Material need stop in press usually and compare in 10～20 minutes when preparing friction materials with pressure sintering, and the friction materials of cold press process preparation only needs to stop 5～30 seconds in press, so the production efficiency of cold press process can significantly improve; The inventive method prepares friction materials and do not need to adopt anchor clamps in heat treatment process, has avoided the trouble of installation and removal anchor clamps in the production process, has also saved the cost of equipment of anchor clamps in enormous quantities simultaneously; In addition, the inventive method has good guarantor's type effect too in the treating processes that is heating and curing except have good typing effect when colding pressing.In sum, method of the present invention has obvious superiority: the friction materials of (1) preparation has good performance; (2) preparation technology can reduce production energy consumption significantly; (3) preparation technology can increase substantially production efficiency.
Below in conjunction with embodiment and accompanying drawing the present invention is described in further detail.
Thermal treatment heating curve synoptic diagram in Fig. 1 the inventive method.The every lattice of X-coordinate are represented 0.5～3 hour among the figure, and wherein curve 1 expression thermal treatment top temperature is 160 ℃, and curve 2 expression thermal treatment top temperatures are 180 ℃, and curve 3 expression thermal treatment top temperatures are 200 ℃.
The preparation of embodiment one asbestos brake friction material
(1) preparation of first components resin
In parts by weight, with 100 parts of cashew nut shell oils, 2 parts in 90% concentration sulfuric acid, 0.2 part of tosic acid add in the reactor, are warmed up to 250 ℃, are incubated 4～6 hours, and sampling and measuring viscosity, viscosity controller are in index: be 1000～4000MPas in the time of 80 ℃.Reach needed viscosity, be cooled to 130 ℃, add 30 parts of dimethylbenzene, stir.When temperature in the kettle drops to 95 ℃, add 50 parts of 80～90 ℃ of hot water, stirred 10 minutes, stop to stir, treat water and resin layering, separate water outlet.Wash repeatedly 3 times.Be warmed up to 180 ℃, steam unsegregated moisture and dimethylbenzene, be cooled to 95 ℃, add 22 parts of toluene.By the cashew nut shell oil resin of this operation steps preparation, solid content is about 80 ± 2%, and viscosity is 1500～15000MPas (25 ℃).
(2) preparation of component B resin
In parts by weight, with 100 parts of phenol, 122 parts in 37% concentration formaldehyde, 1.5 parts of hydrated bartas add in the reactor simultaneously, are warmed up to 85 ℃, react sampling and measuring polymerization velocity, polymerization velocity degree controlling index: be 80～250 seconds in the time of 150 ℃ 3～4 hours.Reach desired index, add oxalic acid, making the ph value is 6～7.Decompression dehydration when temperature in the kettle reaches 92 ℃, when vacuum tightness is the 10mm mercury column, stops decompression dehydration, adds 20 parts of industrial spirit dilutions.By the liquid phenolic resin of this operation steps preparation, solid content is 80 ± 2%, and viscosity is 300～1500MPas (25 ℃).
(3) preparation of friction materials
By following formulation asbestos brake friction material
15 parts of first components resin
10 parts of component B resins
0.8 part of hexamethylenetetramine
45 parts in asbestos
3 parts of tyre talcs
1 part in zinc oxide
5 parts of coke powders
2 parts of amorphous graphites
11.2 parts of feldspars
13 parts in barite
Above-mentioned raw materials is added kneader in proportion, open kneader and heating unit thereof, stirred 30～40 minutes, when temperature is raised to 80 ℃, start vacuum pump, vacuumize mediating in the chamber, vacuum tightness maintains the 20mm mercury column, continues to mediate 60 minutes.The molding compound that mixes delivered on the press suppress.During compacting, molding compound and die temperature are 25 ℃, and pressure is 60Mpa, and the dwell time is 10 seconds.The molding mass that suppresses is sent into baking oven, heat-treats by curve shown in Figure 13, get final product the brake facing work in-process.
The preparation of embodiment two no asbestos automobile brake sheets
(1) preparation of modification cashew nut shell oil resin (first component)
In parts by weight,, be warmed up to 230 ℃ with 100 parts of cashew nut shell oils, 11 parts of boric acid, 5 parts of 90% concentration phosphoric acid, in 0.4 part of adding reactor of methylsulphonic acid, under 230 ℃ of temperature, reacted 3～5 hours, sampling and measuring viscosity, viscosity controller index: be 600～2000MPas in the time of 80 ℃, reach the viscosity of defined, be cooled to 95 ℃, add 4 parts in calcium hydroxide, continue to be warmed up to 180 ℃, kept 0.5 hour under 180 ℃ of temperature, be cooled to 80 ℃, add 24 parts of industrial spirit.By the resin of this step preparation, solid content is 80 ± 2%, and viscosity is 800～8000MPas (25 ℃).
(2) preparation of cyanurotriamide modified liquid phenolic resin (component B)
In parts by weight, with 100 parts of phenol, 15 parts of trimeric cyanamides, 140 parts in 37% concentration formaldehyde, 3 parts of 25% concentration ammoniacal liquor, add in the reactor simultaneously, be warmed up to 85 ℃, 85 ℃ of reactions 3～4 hours, the sampling and measuring polymerization velocity, polymerization velocity degree controlling index: be 100～300 seconds in the time of 150 ℃.Reach desired index, add MALEIC ANHYDRIDE, making the ph value is 6～7.Decompression dehydration when temperature in the kettle reaches 92～95 ℃, when vacuum tightness is the 60mm mercury column, stops decompression dehydration, adds 24 parts of industrial spirit dilutions.By the liquid phenolic resin of this operation steps preparation, solid content is 80 ± 2%, and viscosity is 200～1000MPas (25 ℃).
(3) preparation of friction materials
By following formulation asbestos-free friction material
2 parts in 18 parts of magnesium oxide of first component
5 parts of 10 parts of coke powders of component B
0.5 part of 16 parts of hexamethylenetetramine of steel fiber
4.5 parts of 14 parts of Sodium Fluorides of vermiculite
5 parts of 5 parts of feldspars of chromite powder
8 parts of 5 parts of process whites of friction powder
2 parts in 8 parts of nitrile rubber powder of graphite
Above-mentioned raw materials is added kneader in proportion, open the kneader heating unit and mediate oar, mediated 30～40 minutes, when temperature is raised to 80 ℃, start vacuum pump, to vacuumizing in the kneader chamber, vacuum tightness maintains the 20mm mercury column, continues to mediate 60 minutes.The molding compound that mixes delivered on the press suppress.During compacting, molding compound and die temperature are 25 ℃, and pressure is 80Mpa, and the dwell time is 12 seconds.The molding mass that suppresses is sent into baking oven, heat-treat, can obtain the non-asbestos brake block work in-process by curve shown in Figure 12.
The preparation of embodiment three asbestos winding clutch sheets
(1) preparation of boron, the two modification cashew nut shell oil resins (first component) of phenol
In parts by weight, with 100 parts of cashew nut shell oils, 20 parts of phenol, 8 parts of boric acid, 2 parts of zinc chloride, 0.4 part of tosic acid, add in the reactor, be warmed up to 185 ℃, 185 ℃ of reactions 2 hours, be warmed up to 220 ℃, 220 ℃ of reactions 3～5 hours, sampling and measuring viscosity, viscosity controller index: be 500～1500MPas in the time of 80 ℃.After reaching needed viscosity, 180～220 ℃ of underpressure distillation 0.5～1 hour, vacuum tightness was the 40mm mercury column, to remove unreacted free phenol.Be cooled to 95 ℃, add 4.5 parts of hydrated bartas, continue to be warmed up to 180 ℃, 180 ℃ are incubated 0.5 hour, are cooled to 95 ℃, add 27 parts of non-leaded gasolines.By the resin of this operation steps preparation, solid content is about 80 ± 2%, and viscosity is 1000～10000MPas (25 ℃).
(2) aniline modified liquid resol
In parts by weight, with 100 parts of technical phenols (phenol 70%, cresols 30%), 12 parts of aniline, 135 parts in 37% concentration formaldehyde, 0.5 part in sodium hydroxide, add in the reactor simultaneously, be warmed up to 85 ℃, 85 ℃ of reactions 3～5 hours, the sampling and measuring polymerization velocity, polymerization velocity controlling index: be 100～300 seconds in the time of 150 ℃.Reach desired index, add sulfuric acid, making the ph value is 6～7.Decompression dehydration when temperature in the kettle reaches 92～95 ℃, when vacuum tightness is the 40mm mercury column, stops decompression dehydration, adds 22 parts of non-leaded gasoline dilutions.By the liquid modifying resol of this operation steps preparation, solid content is 80 ± 2%, and viscosity is 150～1000MPas (25 ℃).
(3) preparation of clutch surface
3.1 the preparation of steeping fluid for the first time
The prescription of dipping is as follows for the first time
First components resin component B resin solvent (gasoline)
15 parts 25 parts 60 parts
Above-mentioned prescription is mixed in proportion, stirs and get final product.
3.2 the preparation of steeping fluid for the second time
By the following formulated steeping fluid second time
4.5 parts of 26 parts of Sodium Fluorides of first components resin
10 parts of 9 parts of coke powders of component B resin
10 parts in 8 parts of potter's clay of styrene-butadiene rubber(SBR)
5.4 parts of 1.5 parts of chromite powders of hexamethylenetetramine
0.4 part in 1 part of aluminum oxide of sulphur
0.1 part of N-phenyl-β-naphthalene of tetramethyl-thiuram disulfide is by 0.1 part
7 parts of 1 part of feldspars of zinc oxide
2 parts in 4 parts of magnesium oxide of carbon black
30 parts of 15 parts of solvents of barium sulfate (gasoline)
Rubber through over-mastication, is dissolved it with solvent, and add sulphur in the above-mentioned prescription and make vulcanizing agent, tetramethyl-thiuram disulfide and make promotor and N-phenyl-β-naphthalene by making anti-aging agent.When batch mixing, elastomer latex and first, the component B resin for preparing added mixer simultaneously.Above-mentioned prescription is prepared into the heavy-gravity slurry in hollander.
Behind the dipping of asbestos yarn through single-steeping liquid and double-steeping liquid, deliver to the drying tunnel inner drying, drying temperature is 80 ℃, and be 60 minutes time of drying.Use wrapping machine that dried asbestos yarn process is twined, can deliver on the press and suppress.During compacting, molding compound and die temperature are 25 ℃, and pressure is 100Mpa, and the dwell time is 15 seconds.The molding mass that suppresses is sent into baking oven, heat-treat,, can make and twine the asbestos clutch surface through ground by curve shown in Figure 13.
The main kind of filler that is adopted in the inventive method or friction modifier has: aluminum oxide, silicon carbide, chromite powder, powdered iron ore, barite, vermiculite, graphite, feldspar, quartz, wollastonite, potter's clay, carbon black, coke powder, magnesium oxide, zinc oxide, fluorite, Sodium Fluoride, iron sulphide and friction powder etc.
In the inventive method, phenol and two kinds of phenol of cresols can be used for the modification cashew nut shell oil simultaneously, also boric acid and boron trioxide can be used for the modification cashew nut shell oil simultaneously, cresols can meta-cresol, ortho-cresol, p-cresol or three's mixing.Except phenol and cresols, the phenol that is used for the modification cashew nut shell oil in the inventive method can also be the phenol of other kind, for example Resorcinol, xylenol etc.In the synthetic component B resin, cresols and phenol also can mix use simultaneously.
Claims (7)
1, adopts phenolic resin as adhesive to cold pressing and prepare the method for friction materials, after tackiness agent, fiber, filler mixing, compression molding, heat-treat again and make friction materials, it adopts the two components resin of first, second as tackiness agent, described first components resin is a kind of in the two modification cashew nut shell oil liquid resins of cashew nut shell oil liquid resin, boride modification cashew nut shell oil liquid resin, phenol modification cashew nut shell oil liquid resin or boron and phenol, and described component B resin is phenolic aldehyde liquid resin or aminated compounds modified phenolic liquid resin; The weight ratio scope of described first components resin and component B resin is 5: 1～1: 2, it is characterized in that, described boride is boric acid or boron trioxide, described phenol modification refers to phenol or cresol modified, the two modifications of described boron and phenol refer to each a kind of material modification simultaneously of using in above-mentioned boride and the above-mentioned phenol modification, and described aminated compounds refers to trimeric cyanamide or aniline.
2, employing phenolic resin as adhesive as claimed in claim 1 is colded pressing and is prepared the method for friction materials, it is characterized in that, described first components resin can adopt a kind of preparation the in following four kinds of methods:
(1) preparation method of described cashew nut shell oil resin: with cashew nut shell oil and catalyzer at the reactor internal heating, the part by weight of described cashew nut shell oil and catalyzer is 100: (0.5～6), carry out heat polymerization under 180～280 ℃ temperature, the reaction times is 2～10 hours; Adopt viscosity measurement control cashew nut shell oil auto-polymerization reaction end.After reaching needed viscosity, resin temperature is cooled to 80～140 ℃, removes catalyzer, add an amount of solvent cut and be first component finished product;
(2) preparation method of described boron modification cashew nut shell oil resin: one or both and catalyzer of cashew nut shell oil, boric acid or boron trioxide are added reactor simultaneously, and one or both of described cashew nut shell oil, boric acid or boron trioxide, catalyzer three's weight ratio is 100: (2～15): (0.5～6); Carry out polyreaction under 180～280 ℃ temperature, the reaction times is 2～10 hours; Adopt viscosity measurement control resin polymerization reaction end.After reaching needed viscosity resin is cooled to 80～140 ℃, removes catalyzer, add an amount of solvent cut and be first component finished product;
(3) preparation method of described phenol modification cashew nut shell oil resin: with cashew nut shell oil, one or both of phenol or cresols and catalyzer add reactor simultaneously, described cashew nut shell oil, one or both of phenol or cresols, catalyzer three's weight ratio is 100: (5～50): (0.5～6), under 180～280 ℃ temperature, carry out polyreaction, reaction times is 2～10 hours, adopt viscosity measurement control resin polymerization reaction end, after reaching needed viscosity, 180～220 ℃ of underpressure distillation 0.5～1 hour, vacuum tightness is 5～70mm mercury column, to remove unreacted free phenol, resin is cooled to 80～140 ℃, remove catalyzer, add an amount of solvent cut and be first component finished product;
(4) the two component modification cashew nut shell oil resins of described boron and phenol adopt following method preparation: with cashew nut shell oil, phenol or cresols one or both, boric acid or boron trioxide one or both, catalyzer adds earlier simultaneously, the weight ratio of one or both of one or both of described cashew nut shell oil, boric acid or boron trioxide, phenol or cresols, catalyzer is 100: (2～25): (5～50): (0.5～6), carry out polyreaction under 180～280 ℃ temperature, the reaction times is 2～10 hours; Adopt viscosity measurement control resin polymerization reaction end, reach needed viscosity after, 180～220 ℃ of underpressure distillation 0.5～1 hour, to remove unreacted free phenol; Be cooled to 80～140 ℃, remove catalyzer, add an amount of solvent cut and be first component finished product;
Used diluting solvent can be a kind of in ethanol, ethyl acetate, toluene, dimethylbenzene or the gasoline in the synthetic described first component liquid resin method, and the solid content of resin is controlled at 75～85% during dilution; Used catalyzer is lewis acid catalyst or organic sulfonic acid class catalyzer; The method of removing catalyzer in the described first components resin is a kind of in following two kinds: (1) is cooled to 100～140 ℃ with described first components resin, add toluene or dimethylbenzene, be cooled to 90～95 ℃ again, hot water with 85～95 ℃, wash several times, after the water precipitation separation, distill out remaining moisture and solvent; (2) adopt the alkaline conditioner catalyst neutralisation, alkaline conditioner is a kind of in sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, hydrated barta, sodium bicarbonate, aliphatic amide or the aromatic amine, earlier described first components resin is cooled to 80～95 ℃ during operation, adds described alkaline conditioner again.
3, employing phenolic resin as adhesive as claimed in claim 1 or 2 is colded pressing and is prepared the method for friction materials, it is characterized in that, described component B resin can adopt a kind of preparation the in following two kinds of methods:
(1) preparation method of described phenolic aldehyde liquid resin: a kind of of phenol or cresols or two kinds, formaldehyde, basic catalyst are added reactor simultaneously, the mol ratio of described phenol or cresols and formaldehyde is 1: (1.05～1.5), the part by weight of described phenol or cresols and basic catalyst is 100: (0.2～4), carry out condensation reaction under 65～95 ℃ condition, the reaction times is 1～6 hour; The polymerization velocity of measuring reactant is with the control reaction end, and the polymerization velocity of resin on 150 ℃ of metal hot plates is 80～250 seconds reaction ends; After reaching desired reaction end, add corresponding acid regulator with in and basic catalyst, decompression dehydration to 80～95 ℃, vacuum tightness is 5～70mm mercury column, is second component finished product;
(2) described aminated compounds modified phenolic liquid resin adopts following method preparation: a kind of of phenol or cresols or two kinds, aminated compounds, formaldehyde, basic catalyst are added reactor simultaneously, described phenol or cresols, aminated compounds, formaldehyde three's mol ratio is 1: (0.02～0.2): (1.05～1.6), the weight ratio of described phenol or cresols and basic catalyst are 100: (0.2～4); Reacted under 65～95 ℃ condition 1～6 hour, the polymerization velocity of measuring reactant is with the control reaction end, and the polymerization velocity of resin on 150 ℃ of metal hot plates is 100～300 seconds reaction ends; Add corresponding acid regulator with in and basic catalyst, decompression dehydration to 80～95 ℃, vacuum tightness is 5～70mm mercury column, is second component finished product.
Among the preparation method of described component B liquid resin, the synthetic used basic catalyst of described component B resin is a kind of in ammoniacal liquor, sodium hydroxide, calcium hydroxide, hydrated barta or the magnesium hydroxide; Described acid regulator can be a kind of in oxalic acid, MALEIC ANHYDRIDE or the sulfuric acid.
4, employing phenolic resin as adhesive as claimed in claim 1 or 2 is colded pressing and is prepared the method for friction materials, it is characterized in that, adds an amount of hexamethylenetetramine in described pair of components resin, and consumption is 0～6% of a described first components resin weight.
5, employing phenolic resin as adhesive as claimed in claim 1 or 2 is colded pressing and is prepared the method for friction materials, it is characterized in that, described abrasives is that staple fibre strengthens clutch surface or brake friction material, the mixer that adopts is kneader or the Banbury mixer that has chuck, chuck and vacuum extractor are housed on the mixer, the time that batch mixing stirs is 0.5～3 hour, and vacuum tightness is 10～70mm mercury column; The temperature of mould cavity temperature and molding compound is colded pressing required pressure between 40～80Mpa between 15～25 ℃, the time that molding compound is kept under pressure is 8～12 seconds.
6, employing phenolic resin as adhesive as claimed in claim 1 or 2 is colded pressing and is prepared the method for friction materials, it is characterized in that, described abrasives is that macrofiber strengthens clutch surface, it adopts a step pickling process manufacturing process, and the weight ratio of described first component and described component B is between 1.5: 1～3: 1.
7, employing phenolic resin as adhesive as claimed in claim 1 or 2 is colded pressing and is prepared the method for friction materials, it is characterized in that, described abrasives is that macrofiber strengthens clutch surface, it adopts two step pickling process manufacturing process, the weight ratio of first component and described component B described in the steeping fluid is at 2: 1～1: 2 for the first time, and the weight ratio of first component and described component B described in the steeping fluid was at 2: 1～5: 1 for the second time.
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2001
- 2001-06-11 CN CNB011134305A patent/CN1170910C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100335517C (en) * | 2005-09-29 | 2007-09-05 | 江苏大学 | Linseed oil modified phenol formaldehyde resin for friction material and its preparation method |
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Assignee: Ningguo Feiying Auto Spare Parts Co., Ltd. Assignor: Haiyan Huaqiang Resin Co., Ltd. Contract record no.: 2012340000213 Denomination of invention: Cold pressing process of preparing friction material by using phenolic resin as adhesive Granted publication date: 20041013 License type: Exclusive License Open date: 20011128 Record date: 20120702 |
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