CN102702588A - Damping rubber material with low hardness, high-temperature static torque and good durability and preparation method thereof - Google Patents
Damping rubber material with low hardness, high-temperature static torque and good durability and preparation method thereof Download PDFInfo
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- CN102702588A CN102702588A CN2012102051742A CN201210205174A CN102702588A CN 102702588 A CN102702588 A CN 102702588A CN 2012102051742 A CN2012102051742 A CN 2012102051742A CN 201210205174 A CN201210205174 A CN 201210205174A CN 102702588 A CN102702588 A CN 102702588A
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Abstract
The invention relates to a damping rubber material with low hardness, high-temperature static torque and good durability and a preparation method thereof. The damping rubber material comprises the following components in mass parts: 100 parts of nitrile rubber and butadiene styrene rubber composite, 40-70 parts of reinforcement bulking agent, 5-10 parts of nano white carbon black, 1-3 parts of coupling agent and processing agent, 10-15 parts of softened plasticizer, 2-3 parts of anti-aging agent, and 8-10 parts of curing agent and auxiliary agent; and moreover, the technological parameters of rubber material vulcanization are as follows: a press vulcanizer is adopted for vulcanization, the vulcanization time is 10-20 minutes, the vulcanization temperature is 150-160 degree C, and the vulcanization pressure is 10-14 MPa. The damping rubber material disclosed by the invention has the advantages of low hardness, high static torque at 80 degree C, good durability at high temperature of 130 degree C, as well as good processability. The material can be used as damping rubber materials used in rubber torque vibration dampers of engines, and solves the problems of high hardness, difficulty in press fitting, low static torque at high temperature, poor durability and the like in the existing rubber composite material.
Description
Technical field
The present invention relates to a kind of soft, high damping ratio and high gentle and quiet moment of torsion, the good yielding rubber material of weather resistance and preparation method thereof; This material can be used as mover rubber torsional balancer and uses with the damping rubber material, belongs to rubber-like Composite Preparation technical field.
Background technology
Oil engine develops to high-power, high speed direction at present; The total driving torque amplitude of caused each humorous the twisting vibration of explosion pressure strengthens in its reciprocal inertia force and the cylinder; Lower main humorous torsional resonance gets in the engine operation speed range, can bring more serious problems to engine reliability.According to the data introduction, axle system wants the net horsepower of consumption of engine when the torsional oscillation vibration takes place, and when the humorous subresonance of master appears in the multi-cylinder vehicular engine, generally understands 3%~5% of consumption of engine net horsepower.And strong resonance can consume about 10%.
The rubber torsional balancer is to be contained in the engine crankshaft free end to be used to regulate the variation of crankshaft system quick passage critical speed, suppresses the crankshaft torsional vibrations amplitude, and utilizes the elastomeric material damping characteristic to absorb amount of torsional energy; With the crankshaft torsional vibrations stress control the permission scope in; Ensure the bent axle safe handling, be mainly used in the product such as passenger car mover, constitute by wheel hub, rubber ring and inertia ring three parts; Rubber layer is set rubber ring; Rubber ring is by being pressed between interior wheel and the inertial mass, and wherein rubber ring is the core component of rubber absorbers, and the quality of rubber performance is confirming that directly the performance of vibroshock is good and bad.
Because China's mechanical workout is started late with the equipment manufacturing industry; Especially the research to high performance internal combustion engine just began to pay close attention in last century Mo; Technical capacity still has no small gap than advanced international standard; Wherein oil engine has seriously hindered the localization process of general-purpose engine especially with the manufacturing of torsional vvibration dampeer, and lags far behind the foreign same type product especially as the rubber ring of the core component of oil engine torsional balancer.
With the automobile industry is example; Along with China's rapid development of economy, automobile industry has progressively occupied the pillar status of China's Economic development, introduces external advanced production equipment and technology in a large number; Set about starting brand name computer motor vehicle energetically with independent intellectual property right; The demand of component production domesticization is urgent and important, and annual hundreds of millions high-performance Vehicular internal combustion engine height dependence on import shock absorber rubber ring seriously restricts the step of automobile industry spontaneous development.
American-European countries to the research of torsional balancer early, China begins to introduce the rubber torsional balancer the eighties in last century, receives many-sided effects limit such as starting material and analytical test means, global design, develops comparatively slow.In practical application; The major control index of rubber absorbers is dynamic thermal fatigue properties of natural frequency, subsidence ratio, quiet moment of torsion and rubber ring; Each performance requriements more than at present the U.S., Britain, German equivalent type product have all possessed under than the soft condition, and its high fatigue performance is that product provides high reliability particularly outstanding.
The internal damping of rubber layer is decided by the kind and the hardness of rubber, considers that from manufacturability the rubber ring of forced rubber torsional balancer can only adopt the lower rubber of shore hardness.Simultaneously; Rubber torsional balancer working position is near IC engine airframe, and oil engine needs long-time reliable and stable work, and working temperature is generally between 60 ℃~80 ℃; Under hot environment; Performances such as the subsidence ratio of rubber ring, natural frequency all decrease than the normal temperature state, and because the internal friction that damped motion brings also can cause the rubber ring temperature to increase sharply, therefore the dynamic fatigue performance of rubber ring are had higher requirement.
For this reason; Use the damping rubber material to be target with the oil engine torsional balancer, system carries out research and inquirement to the damping rubber material, through the cooperation research to rubber damping material; Promote the damping capacity of rubber torsional balancer rubber ring; Promote the safety of rubber ring, will provide and satisfy existing oil engine torsional balancer requirement, satisfy the bottleneck restriction that vibroshock brought in the homemade oil engine independent development; Promote safety, the economy of homemade torsional balancer comprehensively, also will have very economic benefit and social benefit.
Summary of the invention
The object of the present invention is to provide a kind of torsional balancer with elastomeric material and preparation method thereof, solved that existing rubber composite hardness high-leveled and difficultly press-fits, problem such as little, endurance quality difference of quiet moment of torsion under the high temperature.
Soft of the present invention, high gentle and quiet moment of torsion, the good yielding rubber material of weather resistance comprise following composition (in mass fraction):
100 parts of paracril and styrene-butadiene rubber composite materials;
40~70 parts of reinforcing fillers;
5~10 parts of Nano carbon whites;
1~3 part of coupling agent and processing aid;
10~15 parts in softening softening agent;
2~3 parts in anti-aging agent;
8~10 parts of sulfuration and auxiliary agents;
Base rubber of the present invention adopts to have excellent in resistance oiliness and the fireballing paracril of rubber vulcanization as main raw, adopts the styrene-butadiene rubber(SBR) with excellent tensile strength, abrasion performance and flexural property as subsidiary material.Wherein the content of paracril in base rubber is not less than 70%.Paracril is the multipolymer of divinyl and vinyl cyanide, and acrylonitrile content is 28~33%.Styrene-butadiene rubber(SBR) is divinyl and cinnamic random copolymers.
The reinforcing filler that the present invention adopts is carbon black N550 or carbon black N330 and carbon black N550 and uses and light calcium carbonate that wherein the carbon black mass umber is at least 40 parts, and the light calcium carbonate umber is 0~30 part.Strengthening agent is filled the mechanical property that can improve base rubber, improves the ageing-resistant and tear resistance of elastomeric material simultaneously.
Nano carbon white particle diameter 10~30 nanometers that the present invention adopts can be the preparations of the precipitator method and sol-gel processing, the WHITE CARBON BLACK large usage quantity of sol-gel processing preparation wherein, and the WHITE CARBON BLACK consumption that the vapor phase process and the precipitator method prepare is less.An amount of filling white carbon black can improve mechanical property, particularly elongation at break and the tear resistance of elastomeric material.
The coupling agent that the present invention adopts is any in silane coupling agent, titanate coupling agent, aluminate coupling agent and the phosphate coupling agent, comprises the coupling agent that contains the two keys of C=C, wherein preferred silane class coupling agent.Directly contact with mineral filler through coupling agent, under the high shear of rubber mixing machine, comparatively high temps, realize the situ-formed graft reaction, play bridge joint effect between mineral ion and the base rubber.Processing aid is a kind of among the mixture processing aid l-24, metallic soap class mixture processing aid D-S of hydrocarbon polymer.Processing aid l-24, processing aid D-S can improve the consistency of rubber and reinforcing filler, obtain the good distribution effect, and energy efficient.
Described softening softening agent is any one or two kinds among Witcizer 300, DOP or the TP95.
The anti-aging agent that the present invention adopts is any one usefulness also in chemical antiager RD and antioxidant 4010NA and the anti-aging agent 4020, and wherein the anti-aging agent RD mass fraction is at least 1 part.The anti-aging agent combination of two kinds of different chain rupture mechanism is used, produce synergistic effect, and the effect of usefulness is made elastomeric material in longer period, bring into play heat-resisting and anti-flex crack effect effectively greater than the effect of single use.
Vulcanizing agent is organo-peroxide DCP (Di Cumyl Peroxide 99), tasteless DCP (tert-butyl peroxide diisopropyl benzene), two 25 (2 in described sulfuration of the present invention and the auxiliary agent; 5-dimethyl--2; One of 5-bis(t-butylperoxy) hexane), at least 2 parts of consumptions; Vulcanization aid comprises promotor, promoting agent, wherein promotor be promotor TAIC, vulkacit H VA-2 any, mass fraction is 1~2 part; Promoting agent comprises inorganic active agent zinc oxide and organic active agent Triple Pressed Stearic Acid, and wherein zinc oxide is 4~6 parts; 1~2 part of Triple Pressed Stearic Acid.There are two keys on butyronitrile and the styrene-butadiene rubber(SBR) molecular chain, can select sulfur cross-linking, peroxide vuleanization, compound system sulfuration.When selecting superoxide, it is less to help under the high temperature decay of elastomeric material mechanical property.
Elastomeric material of the present invention is prepared into through the following steps complete processing; Comprise and close three steps such as refining, mixing, sulfuration: at first; With paracril and styrene-butadiene rubber(SBR) press mass fraction in mill, mesh, thin logical repeatedly after, until blend glue stuff at 100 ℃ mooney viscosity viscosity ML
1+4In 40~60 scopes.Then; The above-mentioned rubber master batch that closes after the refining is moved into the Banbury mixer engagement; Then reinforcing filler and Nano carbon white, coupling agent and processing aid, softening softening agent, anti-aging agent, vulcanization aid etc. are added Banbury mixeies, under high temperature, shear conditions, mix, wherein rotor speed of banbury mixer is controlled at 50~120r/min; Temperature is controlled at 120~140 ℃, and mixing time is discharge behind the 5min at least.In mill, add vulcanizing agent, mixingly obtain rubber unvulcanizate after evenly.Be sulfurating stage at last, the rubber unvulcanizate of above-mentioned test gained is packed in the mould, on vulcanizing press, vulcanize, curing time 10~20min, 150~160 ℃ of curing temperatures, sulfide stress 10~14Mpa promptly obtains the rubber damping circle of this material.
The present invention is through choosing suitable glue kind, and the reasonable technology design is optimized material and formed, and realizes obtaining high moment of torsion and subsidence ratio under the soft, and bigger economic worth is arranged.Select for use the combination of paracril and styrene-butadiene rubber(SBR) as base rubber; Add carbon black, Nano carbon white and auxiliary agent; Realize carbon black filler homodisperse in base rubber, and form the bonding force between strengthening agent-rubber interface, improve physical strength, ageing-resistant, the oil resistance of sizing material; Through add vulcanizing agent, vulcanization aid, softening agent, etc., obtain other performances of crosslinking degree that suitable curing temperature is controlled rubber parts, to satisfy the anti-deformation of material.It is good and have an elastomeric material of good damping performance finally to obtain weather resistance.
Embodiment
Below through embodiment the present invention is further specified; But should not be construed as is limitation of the present invention, and the technical scheme that modification, replacement or change realized of every other various ways of making based on technological basic thought of the present invention all belongs to scope of the present invention.
Embodiment 1
The ratio that paracril (trade mark 1043, acrylonitrile content are 30%) and styrene-butadiene rubber(SBR) (trade mark 1052) are respectively 70:30 in the mass fraction proportioning in mill, mesh certain hour, thin logical repeatedly after, until epoxy glue at 100 ℃ of mooney viscosity viscosity ML
1+4In 40~60 scopes.
The above-mentioned rubber master batch that closes after the refining is moved into Banbury mixer; The mass fraction of rubber master batch is by 100 parts; With 30 parts of N550 carbon blacks, 15 parts of N330 carbon blacks, 8 parts of Nano carbon white, 10 parts of light calcium carbonates, 1 part of silane coupling agent KH550,1 part of processing aid l-24,5 parts of zinc oxide, 1 part of Triple Pressed Stearic Acid adding Banbury mixeies that particle diameter is 10~30nm, add respectively 1.5 parts of 10 parts of softening plasticizer phthalic acid dibutylesters, chemical antiager RD and antioxidant 4010NAs subsequently; Under high temperature, shear conditions, mix, wherein rotor speed of banbury mixer is controlled at 50~120r/min, and temperature is controlled at 120~140 ℃, and mixing time is discharge behind the 5min at least; Add 2 parts of vulcanizing agent organo-peroxide DCP and 1 part of promotor TAIC in the mill, 60~80 ℃ of controlled temperature, mixing time is 5min at least, mixingly obtains rubber unvulcanizate after evenly.
The rubber unvulcanizate of above-mentioned gained is packed in the damped ring mould, on vulcanizing press, vulcanize, curing time 15min, 155 ± 2 ℃ of curing temperatures, sulfide stress 12 ± 1Mpa promptly obtains the damped ring of this elastomeric material.
Embodiment 2 ~ 7
Embodiment 2 ~ 7
In a word, the present invention provides good yielding rubber material of soft, high gentle and quiet moment of torsion and weather resistance and preparation method thereof, and implementing process is simple, has industrialization value preferably.
Claims (9)
1. soft, high gentle and quiet moment of torsion and the good yielding rubber material of weather resistance is characterized in that: comprise following composition and mass fraction thereof:
100 parts of paracril and styrene-butadiene rubber composite materials;
40~70 parts of reinforcing fillers;
5~10 parts of Nano carbon whites;
1~3 part of coupling agent and processing aid;
10~15 parts in softening softening agent;
2~3 parts in anti-aging agent;
8~10 parts of sulfuration and auxiliary agents.
2. elastomeric material according to claim 1; It is characterized in that: described paracril and styrene-butadiene rubber composite material are base rubber; Wherein the content of paracril in base rubber is not less than 70%; Paracril is the multipolymer of divinyl and vinyl cyanide, and acrylonitrile content is 28~33%, and styrene-butadiene rubber(SBR) is divinyl and cinnamic random copolymers.
3. elastomeric material according to claim 1 is characterized in that: described reinforcing filler is carbon black N550 or carbon black N330 and carbon black N550 and uses and light calcium carbonate that wherein the carbon black mass umber is at least 40 parts, and the light calcium carbonate umber is 0~30 part.
4. elastomeric material according to claim 1 is characterized in that: described Nano carbon white is the precipitator method and sol-gel method preparation, wherein particle diameter 10~30nm.
5. elastomeric material according to claim 1; It is characterized in that: described coupling agent is any in silane coupling agent, titanate coupling agent, aluminate coupling agent and the phosphate coupling agent, and processing aid is a kind of among the mixture processing aid l-24, metallic soap class mixture processing aid D-S of hydrocarbon polymer.
6. elastomeric material according to claim 1 is characterized in that: described softening softening agent is any one or two kinds among Witcizer 300, DOP or the TP95.
7. elastomeric material according to claim 1 is characterized in that: described anti-aging agent is any one and a usefulness in anti-aging agent RD and antioxidant 4010NA and the anti-aging agent 4020, and wherein the anti-aging agent RD mass fraction is at least 1 part.
8. elastomeric material according to claim 1; It is characterized in that: vulcanizing agent is organo-peroxide DCP (Di Cumyl Peroxide 99), tasteless DCP (tert-butyl peroxide diisopropyl benzene), two 25 (2 in described sulfuration and the auxiliary agent; 5-dimethyl--2; One of 5-bis(t-butylperoxy) hexane), at least 2 parts of consumptions; Vulcanization aid comprises promotor, promoting agent, and wherein promotor is any among promotor TAIC, the vulkacit H VA-2, and mass fraction is 1~2 part; Promoting agent comprises inorganic active agent zinc oxide and organic active agent Triple Pressed Stearic Acid, and wherein zinc oxide is 4~6 parts; 1~2 part of Triple Pressed Stearic Acid.
9. soft according to claim 1, high gentle and quiet moment of torsion and the good yielding rubber preparation methods of weather resistance is characterized in that; Comprise and close refining, mixing, three steps of sulfuration:
(1) closes refining: paracril and styrene-butadiene rubber(SBR) are pressed mass fraction meshes, thin logical certain hour in mill, until 100 ℃ of mooney viscosity viscosity ML
1+440~60;
(2) mixing: that the above-mentioned rubber master batch that closes after the refining is moved into Banbury mixer; Then reinforcing filler, Nano carbon white, coupling agent and processing aid, softening softening agent, anti-aging agent and vulcanization aid are added Banbury mixer, under high temperature, shear conditions, mix, wherein rotor speed of banbury mixer is controlled at 50~120r/min; Temperature is controlled at 120~140 ℃; Mixing time is the 5min discharge at least, in mill, adds vulcanizing agent, mixingly obtains rubber unvulcanizate after evenly;
(3) sulfuration: the rubber unvulcanizate of above-mentioned test gained is packed in the mould, on vulcanizing press, vulcanize curing time 10~20min, 150 ~ 160 ℃ of curing temperatures, sulfide stress 10~14MPa.
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Cited By (6)
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CN103467787A (en) * | 2013-06-24 | 2013-12-25 | 西安汉华橡胶科技有限公司 | Formula of nano-zinc oxide and rubber composite vibration absorption rubber material |
CN104629121A (en) * | 2015-02-02 | 2015-05-20 | 柳州市颖航汽配有限公司 | Damping rubber composition used for automobile engines |
CN106009115A (en) * | 2016-08-05 | 2016-10-12 | 咸阳时代特种密封科技有限公司 | High-hardness rubber, and preparation method and application thereof |
CN107118409A (en) * | 2017-06-20 | 2017-09-01 | 南京金三力高分子科技有限公司 | A kind of colored nitrile rubber and preparation method thereof |
CN109337143A (en) * | 2018-08-15 | 2019-02-15 | 苏州闪联高压电器有限公司 | The track insulation pad new material and its production technology of isolation fan stream and resistance to vibration function |
CN114524982A (en) * | 2021-12-30 | 2022-05-24 | 安徽志诚机电零部件有限公司 | Novel damping composite material for vehicle and preparation method thereof |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103467787A (en) * | 2013-06-24 | 2013-12-25 | 西安汉华橡胶科技有限公司 | Formula of nano-zinc oxide and rubber composite vibration absorption rubber material |
CN104629121A (en) * | 2015-02-02 | 2015-05-20 | 柳州市颖航汽配有限公司 | Damping rubber composition used for automobile engines |
CN106009115A (en) * | 2016-08-05 | 2016-10-12 | 咸阳时代特种密封科技有限公司 | High-hardness rubber, and preparation method and application thereof |
CN106009115B (en) * | 2016-08-05 | 2018-02-09 | 咸阳时代特种密封科技有限公司 | High durometer rubber and its preparation method and application |
CN107118409A (en) * | 2017-06-20 | 2017-09-01 | 南京金三力高分子科技有限公司 | A kind of colored nitrile rubber and preparation method thereof |
CN107118409B (en) * | 2017-06-20 | 2019-01-25 | 南京金三力高分子科技有限公司 | A kind of nitrile rubber and preparation method thereof |
CN109337143A (en) * | 2018-08-15 | 2019-02-15 | 苏州闪联高压电器有限公司 | The track insulation pad new material and its production technology of isolation fan stream and resistance to vibration function |
CN114524982A (en) * | 2021-12-30 | 2022-05-24 | 安徽志诚机电零部件有限公司 | Novel damping composite material for vehicle and preparation method thereof |
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Application publication date: 20121003 |