CN103772767B - A kind of rubber composition and preparation method thereof and its vulcanizate - Google Patents
A kind of rubber composition and preparation method thereof and its vulcanizate Download PDFInfo
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- CN103772767B CN103772767B CN201210402963.5A CN201210402963A CN103772767B CN 103772767 B CN103772767 B CN 103772767B CN 201210402963 A CN201210402963 A CN 201210402963A CN 103772767 B CN103772767 B CN 103772767B
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Abstract
The invention provides a kind of rubber composition and preparation method thereof and its vulcanizate. Described rubber composition comprises uncrosslinked rubber and is dispersed in the rubber particles with cross-linked structure wherein with average grain diameter 50～300nm; The rubber particles wherein with cross-linked structure is carboxylic styrene-butadiene rubber particle, and gel content is 60% weight or higher; Wherein uncrosslinked rubber is butadiene-styrene rubber; Described have the rubber particles of cross-linked structure and the weight ratio of uncrosslinked rubber is 1 ︰ 99-20 ︰ 80. Described rubber composition including by uncrosslinked rubber latex with there is component the latex of rubber particles of cross-linked structure and mix after coalescence and obtaining. The latex wherein with the rubber particles of cross-linked structure is the rubber latex obtaining after cross-linking radiation. The vulcanizate resistance to rolling of described rubber composition, wet and slippery performance, anti-wear performance can be improved simultaneously, can be for the preparation of high-performing car tread rubber.
Description
Technical field
The present invention relates to rubber materials, say further, relate to a kind of rubber composition by rubber particles modification andPreparation method and its vulcanizate.
Background technology
Automobile more and more becomes the indispensable instrument of the modern life, and automobile power used comes from oil substantially,Petroleum resources are limited, and the fast development of auto industry simultaneously also faces CO2 emission decrement pressure, how to reduce vapourCar fuel consume becomes more and more urgent. Reduce fuel consume, not only can reduce automobilism cost, and can reduce twoThe pressure of carbonoxide discharge capacity and alleviation petroleum resources. Vehicle fuel consume is except being affected by automobile self design factorOutward, tire drag is also one of key factor, and tire drag fuel consume accounts for 14～17% of vehicle fuel consume,The every reduction by 10% of tire drag, can reduce fuel consume 1～2% conventionally. Therefore, reduction tire drag is used as and fallsOne of important measures of low fuel consume.
But run into very stubborn problem in the resistance to rolling research of reduction tyre stock (being mainly tread rubber). RollDynamic resistance, wet and slippery performance, conflicting so-called " Magic triangle " problem of anti-wear performance. The simple softening agent consumption that increases, canTo improve the anti-slippery of tire, but its wearability reduces and resistance to rolling increases. Improve reinforced filling (carbon black or white carbon)Consumption, can reduce to a certain extent resistance to rolling, but make reinforced filling in sizing material, be difficult to be uniformly dispersed, and make moisture-resistantSlip reduces. The consumption that strengthens vulcanizing agent, improves crosslink density, and the same with the effect that increases reinforced filling consumption, reduction is rolledDynamic resistance makes anti-slippery variation simultaneously. In order to realize the balance of three aspects: performance, except Design of Tire Structure is optimizedAlso sizing material (taking tread rubber as main) formula is carried out to research extensively and profoundly both at home and abroad outward. On the one hand synthetic applicable rubberRaw material (as solution polymerized butadiene styrene rubber SSBR, using trans-polyisoprene TPI, butadiene-isoprene-styrene integrated rubber SIBR,High-vinyl butadiene rubber HVBR etc.), set about on the other hand seeking to have modifier and the practical formulation of better combination property. ?In formulating, obtain some progress, more representational: solution polymerized butadiene styrene rubber (SSBR) etc. and carbon black and hard charcoalBlack and with or reciprocal (reversion) carbon black system, system feature is that main formula is substantially constant, just different on reinforced filling,Easily in industrial realization; Its shortcoming is that need to use more silane coupler and refining glue time, machine utilization is large, vulcanizateWearability is also undesirable.
Rubber gels prepared by the Chemical Crosslinking Methods such as employing direct polymerization method or peroxide, can in the time that formula is suitableTo improve the performance of vulcanizate. For example, in European patent EP 405216 and German patent DE 4220563, reported respectively at rubberIn composition, add respectively neoprene gel and butadiene rubber gel to improve wearability and the fatigue temperature rise of vulcanizate, stillLose moisture-proof slip.
For example, so a lot of patents start to adopt the rubber gels of modification to improve the performance of vulcanization of rubber glue, United States Patent (USP)US6184296 uses suitable fourth and butadiene-styrene rubber gel (latex particle swelling index 4～5 in gel, the particle diameter through surface modification60～450nm), the resistance to rolling of natural rubber (NR) formula system vulcanizate is reduced, and strength property is uninfluenced.
In US Patent No. 6133364,1-chloro-4-methyl-benzene is grafted in butadiene-styrene rubber gel surface, then by its useIn NR formula system, the resistance to rolling of vulcanizate is reduced, and anti-slippery improve.
The butadiene-styrene rubber gel of US Patent No. 6207757 use 1-chloro-4-methyl-benzene modifications has reached reduction NR formula systemThe effect of vulcanizate resistance to rolling has improved hauling ability and the durability of tire simultaneously.
US Patent No. 6242534 containing carboxyl and amino butadiene-styrene rubber gel in the lump for NR formula system, not onlyThe resistance to rolling that has reduced system vulcanizate, has improved anti-slippery, and has obviously improved stress at definite elongation.
European patent EP 1431075 use butadiene-styrene rubber gels and plasticized starch improve butadiene-styrene rubber (SBR) and suitable fourth rubberThe performance of the white carbon system of glue (BR) use, result wearability is improved, and resistance to rolling reduces, and the proportion of vulcanizate is alsoLess.
US Patent No. 6699935 use modification by copolymerization butadiene-styrene rubber gels make modified styrene butadiene rubber formula system have low rollingDynamic resistance has outstanding anti-slippery and wearability concurrently.
The rubber gels that above-mentioned patent documentation is mentioned all adopts Chemical Crosslinking Methods crosslinked, and this method need to be used valencyCross-linking monomer and energy consumption that lattice are higher are larger, and relate generally to the white carbon system of natural rubber formulations system or butadiene-styrene rubberAnd modified styrene butadiene rubber formula system. And importantly the rubber gels obtaining after crosslinked just must can after modification carrying outImprove reaching resistance to rolling, anti-slippery and wearability when. Although there is report rubber gels in these patentsParticle diameter, but in the time that these rubber gels are distributed in vulcanizate, can reach the dispersion of initial stage particle diameter, can be trueJust bringing into play the modifying function of nano-rubber gel, in any patent, do not reporting.
Summary of the invention
For the problem of prior art, one of object of the present invention is to provide a kind of rubber composition. This rubber compositionVulcanizate anti-slippery, resistance to rolling and wearability be improved simultaneously, can be used as good automobile tread rubber and use.
Another object of the present invention is to provide the preparation method of described rubber composition.
A further object of the present invention is to provide the vulcanizate of described rubber composition.
The International Patent Application WO 01/40356(priority date 1999 12 that the applicant submitted on September 18th, 2000Months 3 days) and the International Patent Application WO 01/98395(priority date submitted June 15 calendar year 2001 of the applicant 2000 6Months 15 days) in a kind of fully vulcanized powder rubber is disclosed. Propose when adopting after irradiance method cross-linked rubber latex, because irradiation is handed overConnection makes the latex particle (rubber particles) in rubber latex reach certain gel content, under the particle diameter of its latex particle is fixedCome, not can after dry run in adhesion or coalescence. Inventor finds under study for action, by the carboxyl after this cross-linking radiationStyrene butadiene rubber latex and uncrosslinked styrene butadiene rubber latex mix, and coalescence obtains a kind of crosslinked carboxylic styrene-butadiene rubber grain altogether afterwardsThe rubber composition of sub-modified styrene butadiene rubber. Wherein due to the carboxylic styrene-butadiene rubber particle with cross-linked structure of cross-linking radiation itBetween can adhesion and coalescence, and the latex particle of common uncrosslinked styrene butadiene rubber latex can coalescence, therefore has cross-linked structureCarboxylic styrene-butadiene rubber particle just can after uncrosslinked styrene butadiene rubber latex coalescence, obtain with the particle size dispersion of its predecessorRubber matrix in, and the degree that is uniformly dispersed than directly by fully vulcanized powder rubber and the mixing mixture obtaining of rubberIn much better. The rubber composition sulfuration obtaining after described two kinds of latex coalescences is finally prepared into vulcanizate, because irradiation is handed overCarboxylic styrene-butadiene rubber particle after connection has had cross-linked structure, does not need to consider the sulfuration of decentralized photo, has so just solved notThe co-vulcanization problem of the composition forming with rubber; The carboxylic styrene-butadiene rubber particle with cross-linked structure of cross-linking radiation is complied with simultaneouslySo be evenly dispersed in styrene-butadiene vulcanized rubber very much with initial size that can be very little, so the vulcanizate finally obtainingAnti-slippery, resistance to rolling and wearability can side by side be improved.
Specifically, a kind of rubber composition of the present invention, comprises uncrosslinked rubber and divides with average grain diameter 50～300nmBe dispersed in the rubber particles with cross-linked structure wherein. Uncrosslinked rubber is continuous phase, and the rubber particles with cross-linked structure isDecentralized photo. The rubber particles wherein with cross-linked structure is carboxylic styrene-butadiene rubber particle, and gel content is 60% weight or higher;Wherein uncrosslinked rubber is butadiene-styrene rubber; Described have the rubber particles of cross-linked structure and the weight ratio of uncrosslinked rubber is 1 ︰99-20 ︰ 80, preferably 1 ︰ 99-10 ︰ 90, more preferably 2 ︰ 98-8 ︰ 92, most preferably 2 ︰ 98-5 ︰ 95.
The above rubber particles with cross-linked structure is equal phase structure. And do not carry out any graft modification, surfaceModification. Preferred, described in there is the carboxylic styrene-butadiene rubber particle of cross-linked structure gel content be 75% weight or higher, itsAverage grain diameter is preferably 50 ~ 200nm, and more preferably 70 ~ 200nm, most preferably is 80 ~ 150nm.
The preparation of rubber composition of the present invention is to comprise uncrosslinked rubber latex and the rubber with cross-linked structureThe latex of micelle mixes rear coalescence and obtains in interior component: the latex wherein with the rubber particles of cross-linked structure is process spokeAccording to the rubber latex obtaining after crosslinked.
Specifically, the preparation method of rubber composition of the present invention, comprises the following steps:
(1) by carboxylic styrene-butadiene rubber latex process cross-linking radiation, make the carboxylic styrene-butadiene rubber particle in latex have crosslinkedStructure, reaches described gel content, and the carboxylic styrene-butadiene rubber particle in latex is fixed in described average particle size range;
(2) then by the weight ratio of described rubber particles and the uncrosslinked butadiene-styrene rubber with cross-linked structure, get above-mentionedThe carboxylic styrene-butadiene rubber latex of cross-linking radiation and uncrosslinked styrene butadiene rubber latex are mixed to evenly;
(3) above gained mixing latex is carried out to common coalescence and obtain described rubber composition.
The preparation method of above-described rubber composition, wherein styrene butadiene rubber latex and not cross-linking radiation carboxyl beforeStyrene butadiene rubber latex is synthetic rubber latex common in prior art. Wherein styrene butadiene rubber latex comprises breast in prior artThe glue obtaining after the block latex of butylbenzene prepared by the poly-styrene-butadiene latex of breast that liquid polymerization is directly prepared and any existing methodBreast; Be preferably the latex of emulsion polymerized styrene butadiene rubber in prior art. Before and after cross-linking radiation, the solid content of carboxylic styrene-butadiene rubber latex does not haveChange; Before irradiation, the solid content of carboxylic styrene-butadiene rubber latex contains with the consolidating of carboxylic styrene-butadiene rubber latex with cross-linked structureAmount, the weight ratio of the solid content of itself and styrene butadiene rubber latex is 1 ︰ 99 ~ 20 ︰ 80, preferably 1 ︰ 99 ~ 10 ︰ 90, more preferably 2 ︰ 98 ~ 8 ︰92, most preferably 2 ︰ 98-5 ︰ 95.
In the above step (1), the cross-linking radiation of carboxylic styrene-butadiene rubber latex picks up from according to International Patent Application WO 01/40356(priority date on December 3rd, 1999) identical cross-linking radiation in the preparation method of disclosed fully vulcanized powder rubberThe method of rubber latex. Carboxylic styrene-butadiene rubber latex after the cross-linking radiation of gained is not with dry after irradiation in WO01/40356 yetRubber latex before.
Specifically, can not use crosslinking coagent at carboxylic styrene-butadiene rubber latex, also can use crosslinking coagent. UsedCrosslinking coagent to be selected from simple function group crosslinking coagent, two functional group's crosslinking coagents, trifunctional crosslinking coagent, four-functional group crosslinkedAuxiliary agent or polyfunctional group crosslinking coagent and any combination thereof. The example of described simple function group crosslinking coagent comprises (but not to be limitIn): (methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) glycidyl acrylate; Two described functional groupsThe example of crosslinking coagent includes, but is not limited to: BDO two (methyl) acrylate, 1,6-hexylene glycol two (methyl) thirdOlefin(e) acid ester, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) propyleneAcid esters, divinylbenzene; The example of described trifunctional crosslinking coagent includes, but is not limited to: trimethylolpropane tris (firstBase) acrylate, pentaerythrite three (methyl) acrylate; The example of described four-functional group crosslinking coagent comprises (but not to be limitIn): pentaerythrite four (methyl) acrylate, ethoxyquin pentaerythrite four (methyl) acrylate; Described polyfunctional group is handed overThe example of connection auxiliary agent includes, but is not limited to: dipentaerythritol five (methyl) acrylate. In this article, " (methyl) acrylic acidEster " refer to acrylate or methacrylate. These crosslinking coagents can use in the mode of any combination, as long as they are at spokeAccording under contribute to crosslinked.
The addition of the above crosslinking coagent is generally 0.1 ~ 10% weight of dry glue weight in latex. Be preferably 0.5 ~9% weight, more preferably 0.7 ~ 7% weight.
The high-energy ray source that described irradiation is used is selected from cobalt source, ultraviolet or high-energy electron accelerator, preferably cobalt source. The agent of irradiationAmount can be 0.1～30Mrad, preferably 0.5～20Mrad. Generally, irradiation dose should make rubber latex cross-linking radiationAfter rubber particles gel content reach 60% weight or higher, preferably 75% weight or higher, more preferably 80% weight or higher.
Thus, mixed with common uncrosslinked styrene butadiene rubber latex by the carboxylic styrene-butadiene rubber latex after this kind of cross-linking radiationClose rear coalescence and rubber composition in, the carboxylic styrene-butadiene rubber particle being dispersed in the continuous phase that uncrosslinked rubber forms dividesLoose phase, also has the characteristic of the disclosed full sulfuration Carboxy powdered rubber of WO01/40356. This kind has cross-linked structureRubber particles be that gel content reaches 60% weight or higher, more excellent is 75% weight or higher rubber particles. This kind has friendshipEach particulate in the carboxylic styrene-butadiene rubber particle of connection structure is homogeneous phase, and single particulate is all homogeneous on composition, under the observation of existing microtechnic, in particulate, do not find layering, divide the phenomenon that equates uneven phase. This has cross-linked structureCarboxylic styrene-butadiene rubber particle be by corresponding carboxylic styrene-butadiene rubber latex cross-linking radiation is fixed rubber particles particle diameter, its particle diameter is consistent with the particle diameter of the latex particle in original carboxylic styrene-butadiene rubber latex. In original carboxylic styrene-butadiene rubber latexThe average grain diameter of rubber particles (latex particle) be generally 50 ~ 300nm, be preferably 50 ~ 200nm, more preferably 70 ~ 200nm,Preferably 80 ~ 150nm. The average grain diameter of the rubber particles with cross-linked structure after cross-linking radiation is generally 50 ~ 300nm,Be preferably 50 ~ 200nm, more preferably 70 ~ 200nm, most preferably 80 ~ 150nm. Owing to utilizing two kinds of latex to mix in the methodAnd coalescence, in this rubber latex of carboxyl fourth after cross-linking radiation, carboxylic styrene-butadiene rubber particle is crosslinked, has certain gelContent, can be in latex coalescence process adhesion or coalescence, and can in uncrosslinked butadiene-styrene rubber, be uniformly dispersed, because ofThis, in the rubber composition finally obtaining, wherein as the average grain diameter of the rubber particles with cross-linked structure of decentralized photo alsoAt 50 ~ 300nm, be preferably 50 ~ 200nm, more preferably 70 ~ 200nm, most preferably in the scope of 80 ~ 150nm.
The present invention according to described weight ratio by this rubber latex of carboxyl fourth after uncrosslinked styrene butadiene rubber latex, cross-linking radiationAfter mixing, be total to coalescence, prepare this rubber composition. In its preparation process, two kinds of used mixing of rubber latex blend stepThe equipment of closing is exactly conventional mixing apparatus, is selected from homogenizer of the prior art, kneader etc. mechanical mixing equipment. GlueCoalescence condition and the equipment of breast just adopt latex coalescence condition and equipment conventional in existing rubber industry.
Never cross-linked rubber latex and there is prepared by the rubber latex mixing coalescence of rubber particles of cross-linked structure thisBright rubber composition also can contain filler conventional in rubber processing. Following substances is preparation elastomeric compound of the present inventionWith the suitable especially filler of vulcanized rubber, comprise carbon black, white carbon, metal oxide, silicate, carbonate, sulfate,A kind of or its mixture in hydroxide, glass fibre or glass microballoon etc. Wherein said metal oxide preferential oxidation titanium,At least one in aluminium oxide, magnesia, calcium oxide, barium monoxide and zinc oxide etc. All right in rubber composition of the present inventionContain for example crosslinking agent, vulcanization accelerator, antioxidant, heat stabilizer, light stabilizer, ozone stabilizing agent, processing aid, plasticisingThe rubber such as agent, softening agent, anti-blocking agent, blowing agent, dyestuff, pigment, wax, extender, organic acid, fire retardant and coupling agent addConventional auxiliary agent in work sulfidation. Adjuvant used consumption is conventional amount used, or adjusts according to the requirement of actual conditions.
Adding of above-described various auxiliary agents can just add in the time that two kinds of rubber latexs mix, also can be two kinds of rubbersAfter glue latex mixing coalescence, add by the common calendering process of rubber, equipment can adopt method conventional in rubber industry and normalWith mixing facilities, can make mill, banbury, single screw extrusion machine or double screw extruder etc.
By the vulcanizate of the preparation of rubber composition of the present invention, include by described weight ratio, sulfuration fourthBenzene rubber matrix and be dispersed in the carboxylic styrene-butadiene rubber particle with cross-linked structure wherein with described average grain diameter.
Specifically, the Micro of rubber composition of the present invention is as previously mentioned: described uncrosslinked butylbenzeneRubber is continuous phase, and the described carboxylic styrene-butadiene rubber particle with cross-linked structure is decentralized photo, and tiny with 50 ~ 300nmParticle size dispersion. In the vulcanizate making at this rubber composition, still there is identical microstructure.
Vulcanizate prepared by rubber composition of the present invention is not subject to the impact of vulcanizing system, can be at conventional sulfur cross-linking bodyIn system or non-sulfur cross-linking system, vulcanize. Vulcanizate prepared by rubber composition of the present invention is not subject to the impact of sulfuration process, canCompression molding, injection sulfurization, sulfurizing pot vulcanization, individual vulcanizer sulfuration, the sulfuration of congruent melting salt, fluidized bed vulcanization, microwave vulcanization withAnd high-energy ray sulfuration etc.
Mixing and the sulfidation of being prepared vulcanizate by rubber composition of the present invention adopts conventional method in rubber industryWith conventional mixing facilities, can make mill, banbury, single screw extrusion machine or double screw extruder etc.
Rubber composition of the present invention can also be served as solid rubber master batch, then with uncrosslinked niggerhead by banbury,The blending technology such as end runner mill, screw extruder obtains elastomeric compound. Such as, by the side of carboxylic styrene-butadiene rubber latex employing irradiationMethod is crosslinked, makes the rubber particles in latex have cross-linked structure, then by the rubber latex after cross-linking radiation with uncrosslinkedRubber latex adopts the conventional coalescence method coalescence of rubber latex to obtain solid rubber master batch after mixing on conventional mixing apparatus. WillThis solid rubber master batch adopts compounding process conventional in rubber industry to join in uncrosslinked niggerhead again, then adds conventionalRubber processing aids is mixing, obtain vulcanizate after sulfuration. The elastomeric compound so obtaining, also can ensure the friendship that has of cross-linking radiationDispersion situation in particle size range described in the rubber particles of connection structure reaches in uncrosslinked rubber matrix.
Due to the particle diameter that makes rubber particles in carboxylic styrene-butadiene rubber latex with original latex particle by cross-linking radiationBe fixed up, so in the sulfidation of preparing with follow-up vulcanizate in coalescence process, the carboxylic styrene-butadiene rubber of cross-linking radiationParticle, so just have such microscopic pattern, just can make with the tiny particle diameter of 50 ~ 300nm in uncrosslinked butadiene-styrene rubberThe carboxylic styrene-butadiene rubber particle performance effect with cross-linked structure, makes the vulcanizate of rubber composition of the present invention anti-slipperyProperty, resistance to rolling and wearability can side by side be improved.
Say further, by the prepared vulcanized rubber of rubber composition of the present invention not only have low resistance to rolling andExcellent moisture-proof slip has excellent wearability simultaneously, can be used as high-performing car tread rubber and uses.
The preparation method of rubber composition of the present invention and vulcanizate thereof is simple, processing ease, and process conditions are conventionallyCondition, is easy to extensive use.
Brief description of the drawings:
Fig. 1 is Micro transmission electron microscope (TEM) picture of the rubber composition vulcanizate that makes of embodiment 1.
Specific implementation method:
Further described the present invention with embodiment below, but scope of the present invention is not subject to the restriction of these embodiment.Scope of the present invention is determined by accompanying claims.
(1) in embodiment, experimental data is measured with following instrument and equipment and assay method:
(1) resistance to rolling: use RSS-II rubber rolling resistance test machine (the limited public affairs of Beijing all things on earth one side's development in science and technologyDepartment) mensuration rolling power loss.
To under constant load, garden colyliform rubbery sample and the wheel hub close contact of constant motion are done relative motion. Rubber examinationThe surface that sample contacts with wheel hub produces distortion under pressure load, and distortion increases to intermediate point gradually from starting contact point; Again fromIntermediate point is a little gradually reduced to zero to leaving. Due to the viscous-elastic behaviour of various rubber compoundings, rubbery sample arrives at beginning contact pointTo make a concerted effort highly to what leave a recovery period making a concerted effort between intermediate point deformation phases than intermediate point, and this power parallel with load forces isFor the power attenuation value (J/r) of rubbery sample. Can characterize accordingly the resistance to rolling of this rubber compounding.
Rolling resistance index (%): be radix by the rolling resistance measurement value of gum, the measured value of other modified adhesive accounts for pureThe percentage of rubber rolling resistance measurement value is rolling resistance index.
(2) anti-wear performance test: according to GB/T1689-1998, adopt WML-76 type Akron abrasion machine to measure sulphurChange the wearing valve of glue.
Principle is: sample and emery wheel are rubbed under certain angle of inclination and certain load effect, measure oneDetermine the abrasion volume of mileage. Abrasion volume is calculated as follows:
V-sample abrasion volume, cm3
m1Quality before the wearing and tearing of-sample, g
m2Quality after the wearing and tearing of-sample, g
ρ-sample density, cm3
Sample abrasion index calculates:
Vs--the abrasion volume of standard recipe rubber.
Vt--the abrasion volume of modified rubber.
Abrasion index (%): be radix by the abrasion stereometry value of gum, the abrasion stereometry value of other modified adhesiveThe percentage that accounts for gum measured value is abrasion index.
(3) dynamic mechanical test (measuring wet and slippery): adopt RheometricScientific company of the U.S. to produceDMTAIV(dynamic mechanical analysis instrument) test, experimental condition is 10Hz, 0.5% strain, 2 DEG C/min of programming rate.
Sizing material is relevant with hysteresis loss in wet lip-deep friction, conventionally adopts the tan δ at 0 DEG C to characterize wet-sliding resistant performance.Tan δ value at 0 DEG C is larger, and the hauling ability of tire on wet road surface is better.
Anti-slippery index (%): be radix by the anti-slippery measured value tan δ of gum, the anti-slippery mensuration of other modified adhesiveThe percentage that value accounts for the anti-slippery measured value of gum is anti-slippery index.
(4) mechanical property: measure by related standard requirements.
(5) mensuration of the gel content of cross-linking radiation rubber latex: styrene-butadiene latex is carried out to irradiation according to certain conditionAfter crosslinked, spray dry, obtain fully vulcanized powder rubber, then according to International Patent Application WO 01/40356(priorityDay on December 3rd, 1999) in disclosed method measure the gel content of full sulfuration butylbenzene powdered rubber, after being exactly this cross-linking radiationThe gel content of styrene butadiene rubber latex.
(2) raw material used in embodiment and comparative example:
Emulsion polymerized styrene butadiene rubber latex SBR1502: solid content 20wt%, in conjunction with styrene-content 23wt%, Mooney viscosity 50, neatShandong rubber plant of petro-chemical corporation produces.
Carboxylic styrene-butadiene rubber latex: the trade mark is butylbenzene-70, Henan, Yanshan Mountain Yanshi rubber plant produces.
Carbon black: N234 Haitun Carbon Black Co., Ltd. Tianjin.
Zinc oxide: commercially available.
Stearic acid: commercially available.
Sulphur: Linyi City Luo Zhuan chemical plant.
Accelerator TBBS: the N-tert-butyl group-2-[4-morpholinodithio time yellow acid amides, chemical plant, Kingsoft, Zhengzhou.
Calcium chloride: commercially available.
Starch: commercially available.
Glycerine: commercially available.
5% carbolic acid liquid: commercially available.
Cumyl peroxide: commercially available.
(3) latex coalescence method:
According to the recipe configuration coalescence agent solution of table 1, then according to adding with the rubber latex of coalescence agent solution identical weightEnter in this coalescence agent solution, stir after 15 minutes, filter, wash, be dried, obtain solid rubber (rubber).
Table 1
| Calcium chloride | Starch | Glycerine | 5%wt carbolic acid liquid | Water |
| 8 parts | 0.8 part | 0.3 part | 2 parts | Being adjusted to coalescence agent solution gross weight is 100 parts |
Note: be parts by weight in table 1
(4) preparation of elastomeric compound and the method for sulfuration:
One segment process:
In Banbury banbury (FarrelBridge company of Britain product), carry out volume 1.57L, rotor speed80r·min-1; Its process is: add butadiene-styrene rubber rubber or rubber composition of the present invention, carbon black and other auxiliary agent (sulphurSulphur, promoter, except), put down floating weight, mixing 3min. Binder removal (temperature is at 150～160 DEG C).
Two step process:
Above-mentioned one section of rubber master batch is added after sulphur, promoter in XK-160 type mill (Shanghai rubber machinery plant product)Thin-pass six times, descends sheet afterwards. Then at 160 DEG C, press sulfurizing time T90Sulfuration, then makes standard by vulcanized rubber printBatten, carries out every Mechanics Performance Testing, and its result is as shown in table 3. The formula of elastomeric compound is in table 2, and unit is parts by weight.
Embodiment 1
1, the preparation of cross-linking radiation carboxylic styrene-butadiene rubber latex
In the carboxylic styrene-butadiene rubber latex that is 48%wt at solid content, add friendship by the 3%wt of carboxylic styrene butadiene latex solid contentAfter connection auxiliary agent trimethylolpropane triacrylate, carry out cross-linking radiation, irradiation dose is 3.0Mrad, obtains cross-linking radiationCarboxylic styrene-butadiene rubber latex, the average grain diameter 100nm of the carboxylic styrene-butadiene rubber particle of cross-linking radiation in latex, gel content is93%。
2, the carboxylic styrene-butadiene rubber latex after cross-linking radiation is joined to uncrosslinked breast according to certain solid content ratioIn poly-styrene butadiene rubber latex SBR1502, wherein the carboxylic styrene-butadiene rubber latex solid content after cross-linking radiation and uncrosslinked breast gatherStyrene butadiene rubber latex solid content weight ratio is 3:97. Agitator high speed stirs after 15 minutes, according to aforementioned latex coalescence methodCoalescence obtains solid rubber composition. Wherein the composition of coalescence agent solution is with table 1.
3, above-mentioned gained rubber composition is added relevant auxiliary agent carry out mixing, obtain elastomeric compound, its formula composition is with heavyAmount umber meter is in table 2, the preparation of elastomeric compound and vulcanization process ditto described in. Then vulcanized rubber print is made to standard batten,Carry out every Mechanics Performance Testing, its result is as shown in table 3.
In addition, in order to prevent that carbon black in the sulfurizing formula of step 3 and zinc oxide and sulphur from affecting final sampleIn Micro transmission electron microscope picture, there is the observation of the rubber particles deployment conditions of crosslinked result, the rubber that step 2 is obtainedComposition vulcanizes by peroxide vulcanizing system, and concrete formula is: in this rubber composition, add cumyl peroxide,In rubber composition 100 weight portions, cumyl peroxide is 1.5 parts. The preparation of elastomeric compound and vulcanization process ditto described in,The vulcanizate sample obtaining is cut into the thick ultra-thin section that is about 0.1 μ m through cryoultramicrotome, then at osmium tetroxide steamMiddle dyeing, after 3 minutes, is made Micro transmission electron microscope (TEM) picture, in such osmium tetroxide steam under dyeing condition, and spokeCarboxylic styrene-butadiene rubber particle dyeing according to sulfuration is more shallow, can come with dark continuous phase butadiene-styrene rubber difference. See accompanying drawing 1,Carboxylic styrene-butadiene rubber particle disperses in butadiene-styrene rubber continuous phase with average grain diameter 100nm.
Comparative example 1
Change latex into simple employing emulsion polymerized styrene butadiene rubber latex SBR1502 by two kinds of latex that mix, other and implementExample 1 is identical, and the elastomeric compound formula composition of concrete rubber composition is listed in table 2. Cured properties is in table 3.
Table 2 comparative example and Example formulations
| Title material | Comparative example 1 | Embodiment 1 |
| *SBR1502 | 100 | 97 |
| Cross-linking radiation carboxylic styrene-butadiene rubber 1 | —— | 3 |
| 3# carbon black | 50 | 50 |
| Zinc oxide | 3 | 3 |
| Stearic acid | 1 | 1 |
| Sulphur | 1.75 | 1.75 |
| TBBS | 1 | 1 |
| Add up to | 156.75 | 156.75 |
The main performance of table 3 comparative example and embodiment
| Project | Comparative example 1 | Embodiment 1 | Testing standard |
| Hardness (Shao Er A) | 66 | 69 | GB/T531.1-2008 |
| 300% stress at definite elongation/MPa | 17.7 | 20.6 | GB/T528-1998 |
| Hot strength/MPa | 27.6 | 24.8 | GB/T528-1998 |
| Compression fatigue temperature rise/DEG C | 37.9 | 38.5 | GB/T1687-1993 |
| Rolling resistance index/% | 100 | 99.3 | —— |
| Abrasion index/% | 100 | 83.6 | GB/T 1689-1998 |
| Anti-slippery index/% | 100 | 102 | —— |
As can be seen from Table 3, adopt the rolling resistance index of its vulcanizate of rubber composition of the present invention, abrasion to refer toSeveral, anti-slippery index can be improved simultaneously, and its reason is exactly the Carboxy rubber with cross-linked structure after cross-linking radiationMicelle with the tiny particle size dispersion of 50 ~ 300nm in the butadiene-styrene rubber matrix of continuous phase. This of rubber composition of the present inventionSpecific character is especially suitable for use as automobile tread rubber.
Claims (10)
1. a rubber composition, is dispersed in the crosslinked knot that has wherein by uncrosslinked rubber with average grain diameter 50～300nmThe rubber particles composition of structure; The rubber particles wherein with cross-linked structure is carboxylic styrene-butadiene rubber particle, and gel content is 60%Weight or higher; Wherein uncrosslinked rubber is butadiene-styrene rubber; The described rubber particles with cross-linked structure and uncrosslinked rubberWeight ratio is 1 ︰ 99-20 ︰ 80.
2. rubber composition according to claim 1, has the rubber particles of cross-linked structure for equal described in it is characterized in thatPhase structure.
3. rubber composition according to claim 1, has rubber particles solidifying of cross-linked structure described in it is characterized in thatGlue content is 75% weight or higher.
4. rubber composition according to claim 1, has rubber particles flat of cross-linked structure described in it is characterized in thatAll particle diameter is 50～200nm.
5. rubber composition according to claim 4, has rubber particles flat of cross-linked structure described in it is characterized in thatAll particle diameter is 70～200nm.
6. rubber composition according to claim 1, described in it is characterized in that, have the rubber particles of cross-linked structure with notThe weight ratio of cross-linked rubber is 1 ︰ 99-10 ︰ 90.
7. rubber composition according to claim 6, described in it is characterized in that, have the rubber particles of cross-linked structure with notThe weight ratio of cross-linked rubber is 2 ︰ 98-8 ︰ 92.
8. according to the rubber composition described in any one of claim 1～7, it is characterized in that described composition comprises not friendshipConnection rubber latex mixes rear coalescence and obtains in interior component with the latex of the rubber particles with cross-linked structure; Wherein have crosslinkedThe latex of the rubber particles of structure is the rubber latex obtaining after cross-linking radiation.
9. according to a preparation method for the rubber composition described in any one of claim 1～8, comprise the following steps:
(1) by carboxylic styrene-butadiene rubber latex process cross-linking radiation, make the carboxylic styrene-butadiene rubber particle in latex there is cross-linked structure,Reach described gel content, and the carboxylic styrene-butadiene rubber particle in latex is fixed in described average particle size range;
(2) then by the weight ratio of described rubber particles and the uncrosslinked butadiene-styrene rubber with cross-linked structure, get above-mentioned irradiationCrosslinked carboxylic styrene-butadiene rubber latex and uncrosslinked styrene butadiene rubber latex are mixed to evenly;
(3) above gained mixing latex is carried out to common coalescence and obtain described rubber composition.
10. a vulcanizate of preparing according to the rubber composition described in any one of claim 1～8, includes by describedThe sulfuration butadiene-styrene rubber matrix of weight ratio meter, and be dispersed in the friendship that has in sulfuration butadiene-styrene rubber matrix with described average grain diameterConnect the carboxylic styrene-butadiene rubber particle of structure.
Priority Applications (12)
| Application Number | Priority Date | Filing Date | Title |
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| CN201210402963.5A CN103772767B (en) | 2012-10-22 | 2012-10-22 | A kind of rubber composition and preparation method thereof and its vulcanizate |
| SG11201401847UA SG11201401847UA (en) | 2011-10-26 | 2012-10-26 | Rubber composition and preparation method and vulcanized rubber thereof |
| PL12843797.7T PL2772512T3 (en) | 2011-10-26 | 2012-10-26 | Rubber composition and preparation method and vulcanized rubber thereof |
| RU2014121110A RU2607581C2 (en) | 2011-10-26 | 2012-10-26 | Rubber mixture, preparation method thereof and cured rubber produced therefrom |
| ES12843797T ES2940461T3 (en) | 2011-10-26 | 2012-10-26 | Rubber composition and method of preparation and vulcanized rubber thereof |
| TW101139749A TWI546343B (en) | 2011-10-26 | 2012-10-26 | Rubber composition and its preparation method and vulcanized rubber |
| CA2853513A CA2853513C (en) | 2011-10-26 | 2012-10-26 | Rubber composition and preparation method and vulcanized rubber thereof |
| US14/354,222 US9453122B2 (en) | 2011-10-26 | 2012-10-26 | Rubber composition, preparation method and vulcanized rubber thereof |
| KR1020147012677A KR101748600B1 (en) | 2011-10-26 | 2012-10-26 | Rubber composition and preparation method and vulcanized rubber thereof |
| JP2014537482A JP6084623B2 (en) | 2011-10-26 | 2012-10-26 | Rubber composition, preparation method thereof and vulcanized rubber |
| EP12843797.7A EP2772512B1 (en) | 2011-10-26 | 2012-10-26 | Rubber composition and preparation method and vulcanized rubber thereof |
| PCT/CN2012/083590 WO2013060290A1 (en) | 2011-10-26 | 2012-10-26 | Rubber composition and preparation method and vulcanized rubber thereof |
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Citations (3)
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|---|---|---|---|---|
| EP0992536A1 (en) * | 1998-10-09 | 2000-04-12 | The Goodyear Tire & Rubber Company | Tread rubber for high traction tires |
| CN101787148A (en) * | 2009-01-22 | 2010-07-28 | 中国科学院化学研究所 | Green tire material containing amphipathic starch derivant and preparation method thereof |
| CN102050973A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Tread rubber composite material and preparation method thereof |
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- 2012-10-22 CN CN201210402963.5A patent/CN103772767B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0992536A1 (en) * | 1998-10-09 | 2000-04-12 | The Goodyear Tire & Rubber Company | Tread rubber for high traction tires |
| CN101787148A (en) * | 2009-01-22 | 2010-07-28 | 中国科学院化学研究所 | Green tire material containing amphipathic starch derivant and preparation method thereof |
| CN102050973A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Tread rubber composite material and preparation method thereof |
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| Title |
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| 《连续液相混炼工艺生产的NR炭黑母炼胶》;王梦蛟;《轮胎工业》;20040331;第24卷(第3期);第135-143页 * |
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