CN104292409A - Modified phenolic resin and friction material containing same - Google Patents
Modified phenolic resin and friction material containing same Download PDFInfo
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- CN104292409A CN104292409A CN201410522721.9A CN201410522721A CN104292409A CN 104292409 A CN104292409 A CN 104292409A CN 201410522721 A CN201410522721 A CN 201410522721A CN 104292409 A CN104292409 A CN 104292409A
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Abstract
The invention provides modified phenolic resin and a preparation method thereof. The modified phenolic resin is prepared by adopting an in-situ intercalation method by taking organic modified montmorillonite as a modifier. The invention further provides a friction material containing the modified phenolic resin as well as a preparation method of the friction material. The heat resistance and wear resistance of the friction material are remarkably enhanced, so that the friction material can be widely used.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of silicate intercalation modifying resol and containing the friction materials of this resol, and their respective preparation method and purposes.
Background technology
Friction materials is made up of the large component of binding agent (body material), strongthener, filler and frictional property regulator four usually.Wherein binding agent is the component of brake friction material most critical, other component (strongthener, filler and frictional property regulator) is closely bonded together to obtain desired properties by it, and its performance quality directly affects the performance of Properties of Friction Materials.Along with the development and progress of science and technology, people wish that friction materials possesses following performance: 1) suitable and stable frictional coefficient; 2) heat resistanceheat resistant decline performance is good; 3) enough intensity; 4) longer work-ing life; 5) low noise and vibration etc.Therefore, in order to obtain desirable friction materials, key is improving of Binder Properties.
Resol (PF) because of its raw material be easy to get, the advantage such as cheap, production unit and technique is simple, product high comprehensive performance, and become the binding agent the most often used in organic-type friction material.But adopt that the friction materials modulus prepared of phenolic resin is high, poor toughness and hardness is large, with bad to the stickiness of the retarding disc that rubs, easily produce vibration and noise.And the heat-resistant limit temperature of phenolic resin is about 250 DEG C, the lower thermolysis of braking is serious at a high speed, and braking ability can be made significantly to decline.
Therefore, occurred in prior art that the multiple beneficial improving resol performance is attempted.Chinese invention patent application (publication date on April 19th, 2006) as publication number CN 1760229A discloses a kind of heat-resistant phenolic resins, with inorganic minerals such as boron and polynite, modified montmorillonoid, anionic additive, zeolites, modification is carried out to resol, improve its resistance toheat.The disclosed a kind of friction materials boron bakelite resin of Chinese invention patent application (publication date on October 24th, 2012) of publication number CN102746479A take boric acid as properties-correcting agent.The friction materials that this boron modified phenolic resin obtains as binding agent, the high and good stability of frictional coefficient, wear rate is low.The Chinese invention patent application of publication number CN1882506A discloses a kind of potassium hexatitanate/sodium hexatitanate whisker composite ceramic frication material at (publication date on December 20th, 2006), carry out modified phenolic resins with potassium hexatitanate/sodium hexatitanate whisker, make friction materials have superiority in stress release treatment and heat fading, prolongation product work-ing life etc.
Foregoing invention mostly only in individual event performance, as the aspect such as heat-resisting, wear-resisting improves friction materials.Be necessary to make further research the modification of resol, to make its thermal property and mechanical property all be enhanced, thus improve the performance of friction materials comprehensively.
Summary of the invention
For the problems referred to above, one object of the present invention is the resol providing a kind of silicate intercalation modifying.The good heat resistance of this modified phenolic resins, compares with unmodified resol, and decomposition temperature improves nearly 100 DEG C, and quality residual rate when 600 DEG C improves more than 3 times.
In order to solve the problems of the technologies described above, present invention employs following technical scheme:
A kind of modified phenolic resins, raw material comprises phenol, formaldehyde, organic montmorillonoid, catalyzer, standby by in-situ inserted legal system.
Preferably, described modified phenolic resins, with raw material gross weight for benchmark, the weight percent of each component is:
Phenol: 40% ~ 45%, preferably 40% ~ 42%;
Formaldehyde: 50% ~ 55%, preferably 52% ~ 53%;
Organic montmorillonoid: 2% ~ 9%, preferably 3% ~ 7%, most preferably 5%;
Catalyzer: 1% ~ 3%, preferably 1.6% ~ 2%.
Preferably, described catalyzer is selected from one or more in sodium hydroxide, potassium hydroxide, hydrated barta, a hydration ammonia.
Described organic montmorillonoid is obtained by reacting by organic modifiers and polynite, and the mass ratio of described organic modifiers and polynite is 1: 10 ~ 5: 10.
Preferably, described organic modifiers is selected from one or more in cetyl trimethylammonium bromide, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane and polyoxyethylene glycol; Preferred, described organic modifiers is selected from cetyl trimethylammonium bromide or polyoxyethylene glycol; Most preferred, described organic modifiers is selected from cetyl trimethylammonium bromide.
Described organic montmorillonoid is prepared by the following method:
Montmorillonite suspension liquid mixes with described organic modifiers, heated and stirred, leaves standstill, and removes supernatant liquor, and filtration cakes torrefaction, to constant weight, is pulverized.
Preferred, described organic montmorillonoid is prepared by the following method:
Getting sodium-based montmorillonite adds in deionized water, and the suspension of 40 ~ 50g/L is made in 70 ~ 90 DEG C of stirrings; Mixed with sodium-based montmorillonite suspension by described organic modifiers, 70 ~ 90 DEG C are stirred 0.5 ~ 3 hour; Leave standstill, remove supernatant liquid; Lower sediment deionized water repetitive scrubbing; Suction filtration, 80 ~ 100 DEG C are dried to constant weight in an oven, and grinding is sieved, and obtains organic montmorillonoid.
When taking cetyl trimethylammonium bromide as organic modifiers, described organic montmorillonoid is prepared by the following method:
Getting sodium-based montmorillonite adds in deionized water, and the suspension of 40 ~ 50g/L is made in 70 ~ 90 DEG C of stirrings; Getting cetyl trimethylammonium bromide is dissolved in deionized water, makes the solution of 10 ~ 50g/L; Mixed with sodium-based montmorillonite suspension by this solution, 70 ~ 90 DEG C are stirred 0.5 ~ 3 hour; Leave standstill, remove supernatant liquid; Lower sediment deionized water repetitive scrubbing, until silver nitrate titration supernatant liquor is without precipitation; Suction filtration, 80 ~ 100 DEG C are dried to constant weight in an oven, and grinding is sieved, and obtains organic montmorillonoid.
Preferred further, when taking cetyl trimethylammonium bromide as organic modifiers, described organic montmorillonoid is prepared by the following method:
Getting sodium-based montmorillonite adds in deionized water, stirs the suspension making 40g/L at 80 DEG C; Getting cetyl trimethylammonium bromide is dissolved in deionized water, makes the solution of 30g/L; This solution is mixed with sodium-based montmorillonite suspension, stirs 1 hour at 90 DEG C; Leave standstill 24 hours, remove supernatant liquor; Add deionized water, stir 1 hour at 90 DEG C, leave standstill 24 hours, remove supernatant liquor, until silver nitrate titration supernatant liquor is without precipitation; Suction filtration, 80 ~ 100 DEG C are dried to constant weight in an oven, and grinding is sieved, and obtains organic montmorillonoid.
The present invention also provides the preparation method of above-mentioned modified phenolic resins, comprise in-situ inserted reaction: phenol, formaldehyde and described organic montmorillonoid add reaction vessel according to weight percent, stir, add catalyzer, slowly be warming up to 80 ~ 100 DEG C, heating reflux reaction 2 ~ 5 hours; Reaction terminates, and adjust pH to neutral with acetic acid, decompression dehydration, 50 ~ 60 DEG C of oven dry, pulverize.
Preferably, the concrete operations of described in-situ inserted reaction are:
Phenol, formaldehyde and described organic montmorillonoid add reaction vessel according to weight percent, high-speed stirring, and rotating speed 200 ~ 300rpm, adds catalyzer, are slowly warming up to 90 DEG C, heating reflux reaction 3 hours; Reaction terminates, and adjust pH to neutral with acetic acid, decompression dehydration, adds appropriate dehydrated alcohol adjusting viscosity, discharging, 50 DEG C of oven for drying, ground 200 ~ 320 mesh sieves.
Another object of the present invention is to provide a kind of friction materials containing above-mentioned modified phenolic resins.
Described friction materials also comprises strongthener, frictional property regulator and filler; Wherein, described strongthener be selected from organic polymer fiber, steel fiber and whisker one or more, described frictional property regulator be selected from graphite, molybdenumdisulphide and aluminum oxide one or more, described filler is selected from flyash and/or barium sulfate.
Preferably, the length of described organic polymer fiber, steel fiber is 100 ~ 300 μm.
Preferably, described organic polymer fiber is selected from aramid fiber and/or polyster fibre.
Preferably, described steel fiber is selected from copper fiber and/or steel fiber.
Preferably, described whisker is selected from calcium sulfate crystal whiskers and/or crystal whisker of hexa potassium titanate.
Preferably, described strongthener is selected from aramid fiber, copper fiber and calcium sulfate crystal whiskers, and described frictional property regulator is selected from graphite, molybdenumdisulphide and aluminum oxide, and described filler is selected from flyash and barium sulfate.
With raw material gross weight for benchmark, the weight percent of each component of described friction materials is:
Modified phenolic resins: 10% ~ 20%;
Aramid fiber: 5% ~ 15%;
Copper fiber: 5% ~ 15%;
Calcium sulfate crystal whiskers: 5% ~ 15%;
Graphite: 5% ~ 10%;
Molybdenumdisulphide: 2% ~ 5%;
Aluminum oxide: 1% ~ 3%;
Flyash: 15% ~ 25%;
Barium sulfate: be filled to 100%.
Preferred, with raw material gross weight for benchmark, the weight percent of each component of described friction materials is:
Modified phenolic resins: 15%;
Aramid fiber: 10%;
Copper fiber: 10%;
Calcium sulfate crystal whiskers: 10%;
Graphite: 5%;
Molybdenumdisulphide: 2%;
Aluminum oxide: 3%;
Flyash: 20%;
Barium sulfate: 25%.
The present invention also has a goal of the invention to be to provide the preparation method of above-mentioned friction materials, comprises batching, batch mixing, hot-forming, thermal treatment.
Preferably, the preparation method of described friction materials, concrete operations are:
Each feed composition is prepared according to formula, all raw materials add stirring 10 ~ 30min in high-speed mixer, the material mixed is put into mould 120 ~ 180 DEG C, carry out under 10 ~ 20MPa hot-forming, pressurize 3 ~ 5min, shaping print is put into air dry oven, slowly be warming up to 160 ~ 200 DEG C, insulation 10 ~ 20h heat-treats, and finally obtains friction materials finished product.
Preferred further, the preparation method of described friction materials, concrete operations are:
Each feed composition is prepared according to formula, all raw materials add in high-speed mixer and stir 20min, the material mixed is put into mould 150 DEG C, carry out under 15MPa hot-forming, pressurize 3 ~ 5min, shaping print is put into air dry oven, slowly be warming up to 180 DEG C, insulation 12h heat-treats, and finally obtains friction materials finished product.
In addition, the present invention also has a goal of the invention to be, provides above-mentioned friction materials preparing the purposes in automobile brake lining plate, automobile brake sheet and clutch disc.
The present invention also provides a kind of automobile brake lining plate, automobile brake sheet or clutch disc, comprises above-mentioned friction materials.
The present invention with specific modified phenolic resins for binding agent, friction materials of the present invention is made to have stable frictional coefficient, low wear rate, good anti-character of heat-fading, resistance toheat is strong and mechanical strength is high feature, compared with traditional friction materials, over-all properties has had significantly to be improved.And raw material of the present invention and explained hereafter cost lower, be applicable to scale operation.
Accompanying drawing explanation
Below, describe embodiment of the present invention in detail by reference to the accompanying drawings, wherein:
Fig. 1 display be the X-diffracting spectrum of the modified phenolic resins that different intercalation method prepares, wherein F1 is the modified phenolic resins that in-situ inserted method prepares, and F2 is the modified phenolic resins that polyalcohol intercalation method prepares.
What Fig. 2 showed is unmodified and X-diffracting spectrum that is modified montmorillonoid, and wherein 1 is unclose balcony, and 2 is CTAB modified montmorillonoids, and 3 is KH-560 modified montmorillonoids, and 4 is poly ethyldiol modified polynites.
Embodiment
The present invention by in-situ inserted method intercalation modifying resol, and then obtains a kind of friction materials containing this modified phenolic resins with organically-modified silicate.Intercalation method, silicate species and the many aspects such as consumption, organic modifiers all can affect the performance of resol and final friction materials.Therefore, invention has been following research:
1. intercalation method is preferred
The intercalation modifying of resol has two kinds of diverse ways: one is in-situ monomer intercalation, and namely phenol, formaldehyde two kinds of monomers enter between silicate layer and carry out polyreaction, utilize polymerization reaction heat to strut interlamellar spacing; Another kind is polyalcohol intercalation, namely under solution state, is directly injected in silicate layer by the polymkeric substance resol of dissolving, carrys out enlargement layer spacing with this.By comparing the modified effect of two kinds of methods, in-situ monomer intercalation method is finally selected to carry out modified phenolic resins.
In-situ inserted: a certain amount of polynite is first dropped in reaction unit, add phenol, formaldehyde vigorous stirring after 3 hours, then add catalyzer sodium hydroxide obtains fabricated in situ organic montmorillonoid/phenolic resin composite with the resol synthetic method of routine.
Polyalcohol intercalation: first prepare water soluble phenol resin, then by polynite mix and blend with it, solidify under certain processing condition, the matrix material of obtained resol and polynite.
Measure the X-diffracting spectrum of the modified resin that two kinds of methods prepare respectively.As shown in Figure 1, wherein F1 is the collection of illustrative plates of the modified phenolic resins that in-situ inserted method prepares to result, and F2 is the collection of illustrative plates of the modified phenolic resins that polyalcohol intercalation method prepares.As seen from Figure 1, the standby matrix material of polyalcohol intercalation legal system is slightly less than by 2 θ angles of the diffraction peak of the X-diffracting spectrum of the standby matrix material of in-situ inserted legal system.Can calculate the mean distance between silicate lamella according to Bragg equation 2dsin θ=λ, wherein d is the mean distance between silicate lamella, and θ is semi diffraction angle, and λ is incident ray wavelength.When λ is certain, the mean distance d between semi diffraction angle θ and lamella is inversely proportional to.Therefore, in-situ inserted method is larger to the increase of the interlamellar spacing of polynite, and resol can more enter between cheating engaging layer, and modified composite property is better, so in-situ inserted method is better than polyalcohol intercalation method.
Therefore, the preferred in-situ inserted legal system of the present invention is for modified phenolic resins.
2. silicate is preferred
Polynite, kaolin, vermiculite etc. all contain silicate, can pass through intercalation modifying resol on chemically forming.The properties-correcting agent that polynite is resol is optimized by experiment below.
Experiment material: polynite, kaolin, vermiculite, phenol, formaldehyde, sodium hydroxide, acetic acid
Experimental procedure:
1) silicate mineral is organically-modified
Getting 10g sodium-based montmorillonite, kaolin, vermiculite is dissolved in 250mL deionized water respectively, stirs 1h and make suspension in 80 DEG C of waters bath with thermostatic control; Get 9gCTAB (cetyl trimethylammonium bromide) to be dissolved in 300mL deionized water, be divided into three parts; Again every part of CTAB solution is mixed with the suspension of polynite, kaolin and vermiculite respectively, in 90 DEG C of waters bath with thermostatic control, stir 2h; Leave standstill 24h, remove supernatant liquor; Add deionized water, stir 1 hour at 90 DEG C, leave standstill 24 hours, remove supernatant liquor, until supernatant liquor silver nitrate titration extremely nothing precipitation, vacuum filtration, filter cake is dried to constant weight respectively in an oven, and grinding is sieved.
2) in-situ inserted method modified phenolic resins
By 79g phenol, 111g formaldehyde (mass ratio=1: 1.4) reaction vessel is put in mixing, and reaction vessel is overlapped in parallel preparation three, then adds the silicate mineral that organises prepared by step respectively, high-speed stirring 1h; Add 1.6gNaOH respectively, be slowly warming up to 90 DEG C, reflux 3h; After reaction terminates, use second acid for adjusting pH in neutral respectively, decompression dehydration at 80 DEG C, adds appropriate dehydrated alcohol adjusting viscosity, then discharging, dries in 50 DEG C of baking ovens.
3) performance test
According to the shock strength testing method in " brake spacer for automobile " in standard GB/T 5763-2008 and friction testing method, the mensuration of mechanical property and frictional behaviour is carried out to the modified phenolic resins material that upper step prepares.
Experimental result: in Table 1-table 4
The mechanics performance determining result of table 1 three kinds of modified phenolic resinss
The frictional behaviour of table 2 montmorillonite modified phenolic resin
The frictional behaviour of table 3 Modification of kaolin resol
The frictional behaviour of table 4 vermiculite modified phenolic resins
Experiment conclusion:
As can be seen from the above table, the ultimate compression strength of imvite modified resol, shock strength, Rockwell hardness is all better than the resol of kaolin and vermiculite modification.Within the scope of 100 ~ 350 DEG C, the stability of the frictional coefficient of imvite modified resol, and the wear rate under 250 DEG C of high temperature is all better than other two kinds of modified resin.Illustrate that the mechanical property of imvite modified resol and frictional behaviour are all obviously better than the resol of kaolin and vermiculite modification.Therefore, the preferred polynite of the present invention is phenolic resin modified dose.3. polynite organic modifiers is preferred
Have studied three kinds of representational organic modifiers, be respectively belong to cats product cetyl trimethylammonium bromide (CTAB), belong to γ-(2, the 3-epoxy third oxygen) propyl trimethoxy silicane (KH-560) of coupling agent and belong to the polyoxyethylene glycol (PEG) of nonionogenic tenside.According to the working method of above-mentioned " silicate mineral organically-modified ", wherein KH-560 and polyoxyethylene glycol directly add polynite suspension, have prepared CTAB, KH-560 and poly ethyldiol modified polynite respectively.
Measure the X-diffracting spectrum of unmodified sodium-based montmorillonite, above-mentioned CTAB, KH-560 and poly ethyldiol modified polynite respectively, measure 2 θ.The X-diffracting spectrum of each test sample is shown in Fig. 2.2 θ of unmodified sodium-based montmorillonite are 6.120 °, and 2 θ of CTAB, KH-560 and poly ethyldiol modified polynite are respectively 5.130 °, 5.450 °, 5.320 °.Utilize the mean distance between Bragg equation 2dsin θ=λ calculating silicate lamella, wherein d is the mean distance between silicate lamella, and θ is semi diffraction angle, and λ is incident ray wavelength 0.154nm.The results are shown in Table 5.
The silicate plate interlamellar spacing of the unmodified and organic modification montmonrillonite of table 5
Polynite silicon-oxy tetrahedron laminated structure interlamellar spacing is larger, its laminated structure hinder polymer molecule produce in thermolysis small molecules motion effect stronger, thus can better strongthener thermostability, raising material heat decomposition temperature.As can be seen from the result of table 5, the sheet interlayer spacing of organically-modified polynite is all greater than unclose balcony.And after organic modifiers intercalation, make the little sequence of vary within wide limits of the silicon-oxy tetrahedron interlamellar spacing of polynite be: the poly ethyldiol modified >KH560 modification of CTAB modification >.Therefore polynite organic modifiers is preferably CTAB and polyoxyethylene glycol, is more preferably CTAB.
4. polynite consumption is preferred
According to the method for above-mentioned in-situ inserted legal system for modified phenolic resins, prepare the modified phenolic resins that organic montmorillonoid content is 0,2%, 3%, 5%, 7%, 8%, 10% respectively.The resistance toheat of modified phenolic resins is measured by TG-DSC.The results are shown in Table 6.
The resistance toheat measurement result of table 6 modified phenolic resins
As can be seen from the above table, add organic montmorillonoid, the resistance toheat of resol can be significantly improved.Compare with unmodified resol, modified resol decomposition temperature improves 35 ~ 97 DEG C; Especially, when organic montmorillonoid consumption is 3% ~ 10%, 600 DEG C of mass excess rates of resol improve 89% ~ 312%.Therefore, organic montmorillonoid content preferably 3% ~ 10%, more preferably 3% ~ 7%, most preferably 5%.
5. modified phenolic resins consumption is preferred
Raw material forms:
Organic montmorillonoid content is the modified phenolic resins of 5%: 10% ~ 20%,
Aramid fiber: 10%,
Copper fiber: 10%,
Calcium sulfate crystal whiskers: 10%,
Molybdenumdisulphide: 2%,
Graphite: 10%,
Aluminum oxide: 3%,
Flyash: 20%;
Barium sulfate: be filled to 100%.
Prepare the friction materials that modified phenolic resins content is 10%, 12%, 15%, 17%, 18%, 20% by the following method:
1. material mixes.After each component raw material is weighed by proportioning, add in high-speed mixer and stir 20min, obtain the uniform mixing raw material of component.
2. hot-forming.The material mixed is put into mould, hot-forming by thermocompressor under the pressure of the temperature of 150 DEG C ± 5 DEG C and 15MPa, dwell time 3 ~ 5min in hot pressing, pressurize first three minute domestic demand breathing a mould 2 ~ 3 times.
3. thermal treatment.Hot-forming print is put into air dry oven, is slowly warming up to 180 DEG C, at 180 DEG C, be incubated 12h heat-treat, after cooling, obtain friction materials finished product.
Meanwhile, prepare according to above-mentioned identical step the friction materials that unmodified phenolic resin content is 15%.
According to the method in standard GB/T 7563-2008, frictional behaviour test is carried out to the friction materials prepared above, the results are shown in Table 7-table 13.
The frictional behaviour of the unmodified phenolic resin friction material of table 7
The frictional behaviour of table 8 10% modified phenolic resins friction materials
The frictional behaviour of table 9 12% modified phenolic resins friction materials
The frictional behaviour of table 10 15% modified phenolic resins friction materials
The frictional behaviour of table 11 17% modified phenolic resins friction materials
The frictional behaviour of table 12 18% modified phenolic resins friction materials
The frictional behaviour of table 13 20% modified phenolic resins friction materials
Conclusion: as can be seen from the frictional behaviour of table 7-table 13, unmodified alkyd resin based friction material is at the intensification frictional coefficient of 100 ~ 350 DEG C of scopes lower than 0.28, and the frictional coefficient of modified alkyd resin based friction material is higher than unmodified.Wherein, content is that the higher and stability of the frictional coefficient of the modified alkyd resin based friction material of 12% ~ 17% is better, and the wear rate simultaneously under high temperature is lower; Content be the intensification frictional coefficient of the modified alkyd resin based friction material of 15% higher than 0.3, mild the fluctuations of 100 ~ 350 DEG C, the wear rate more than 250 DEG C under high temperature is lower than 0.8.To sum up, modified phenolic resins preferred content is 12% ~ 17%, and more preferably content is 12% ~ 15%, and most preferred content is 15%.
6. strongthener is preferred
According to the formula of table 14, prepare the friction materials of different strongthener proportioning, wherein the organic montmorillonoid weight percentage of modified resin is 7%.According to the method in standard GB/T 7563-2008, frictional behaviour test is carried out to preparation-obtained friction materials, the results are shown in Table 14-table 18.
The strongthener formula (weight percent, %) that table 14 is different
The frictional behaviour of table 15 sample F1
The frictional behaviour of table 16 sample F2
The frictional behaviour of table 17 sample F3
The frictional behaviour of table 18 sample F4
Conclusion: as can be seen from table 15-table 18, within the scope of 100 ~ 350 DEG C, the frictional coefficient of sample F4 is higher than other three kinds of samples, and stability is better; And during high temperature more than 250 DEG C, the wear rate of sample F4 is starkly lower than other three kinds of samples.So the proportioning of preferred strongthener is aramid fiber: 10%, copper fiber: 10%, calcium sulfate crystal whiskers: 10%.
By above-mentioned research, the preferred technical scheme of the present invention is:
A kind of modified phenolic resins, raw material comprises phenol, formaldehyde, organic montmorillonoid, catalyzer, standby by in-situ inserted legal system; Catalyzer is selected from sodium hydroxide.
With raw material gross weight for benchmark, the weight percent of each component is:
Phenol: 40% ~ 42%;
Formaldehyde: 52% ~ 53%;
Organic montmorillonoid: 3% ~ 7%, most preferably 5%;
Catalyzer: 1.6% ~ 2%.
Wherein, catalyzer be selected from sodium hydroxide, potassium hydroxide, hydrated barta and a hydration ammonia one or more, be preferably sodium hydroxide.
Organic montmorillonoid is obtained by reacting by organic modifiers and polynite, and the mass ratio of described organic modifiers and polynite is 1: 10 ~ 5: 10.
The preferred cetyl trimethylammonium bromide of described organic modifiers or polyoxyethylene glycol; Be more preferably cetyl trimethylammonium bromide.
The present invention also provides a kind of friction materials containing above-mentioned modified phenolic resins; Described friction materials also comprises strongthener, frictional property regulator and filler.
Preferably, described strongthener is selected from aramid fiber, copper fiber and calcium sulfate crystal whiskers, and described frictional property regulator is selected from graphite, molybdenumdisulphide and aluminum oxide, and described filler is selected from flyash and barium sulfate; With raw material gross weight for benchmark, the weight percent of each component is:
Modified phenolic resins of the present invention: 10% ~ 20%;
Aramid fiber: 5% ~ 15%;
Copper fiber: 5% ~ 15%;
Calcium sulfate crystal whiskers: 5% ~ 15%;
Graphite: 5% ~ 10%;
Molybdenumdisulphide: 2% ~ 5%;
Aluminum oxide: 1% ~ 3%;
Flyash: 15% ~ 25%;
Barium sulfate: be filled to 100%.
Preferred, with raw material gross weight for benchmark, the weight percent of each component is:
Modified phenolic resins of the present invention: 15%;
Aramid fiber: 10%;
Copper fiber: 10%;
Calcium sulfate crystal whiskers: 10%;
Graphite: 5%%;
Molybdenumdisulphide: 2%;
Aluminum oxide: 3%;
Flyash: 20%;
Barium sulfate: 25%.
Referring to specific embodiment, the present invention is described.It will be appreciated by those skilled in the art that these embodiments are only for illustration of the present invention, its scope do not limited the present invention in any way.
Experimental technique in following embodiment, if no special instructions, is ordinary method.Raw material used in following embodiment, reagent material etc., if no special instructions, be commercially available purchase product.
embodiment 1the preparation of organic montmorillonoid
Get 100g sodium-based montmorillonite to be dissolved in and in 80 DEG C of waters bath with thermostatic control, to stir 1h in 2500mL deionized water and make suspension; Get 30gCTAB (cetyl trimethylammonium bromide) to be dissolved in 1000mL deionized water, then this cationic solution is mixed with sodium-based montmorillonite suspension, in 90 DEG C of waters bath with thermostatic control, stir 2h; Leave standstill 24h, remove supernatant liquor; Add deionized water, stir 1 hour at 90 DEG C, leave standstill 24 hours, remove supernatant liquor, until supernatant liquor silver nitrate titration extremely nothing precipitation, vacuum filtration, filter cake is dried to constant weight in an oven, ground 200 mesh sieves.
embodiment 2in-situ inserted legal system is for modified phenolic resins
By 79g phenol, 105g formaldehyde (mass ratio=1: 1.3) reaction vessel is put in mixing, then adds organic montmorillonoid prepared by 10g embodiment 1,300rpm high-speed stirring 1h; Add 3.2gNaOH, be slowly warming up to 90 DEG C, reflux 3h; After reaction terminates, with second acid for adjusting pH in neutral, decompression dehydration at 80 DEG C, adds appropriate dehydrated alcohol adjusting viscosity, then discharging, and after drying in 50 DEG C of baking ovens, grinding is sieved.
embodiment 3a kind of friction materials
Raw material (weight percent):
Modified phenolic resins prepared by embodiment 2: 15%,
Aramid fiber: 10%,
Copper fiber: 10%,
Calcium sulfate crystal whiskers: 10%,
Molybdenumdisulphide: 2%,
Graphite: 10%,
Aluminum oxide: 3%,
Flyash: 20%;
Barium sulfate: be filled to 100%;
Wherein, the length of aramid fiber and copper fiber is 100 ~ 300 μm.
Prepare by the following method:
1. material mixes.After each component raw material is weighed by proportioning, add in high-speed mixer and stir 20min, obtain the uniform mixing raw material of component.
2. hot-forming.The material mixed is put into mould, hot-forming by thermocompressor under the pressure of the temperature of 150 DEG C ± 5 DEG C and 15MPa, dwell time 3 ~ 5min in hot pressing, pressurize first three minute domestic demand breathing a mould 2 ~ 3 times.
3. thermal treatment.Hot-forming print is put into air dry oven, is slowly warming up to 180 DEG C, at 180 DEG C, be incubated 12h heat-treat, after cooling, obtain friction materials finished product.
comparative example 1a kind of friction materials
Raw material (weight percent):
Resol (mass ratio of phenol and formaldehyde is 1:1.3): 15%,
Aramid fiber: 10%,
Copper fiber: 10%,
Calcium sulfate crystal whiskers: 10%,
Molybdenumdisulphide: 2%,
Graphite: 10%,
Aluminum oxide: 3%,
Flyash: 20%;
Barium sulfate: be filled to 100%;
Wherein, the length of aramid fiber and copper fiber is 100 ~ 300 μm.
The step identical according to embodiment 3 prepares.
test example 1the Performance comparision of two kinds of friction materialss
According to the method in standard GB/T 7563-2008, frictional behaviour test is carried out to two kinds of friction materialss of embodiment 3 and comparative example 1, the results are shown in Table 19-table 21:
The friction materials rubs test results of table 19 comparative example 1
The friction materials rubs test results of table 20 embodiment 3
The mechanical experimental results of table 21 bi-material
As can be seen from above test result, modified phenolic resins of the present invention is that the friction materials of binding agent compares with unmodified friction materials, high heat resistance and wear resistance have had obvious improvement, show as and have more stable frictional coefficient, better anti-character of heat-fading and wear resistance.The mechanical property of modified resin base frication material (friction materials of embodiment 3) is significantly promoted simultaneously.In a word, the various aspects of performance of friction materials of the present invention is obtained for improvement.
embodiment 4the preparation of organic montmorillonoid
Get 125g sodium-based montmorillonite to be dissolved in and in 70 DEG C of waters bath with thermostatic control, to stir 3h in 2500mL deionized water and make suspension; Get 62.5gCTAB (cetyl trimethylammonium bromide) to be dissolved in 1250mL deionized water, then this cationic solution is mixed with sodium-based montmorillonite suspension, in 70 DEG C of waters bath with thermostatic control, stir 3h; Leave standstill 24h, remove supernatant liquor; Add deionized water, stir 1 hour at 70 DEG C, leave standstill 24 hours, remove supernatant liquor, until supernatant liquor silver nitrate titration extremely nothing precipitation, vacuum filtration, filter cake is dried to constant weight in an oven, ground 200 mesh sieves.
embodiment 5-9in-situ inserted legal system is for modified phenolic resins
Each raw material is prepared according to table 22.Target product is prepared according to the step of embodiment 2.
Table 22 embodiment 5-9 proportioning raw materials
embodiment 10-15a kind of friction materials
Prepare each raw material according to table 23, wherein, the length of aramid fiber and copper fiber is 100 ~ 300 μm.。Target product is prepared according to the step of embodiment 3.
Table 23 embodiment 10-15 proportioning raw materials
test example 2the performance measurement of the friction materials of embodiment 10-15
According to the method in standard GB/T 7563-2008, frictional behaviour test is carried out to six kinds of friction materialss prepared by embodiment 10-15.Primary friction performance perameter is in Table 24-table 29.
The friction materials rubs test results of table 24 embodiment 10
The friction materials rubs test results of table 25 embodiment 11
The friction materials rubs test results of table 26 embodiment 12
The friction materials rubs test results of table 27 embodiment 13
The friction materials rubs test results of table 28 embodiment 14
The friction materials rubs test results of table 29 embodiment 15
embodiment 16a kind of automobile brake lining plate
Raw material composition (weight percentage):
Modified phenolic resins prepared by embodiment 2: 15%,
Aramid fiber: 10%,
Copper fiber: 10%,
Calcium sulfate crystal whiskers: 10%,
Molybdenumdisulphide: 2%,
Graphite: 10%,
Aluminum oxide: 3%,
Flyash: 20%;
Barium sulfate: be filled to 100%;
Wherein, the length of aramid fiber and copper fiber is 100 ~ 300 μm.
After preparation process according to embodiment 3, the mechanical workout such as sand papering through this area routine obtains.
embodiment 17a kind of automobile brake sheet
Composition: steel plate and friction facing.
Preparation method:
1. the preparation of steel plate.Tailor steel plate, surface treatment is carried out and coating adhesive to it.
2. the preparation formula of friction facing is as follows:
Modified phenolic resins prepared by embodiment 5: 20%,
Aramid fiber: 10%,
Copper fiber: 10%,
Calcium sulfate crystal whiskers: 10%,
Molybdenumdisulphide: 2%,
Graphite: 10%,
Aluminum oxide: 3%,
Flyash: 15%;
Barium sulfate: be filled to 100%;
Wherein, the length of aramid fiber and copper fiber is 100 ~ 300 μm.
Prepare according to the step of embodiment 3.
3. shaping.The steel plate prepared and friction facing are inserted in mould, 200 DEG C, compression moulding under 15MPa.
4. thermal treatment.The brake facing of forming is heat-treated at 180 DEG C.
embodiment 18a kind of car clutch sheet
Composition: friction plate, antithesis sheet
1. preparation method: the preparation of friction plate:
Fill a prescription as follows:
The modified phenolic resins of embodiment 9: 15%,
Aramid fiber: 10%,
Copper fiber: 10%,
Calcium sulfate crystal whiskers: 10%,
Molybdenumdisulphide: 2%,
Graphite: 5%,
Aluminum oxide: 3%,
Flyash: 25%;
Barium sulfate: be filled to 100%;
Wherein, the length of aramid fiber and copper fiber is 100 ~ 300 μm.
Prepare according to the step of embodiment 3.
2. the aftertreatment of friction plate: obtained friction plate is smoothed on press.
3. the preparation of antithesis sheet: according to the method for this area routine, adopts mild steel to prepare antithesis sheet, and carries out nitrogenize thermal treatment.
4. assemble clutch disc: obtained friction plate and antithesis sheet are assembled into clutch disc.
Specific description of embodiments of the present invention does not above limit the present invention, and those skilled in the art can make various change or distortion according to the present invention, only otherwise depart from spirit of the present invention, all should belong to the scope of claims of the present invention.
Claims (10)
1. a modified phenolic resins, raw material comprises phenol, formaldehyde, organic montmorillonoid, catalyzer, standby by in-situ inserted legal system.
2. modified phenolic resins according to claim 1, is characterized in that: described modified phenolic resins, and with raw material gross weight for benchmark, the weight percent of each component is:
Phenol: 40% ~ 45%, preferably 40% ~ 42%;
Formaldehyde: 50% ~ 55%, preferably 52% ~ 53%;
Organic montmorillonoid: 2% ~ 9%, preferably 3% ~ 7%, most preferably 5%;
Catalyzer: 1% ~ 3%, preferably 1.6% ~ 2%;
Preferably, described catalyzer is selected from one or more in sodium hydroxide, potassium hydroxide, hydrated barta, a hydration ammonia.
3. modified phenolic resins according to claim 1 and 2, is characterized in that: described organic montmorillonoid is obtained by reacting by organic modifiers and polynite, and the mass ratio of described organic modifiers and polynite is 1: 10 ~ 5: 10; Prepare by the following method:
Montmorillonite suspension liquid mixes with described organic modifiers, heated and stirred, leaves standstill, and removes supernatant liquor, and filtration cakes torrefaction, to constant weight, is pulverized;
Preferably, described organic modifiers be selected from cetyl trimethylammonium bromide,
γone or more in-(2,3-epoxy third oxygen) propyl trimethoxy silicane and polyoxyethylene glycol; Preferred, described organic modifiers is selected from cetyl trimethylammonium bromide or polyoxyethylene glycol; Most preferred, described organic modifiers is selected from cetyl trimethylammonium bromide.
4. modified phenolic resins according to claim 3, is characterized in that: described organic montmorillonoid is prepared by the following method:
Getting sodium-based montmorillonite adds in deionized water, and the suspension of 40 ~ 50g/L is made in 70 ~ 90 DEG C of stirrings; Mixed with sodium-based montmorillonite suspension by described organic modifiers, 70 ~ 90 DEG C are stirred 0.5 ~ 3 hour; Leave standstill, remove supernatant liquid; Lower sediment deionized water repetitive scrubbing; Suction filtration, 80 ~ 100 DEG C are dried to constant weight in an oven, and grinding is sieved, and obtains organic montmorillonoid;
Preferably, when taking cetyl trimethylammonium bromide as organic modifiers, described organic montmorillonoid is prepared by the following method:
Getting sodium-based montmorillonite adds in deionized water, and the suspension of 40 ~ 50g/L is made in 70 ~ 90 DEG C of stirrings; Getting cetyl trimethylammonium bromide is dissolved in deionized water, makes the solution of 10 ~ 50g/L; Mixed with sodium-based montmorillonite suspension by this solution, 70 ~ 90 DEG C are stirred 0.5 ~ 3 hour; Leave standstill, remove supernatant liquid; Lower sediment deionized water repetitive scrubbing, until silver nitrate titration supernatant liquor is without precipitation; Suction filtration, 80 ~ 100 DEG C are dried to constant weight in an oven, and grinding is sieved, and obtains organic montmorillonoid;
Preferred further, when taking cetyl trimethylammonium bromide as organic modifiers, described organic montmorillonoid is prepared by the following method:
Getting sodium-based montmorillonite adds in deionized water, stirs the suspension making 40g/L at 80 DEG C; Getting cetyl trimethylammonium bromide is dissolved in deionized water, makes the solution of 30g/L; This solution is mixed with sodium-based montmorillonite suspension, stirs 1 hour at 90 DEG C; Leave standstill 24 hours, remove supernatant liquor; Add deionized water, stir 1 hour at 90 DEG C, leave standstill 24 hours, remove supernatant liquor, until silver nitrate titration supernatant liquor is without precipitation; Suction filtration, 80 ~ 100 DEG C are dried to constant weight in an oven, and grinding is sieved, and obtains organic montmorillonoid.
5. the preparation method of the modified phenolic resins according to any one of Claims 1-4, comprises in-situ inserted reaction:
Phenol, formaldehyde and described organic montmorillonoid add reaction vessel according to weight percent, stir, add catalyzer, be slowly warming up to 80 ~ 100 DEG C, heating reflux reaction 2 ~ 5 hours; Reaction terminates, and adjust pH to neutral with acetic acid, decompression dehydration, 50 ~ 60 DEG C of oven dry, pulverize;
Preferably, the concrete operations of described in-situ inserted reaction are:
Phenol, formaldehyde and described organic montmorillonoid add reaction vessel according to weight percent, high-speed stirring, and rotating speed 200 ~ 300rpm, adds catalyzer, are slowly warming up to 90 DEG C, heating reflux reaction 3 hours; Reaction terminates, and adjust pH to neutral with acetic acid, decompression dehydration, adds appropriate dehydrated alcohol adjusting viscosity, discharging, 50 DEG C of oven for drying, ground 200 ~ 320 mesh sieves.
6. contain a modified phenolic resins according to any one of Claims 1-4, or contain the friction materials of modified phenolic resins prepared by with good grounds claim 5;
Preferably, described friction materials also comprises strongthener, frictional property regulator and filler; Wherein, described strongthener be selected from organic polymer fiber, steel fiber and whisker one or more, described frictional property regulator be selected from graphite, molybdenumdisulphide and aluminum oxide one or more, described filler is selected from flyash and/or barium sulfate;
Preferably, the length of described organic polymer fiber and steel fiber is 100 ~ 300 μm;
Preferably, described organic polymer fiber is selected from aramid fiber and/or polyster fibre;
Preferably, described steel fiber is selected from copper fiber and/or steel fiber;
Preferably, described whisker is selected from calcium sulfate crystal whiskers and/or crystal whisker of hexa potassium titanate;
Preferred further, described strongthener is selected from aramid fiber, copper fiber and calcium sulfate crystal whiskers, and described frictional property regulator is selected from graphite, molybdenumdisulphide and aluminum oxide, and described filler is selected from flyash and barium sulfate.
7. friction materials according to claim 6, is characterized in that: with raw material gross weight for benchmark, and the weight percent of each component is:
Modified phenolic resins: 10% ~ 20%;
Aramid fiber: 5% ~ 15%;
Copper fiber: 5% ~ 15%;
Calcium sulfate crystal whiskers: 5% ~ 15%;
Graphite: 5% ~ 10%;
Molybdenumdisulphide: 2% ~ 5%;
Aluminum oxide: 1% ~ 3%;
Flyash: 15% ~ 25%;
Barium sulfate: be filled to 100%;
Preferably, with raw material gross weight for benchmark, the weight percent of each component is:
Modified phenolic resins: 15%;
Aramid fiber: 10%;
Copper fiber: 10%;
Calcium sulfate crystal whiskers: 10%;
Graphite: 5%;
Molybdenumdisulphide: 2%;
Aluminum oxide: 3%;
Flyash: 20%;
Barium sulfate: 25%.
8. the preparation method of the friction materials described in claim 6 or 7, comprises batching, batch mixing, hot-forming, thermal treatment;
Preferably, the preparation method of described friction materials, concrete operations are:
Each feed composition is prepared according to formula, all raw materials add stirring 10 ~ 30min in high-speed mixer, the material mixed is put into mould 120 ~ 180 DEG C, carry out under 10 ~ 20MPa hot-forming, pressurize 3 ~ 5min, shaping print is put into air dry oven, slowly be warming up to 160 ~ 200 DEG C, insulation 10 ~ 20h heat-treats, and finally obtains friction materials finished product;
Preferred further, the preparation method of described friction materials, concrete operations are:
Each feed composition is prepared according to formula, all raw materials add in high-speed mixer and stir 20min, the material mixed is put into mould 150 DEG C, carry out under 15MPa hot-forming, pressurize 3 ~ 5min, shaping print is put into air dry oven, slowly be warming up to 180 DEG C, insulation 12h heat-treats, and finally obtains friction materials finished product.
9. the friction materials described in claim 6 or 7, the purposes in automobile brake lining plate, automobile brake sheet and clutch disc prepared by the friction materials that preparation method prepares according to claim 8.
10. automobile brake lining plate, automobile brake sheet or a clutch disc, comprises the friction materials described in claim 6 or 7, or the friction materials for preparing of preparation method according to claim 8.
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| CN104893230A (en) * | 2015-05-06 | 2015-09-09 | 沈阳市航宇星仪表有限责任公司 | Material used for membrane-type gas meter valve cover and valve seat |
| CN105131517A (en) * | 2015-07-16 | 2015-12-09 | 浙江杭摩合成材料有限公司 | Modified thermoplastic phenolic resin adhesive used in automobile brake pad and preparation method thereof |
| CN105801014A (en) * | 2016-03-17 | 2016-07-27 | 山东金麒麟股份有限公司 | Multielement silane coupling agent-modified phenolic resin base combined disc brake pad and preparation method thereof |
| CN106221122A (en) * | 2016-07-24 | 2016-12-14 | 泉州海岸线新材料科技有限公司 | The formula of a kind of heat-resistant antifriction membrane material and preparation technology |
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| CN107949718A (en) * | 2015-06-25 | 2018-04-20 | 法雷奥摩擦材料公司 | The method for manufacturing friction material |
| CN108724763A (en) * | 2018-05-10 | 2018-11-02 | 来安县隆华摩擦材料有限公司 | A kind of preparation method of car clutch face sheet blank |
| CN109651758A (en) * | 2018-11-06 | 2019-04-19 | 中国神华能源股份有限公司 | A kind of phenol-formaldehyde resin modified and preparation method thereof, phenol-formaldehyde resin modified plate |
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| CN107949718A (en) * | 2015-06-25 | 2018-04-20 | 法雷奥摩擦材料公司 | The method for manufacturing friction material |
| CN105131517A (en) * | 2015-07-16 | 2015-12-09 | 浙江杭摩合成材料有限公司 | Modified thermoplastic phenolic resin adhesive used in automobile brake pad and preparation method thereof |
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| CN109651758B (en) * | 2018-11-06 | 2021-11-30 | 中国神华能源股份有限公司 | Modified phenolic resin, preparation method thereof and modified phenolic resin plate |
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| CN117004173A (en) * | 2023-08-30 | 2023-11-07 | 浙江万赛汽车零部件股份有限公司 | Production process in modified phenolic resin brake pad |
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