CN103524813B - A kind of modified rubber masterbatch and method for making and the oil-filled solution polymerized butadiene styrene rubber composition of one and method for making thereof and cross-linked rubber thereof - Google Patents
A kind of modified rubber masterbatch and method for making and the oil-filled solution polymerized butadiene styrene rubber composition of one and method for making thereof and cross-linked rubber thereof Download PDFInfo
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- CN103524813B CN103524813B CN201210229274.9A CN201210229274A CN103524813B CN 103524813 B CN103524813 B CN 103524813B CN 201210229274 A CN201210229274 A CN 201210229274A CN 103524813 B CN103524813 B CN 103524813B
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Abstract
The invention provides the oil-filled solution polymerized butadiene styrene rubber composition of a kind of modified rubber masterbatch and method for making and one and method for making thereof and cross-linked rubber thereof.Described modified rubber masterbatch comprises uncrosslinked rubber and is dispersed in the paracril particle with crosslinking structure wherein; Described paracril particle, median size is 50 ~ 200nm, and gel content is 60% weight or higher; Uncrosslinked rubber is styrene-butadiene rubber(SBR); The weight ratio of described crosslinking acrylonitrile butadiene particle and uncrosslinked rubber is greater than 20 ︰ 80, is less than or equal to 80 ︰ 20.Described oil-filled solution polymerized butadiene styrene rubber composition includes blended above-mentioned modified rubber masterbatch and oil-filled solution polymerized butadiene styrene rubber; Be 100 parts by weight with oil-filled solution polymerized butadiene styrene rubber, described modified rubber component is 1 ~ 70 part.The wet and slippery performance of cross-linked rubber, the wear resisting property of described oil-filled solution polymerized butadiene styrene rubber composition can be improved simultaneously, and have lower rolling resistance, may be used for preparing high-performance car tread rubber.
Description
Technical field
The present invention relates to rubber materials, say further, relate to a kind of modified rubber masterbatch and method for making, and by the oil-filled solution polymerized butadiene styrene rubber composition and method of making the same of modified rubber masterbatch modification and its cross-linked rubber.
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 automotive industry simultaneously also faces Carbon emission decrement pressure, how to reduce vehicle fuel consume and becomes more and more urgent.Reduce fuel oil consumption, not only can reduce automobilism cost, and the pressure of CO2 emissions and alleviation petroleum resources can be reduced.Vehicle fuel consume is except affecting by automobile design itself factor, tire drag is also one of important factor, tire drag fuel oil consumption accounts for 14 ~ 17% of vehicle fuel consume, and tire drag often reduces by 10%, usually can reduce fuel oil consumption 1 ~ 2%.Therefore, tire drag is reduced by one of important measures as reduction fuel oil consumption.
But in the research of reduction tyre stock (mainly tread rubber) rolling resistance, encounter very stubborn problem.Namely so-called " Magic triangle " problem that rolling resistance, wet and slippery performance, wear resisting property are conflicting.Simple increase tenderizer consumption, can improve the anti-slippery of tire, but its wear resistance reduces and rolling resistance increases.Improve the consumption of reinforced filling (carbon black or white carbon black), rolling resistance can be reduced to a certain extent, but make reinforced filling be difficult to be uniformly dispersed in sizing material, and anti-slippery is reduced.Strengthen the consumption of vulcanizing agent, namely improve cross-linking density, the same with the effect increasing reinforced filling consumption, reduce rolling resistance and make anti-slippery be deteriorated simultaneously.In order to realize the balance of three aspect performances, except Design of Tire Structure is optimized, also research is extensively and profoundly carried out to sizing material (based on tread rubber) formula both at home and abroad.The on the one hand rubber raw materials (as solution polymerized butadiene styrene rubber SSBR, using trans-polyisoprene TPI, butadiene-isoprene-vinylbenzene integrated rubber SIBR, high-vinyl cis-1,4-polybutadiene rubber HVBR etc.) that is suitable for of synthesis, sets about the properties-correcting agent seeking to have better over-all properties and practical formulation on the other hand.Some progress have been obtained in formulating, more representational: solution polymerized butadiene styrene rubber (SSBR) etc. are also used or reciprocal (reversion) carbon black system with carbon black and white carbon black, system feature is that main formula is substantially constant, just different on reinforced filling, easily industrially realizes; Its shortcoming is that when needing to use more silane coupling agent and refine glue, machine utilization is large, and the wear resistance of cross-linked rubber is also undesirable.
The rubber gels adopting the Chemical Crosslinking Methods such as direct polymerization method or superoxide to prepare, when filling a prescription suitable, can improve the performance of cross-linked rubber.Such as, report respectively in European patent EP 405216 and German patent DE 4220563 and in rubber combination, to add chloroprene rubber gel and cis-1,4-polybutadiene rubber gel respectively to improve wear resistance and the fatigue temperature rise of cross-linked rubber, but have lost resistance to wet skidding performance.
So a lot of patent starts to adopt the rubber gels of modification to improve the performance of vulcanization of rubber glue, such as US Patent No. 6184296 uses through the suitable fourth of surface modification and styrene-butadiene rubber(SBR) gel (latex particle swelling index 4 ~ 5 in gel, particle diameter 60 ~ 450nm), the rolling resistance of natural rubber (NR) formula system cross-linked rubber is reduced, and strength property is uninfluenced.
In US Patent No. 6133364,1-chloro-4-methyl-benzene is grafted in styrene-butadiene rubber(SBR) gel surface, then uses it in NR formula system, the rolling resistance of cross-linked rubber is reduced, and anti-slippery improves.
US Patent No. 6207757 reaches the effect reducing NR formula system cross-linked rubber rolling resistance with the styrene-butadiene rubber(SBR) gel of 1-chloro-4-methyl-benzene modification, improve hauling ability and the wearing quality of tire simultaneously.
US Patent No. 6242534 in the lump for NR formula system, not only reduces the styrene-butadiene rubber(SBR) gel containing carboxyl and amino the rolling resistance of system cross-linked rubber, improves anti-slippery, and significantly improve stress at definite elongation.
European patent EP 1431075 improve styrene-butadiene rubber(SBR) (SBR) and cis-1,4-polybutadiene rubber (BR) with styrene-butadiene rubber(SBR) gel and plasticized starch and the performance of white carbon black system, result wear resistance is improved, and rolling resistance reduces, and the proportion of cross-linked rubber is also less.
US Patent No. 6699935 makes modified styrene butadiene rubber formula system have low-rolling-resistance with modification by copolymerization styrene-butadiene rubber(SBR) gel and has outstanding anti-slippery and wear resistance concurrently.
The rubber gels that above-mentioned patent documentation is mentioned all adopts Chemical Crosslinking Methods to be cross-linked, this method needs to use the higher cross-linking monomer of price and energy consumption is comparatively large, and relates generally to white carbon black system and the modified styrene butadiene rubber formula system of natural rubber formulations system or styrene-butadiene rubber(SBR).And importantly must by the rubber gels obtained after crosslinked carry out modified just can reach rolling resistance, anti-slippery and wear resistance while improve.Although there is the particle diameter of report rubber gels in these patents, but when these rubber gels are distributed in cross-linked rubber, the dispersion of initial stage particle diameter can be reached, really can play the modifying function of nano-rubber gel, not report in any patent.
Summary of the invention
For the problem of prior art, an object of the present invention is to provide a kind of modified rubber masterbatch, also can be described as modified rubber component.By the cross-linked rubber of the oil-filled solution polymerized butadiene styrene rubber composition of this master batch processing, not only there is lower rolling resistance and excellent resistance to wet skidding performance, there is excellent wear resistance simultaneously, can use as excellent automobile tread rubber.
Another object of the present invention is to provide the method for making of described modified rubber masterbatch.
Another object of the present invention is to provide the oil-filled solution polymerized butadiene styrene rubber composition including described modified rubber masterbatch.
4th object of the present invention is to provide the preparation method of described rubber combination.
5th object of the present invention is to provide the cross-linked rubber of described oil-filled solution polymerized butadiene styrene rubber composition.
International patent application WO01/40356(priority date on December 3rd, 1999 that the applicant submitted on September 18th, 2000) and the applicant international patent application WO01/98395(priority date on June 15th, 2000 of submitting June 15 calendar year 2001) in disclose a kind of fully vulcanized powder rubber.Propose after adopting irradiance method cross-linked rubber latex, because cross-linking radiation makes the latex particle in rubber latex (rubber particles) reach certain gel content, the particle diameter of its latex particle is fixed up, can not in drying process afterwards adhesion or coalescence.Contriver finds under study for action, and by the paracril latex after this cross-linking radiation and the mixing of uncrosslinked styrene butadiene rubber latex, coalescence obtains the rubber combination of the particle modified styrene-butadiene rubber(SBR) of a kind of crosslinked paracril altogether afterwards.Wherein due to cross-linking radiation the paracril particle with crosslinking structure between can not adhesion and coalescence, and the latex particle meeting coalescence of common uncrosslinked styrene butadiene rubber latex, in the rubber matrix that the paracril particle therefore with crosslinking structure just can obtain after uncrosslinked styrene butadiene rubber latex coalescence with the particle size dispersion of its progenitor, and the degree that is uniformly dispersed than direct by much better in fully vulcanized powder rubber and the mixing mixture obtained of rubber.Obtain a kind of modified rubber masterbatch thus.
Using this modified rubber masterbatch as solid rubber master batch, then obtain rubber unvulcanizate with the oil-filled solution polymerized butadiene styrene rubber of uncrosslinked bulk by blending technologies such as Banbury mixer, end runner mill, screw extrusion presss.The rubber unvulcanizate so obtained, also can ensure the dispersion situation in the particle size range that the rubber particles with crosslinking structure of cross-linking radiation reaches described in uncrosslinked oil-filled solution polymerized butadiene styrene rubber matrix.In this composition, add that conventional rubber processing aids is mixing again, obtain cross-linked rubber after sulfuration.Because the paracril particle after cross-linking radiation has crosslinking structure, do not need the sulfuration considering disperse phase, this addresses the problem the covulcanization problem of the composition of different rubber composition; Simultaneously the paracril particle with crosslinking structure of cross-linking radiation is still evenly dispersed in in the oil-filled solution polymerized butadiene styrene rubber vulcanized rubber that is matrix with very little initial size very much, so the anti-slippery of the cross-linked rubber finally obtained and wear resistance can obtain raising simultaneously, the low-rolling-resistance performance that oil-filled solution polymerized butadiene styrene rubber itself has can be maintained simultaneously and be not affected substantially.
Specifically, a kind of modified rubber masterbatch of the present invention, comprises uncrosslinked rubber and is dispersed in the rubber particles with crosslinking structure wherein.Uncrosslinked rubber is external phase, and the rubber particles with crosslinking structure is disperse phase.The weight ratio of the described rubber particles and uncrosslinked rubber with crosslinking structure is greater than 20 ︰ 80, is less than or equal to 80 ︰ 20; Preferred weight ratio is 30 ︰ 70-80 ︰ 20, is more preferably 40 ︰ 60-80 ︰ 20.
The described rubber particles with crosslinking structure is paracril particle, and median size is 50 ~ 200nm, is preferably 70 ~ 200nm, more preferably 80 ~ 180nm; Gel content is 60% weight or higher, is preferably 75% weight or higher.The rubber particles in the above modified rubber masterbatch with crosslinking structure is equal phase structure.And do not carry out any graft modification, surface modification.Described uncrosslinked rubber is various styrene-butadiene rubber(SBR) in prior art, preferred emulsion polymerized styrene butadiene rubber of the prior art, i.e. the styrene/butadiene copolymers prepared of emulsion polymerisation process (breast poly-method).
The method for making of modified rubber masterbatch of the present invention, be comprise uncrosslinked rubber latex is mixed with the component of latex of the rubber particles with crosslinking structure after coalescence and obtaining: the latex wherein with the rubber particles of crosslinking structure is the rubber latex obtained after cross-linking radiation.
Specifically, the method for making of described modified rubber masterbatch, comprises the following steps:
(1) by paracril latex through cross-linking radiation, make the paracril particle in latex have crosslinking structure, reach described gel content, and make the paracril particle in latex be fixed in described average particle size range;
(2) then have the rubber particles of crosslinking structure and the mass ratio range of described uncrosslinked rubber by described, the latex of the paracril latex and described uncrosslinked rubber of getting above-mentioned cross-linking radiation carries out being mixed to evenly;
(3) above gained mixing latex is carried out common coalescence and obtain described modified rubber masterbatch.
The preparation method of above-described modified rubber masterbatch, wherein the latex of uncrosslinked rubber is styrene butadiene rubber latex.Paracril latex before described styrene butadiene rubber latex and non-cross-linking radiation is synthetic rubber latex common in prior art.Described styrene butadiene rubber latex comprises breast that emulsion polymerisation process in prior art directly prepared and gathers the latex will obtained after block for butylbenzene latex prepared by styrene-butadiene latex and any existing method; Be preferably the latex of emulsion polymerized styrene butadiene rubber in prior art.Wherein the weight ratio of the solid content of paracril latex and the solid content of styrene butadiene rubber latex is greater than 20 ︰ 80, is less than or equal to 80 ︰ 20; Preferred weight ratio is 30 ︰ 70-80 ︰ 20, is more preferably 40 ︰ 60-80 ︰ 20.
The cross-linking radiation of paracril latex picked up from according to international patent application WO01/40356(priority date on December 3rd, 1999 in the above step (1)) disclosed in fully vulcanized powder rubber preparation method in the method for identical cross-linking radiation rubber latex.Paracril latex after the cross-linking radiation of gained is also with the rubber latex before drying non-after irradiation in WO01/40356.
Specifically, can not crosslinking coagent be used at paracril latex, also can use crosslinking coagent.Crosslinking coagent used is selected from simple function group crosslinking coagent, two functional group's crosslinking coagents, trifunctional crosslinking coagent, four-functional group crosslinking coagent or polyfunctional group crosslinking coagent and arbitrary combination thereof.The example of described simple function group crosslinking coagent includes, but is not limited to: (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) glycidyl acrylate; The example of two described functional group's crosslinking coagents includes, but is not limited to: 1,4-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, Vinylstyrene; The example of described trifunctional crosslinking coagent includes, but is not limited to: trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate; The example of described four-functional group crosslinking coagent includes, but is not limited to: tetramethylolmethane four (methyl) acrylate, ethoxyquin tetramethylolmethane four (methyl) acrylate; The example of described polyfunctional group crosslinking coagent includes, but is not limited to: Dipentaerythritol five (methyl) acrylate.In this article, " (methyl) acrylate " refers to acrylate or methacrylic ester.These crosslinking coagents can use in the mode of arbitrary combination, as long as they contribute to crosslinked under irradiation.
The add-on of the above crosslinking coagent is generally 0.1 ~ 10% weight of dry glue weight in latex.Be preferably 0.5 ~ 9% weight, be more preferably 0.7 ~ 7% weight.
The energetic ray source of described irradiation is selected from cobalt source, ultraviolet or high-energy electron accelerator, preferred cobalt source.The dosage of irradiation can be 0.1 ~ 30Mrad, preferably 0.5 ~ 20Mrad.Generally, the rubber particles gel content after irradiation dose should make rubber latex cross-linking radiation reaches 60% weight or higher, preferably 75% weight or higher, more preferably 80% weight or higher.
Thus, in the modified rubber masterbatch obtained with coalescence after common uncrosslinked styrene butadiene rubber latex mixing by the paracril latex after this kind of cross-linking radiation, be dispersed in the paracril particle dispersion phase in the external phase of uncrosslinked butylbenzene rubber formation, also there is the characteristic of the full vulcanised nitrile powdered rubber disclosed in WO01/40356.Namely this kind has the rubber particles of crosslinking structure is that gel content reaches 60% weight or higher, and more excellent is 75% weight or higher rubber particles.Each particulate that this kind has in the paracril particle of crosslinking structure is homogeneous phase, and namely single particulate is all homogeneous on composition, does not find the phenomenon of layering, point equal uneven phase under the observation of existing microtechnique in particulate.This paracril particle with crosslinking structure is by fixing corresponding paracril latex cross-linking radiation rubber particles particle diameter, and its particle diameter is consistent with the particle diameter of the latex particle in original paracril latex.The median size of the rubber particles (latex particle) in original paracril latex is generally 50 ~ 200nm, is preferably 70 ~ 200nm, more preferably 80 ~ 180nm.The median size with the rubber particles of crosslinking structure after cross-linking radiation is also generally 50 ~ 200nm, is preferably 70 ~ 200nm, more preferably 80 ~ 180nm.Mix and coalescence owing to utilizing two kinds of latex in the method, in paracril latex after cross-linking radiation, paracril particle is cross-linked, there is certain gel content, can not in latex coalescence process adhesion or coalescence, and can be uniformly dispersed in uncrosslinked styrene-butadiene rubber(SBR), therefore, in the modified rubber masterbatch finally obtained, wherein as the median size with the rubber particles of crosslinking structure of disperse phase also at 50 ~ 200nm, be preferably 70 ~ 200nm, in the scope of more preferably 80 ~ 180nm.
The present invention is total to coalescence according to described weight ratio by after the paracril latex mixing after uncrosslinked styrene butadiene rubber latex, cross-linking radiation, prepares described modified rubber masterbatch.In its preparation process, the mixing equipment used at two kinds of rubber latex mixing steps is exactly conventional mixing equipment, is selected from homogenizer of the prior art, kneader etc. mechanical mixing equipment.The coalescence condition of latex and equipment just adopt latex coalescence condition conventional in existing rubber industry and equipment.
The oil-filled solution polymerized butadiene styrene rubber composition of one of the present invention, includes blended modified rubber masterbatch of the present invention and oil-filled solution polymerized butadiene styrene rubber; Be 100 parts by weight with oil-filled solution polymerized butadiene styrene rubber, modified rubber masterbatch is 1 ~ 70 part, is preferably 1 ~ 40 part, is more preferably 1 ~ 30 part, most preferably 5 ~ 15 parts.
Described oil-filled solution polymerized butadiene styrene rubber be conventionally in the method commonly used of rubber industry oil-filled and styrene-butadiene rubber(SBR) that is that obtain is carried out to solution polymerized butadiene styrene rubber, the oil filled is at least one in high aromatic oil, aromatic hydrocarbon oil and naphthenic oil.Described solution polymerized butadiene styrene rubber is the styrene/butadiene copolymers that in prior art prepared by solution polymerization process (containing intermingle with method).Oil-filled solution polymerized butadiene styrene rubber is by commercially available and obtain.
The preparation of oil-filled solution polymerized butadiene styrene rubber composition of the present invention comprises: first prepare described modified rubber masterbatch, the method of irradiation is adopted to be cross-linked by paracril latex, the rubber particles in latex is made to have crosslinking structure, then by the paracril latex after cross-linking radiation with after mixing on conventional mixing equipment with uncrosslinked styrene butadiene rubber latex, the conventional coalescence method coalescence of rubber latex is adopted to obtain described modified rubber masterbatch; And then using this modified rubber masterbatch as solid rubber master batch, to adopt in rubber industry conventional method for mixing rubber and the oil-filled rubber of uncrosslinked bulk together with other rubber usual auxiliaries, namely uncrosslinked oil-filled solution polymerized butadiene styrene rubber block glue carries out mixingly obtaining described oil-filled solution polymerized butadiene styrene rubber composition.
Specifically, the preparation method of oil-filled solution polymerized butadiene styrene rubber composition of the present invention, comprises the following steps:
(1) by paracril latex through cross-linking radiation, the paracril particle in latex is made to have crosslinking structure, reach described gel content, and make the paracril particle in latex be fixed in described average particle size range, as at 50 ~ 200nm, be preferably 70 ~ 200nm, in the scope of more preferably 80 ~ 180nm;
(2) then have the rubber particles of crosslinking structure and the mass ratio range of uncrosslinked rubber by described, paracril latex and the uncrosslinked described styrene butadiene rubber latex of getting above-mentioned cross-linking radiation carry out being mixed to evenly; Wherein the weight ratio of the solid content of paracril latex and the solid content of emulsion polymerized styrene butadiene rubber latex is greater than 20 ︰ 80, is less than or equal to 80 ︰ 20; Preferred weight ratio is 30 ︰ 70-80 ︰ 20, is more preferably 40 ︰ 60-80 ︰ 20.
(3) above gained mixing latex is carried out common coalescence and obtain described modified rubber masterbatch;
(4) by above-mentioned gained modified rubber masterbatch by described amount and the mixing composition obtaining oil-filled solution polymerized butadiene styrene rubber of described oil-filled solution polymerized butadiene styrene rubber; Be wherein 100 parts by weight with oil-filled solution polymerized butadiene styrene rubber, modified rubber masterbatch is 1 ~ 70 part, is preferably 1 ~ 40 part, is more preferably 1 ~ 30 part, most preferably 5 ~ 15 parts.
Oil-filled solution polymerized butadiene styrene rubber composition of the present invention also can containing weighting agent conventional in rubber processing.Following substances is the weighting agent suitable especially of preparation the present invention's oil-filled solution polymerized butadiene styrene rubber composition rubber unvulcanizate and cross-linked rubber, comprises a kind of in carbon black, white carbon black, metal oxide, silicate, carbonate, vitriol, oxyhydroxide, glass fibre or glass microballon etc. or its mixture.At least one in wherein said metal oxide preferential oxidation titanium, aluminum oxide, magnesium oxide, calcium oxide, barium oxide and zinc oxide etc.Can also containing auxiliary agent conventional in the Rubber processing sulfidations such as such as linking agent, vulcanization accelerator, antioxidant, thermo-stabilizer, photostabilizer, ozone stabilizers, processing aid, softening agent, tenderizer, anti blocking agent, whipping agent, dyestuff, pigment, wax, extender, organic acid, fire retardant and coupling agent in rubber combination of the present invention.Adjuvant used consumption is conventional amount used, or adjusts according to the requirement of practical situation.
Above-described various auxiliary agent add can modified rubber masterbatch as solid rubber master batch and oil-filled solution polymerized butadiene styrene rubber block glue mixing in add, namely added by the common calendering process of rubber, equipment can adopt method conventional in rubber industry and conventional mixing facilities, can make mill, Banbury mixer, single screw extrusion machine or twin screw extruder etc.
The cross-linked rubber prepared by oil-filled solution polymerized butadiene styrene rubber composition of the present invention is the cross-linked rubber that the vulcanization system that adopts rubber materials to commonly use above-described oil-filled solution polymerized butadiene styrene rubber composition of the present invention and technique are carried out mixing and sulfuration and obtained.
The oil-filled solution polymerized butadiene styrene rubber composition of the present invention prepares cross-linked rubber not by the impact of vulcanization system, can sulfuration in the sulfur cross-linking system of routine or non-sulfur cross-linking system.The cross-linked rubber prepared of rubber combination of the present invention by the impact of sulfuration process, can compression molding, injection sulfurization, sulfurizing pot vulcanization, individual vulcanizer sulfuration, the sulfuration of congruent melting salt, fluidized bed vulcanization, microwave vulcanization and energetic ray sulfuration etc.
Prepare conventional method and conventional mixing facilities in the mixing of cross-linked rubber and sulfidation employing rubber industry by rubber combination of the present invention, mill, Banbury mixer, single screw extrusion machine or twin screw extruder etc. can be made.
Specifically, the Micro of modified rubber masterbatch of the present invention is as previously mentioned: described uncrosslinked styrene-butadiene rubber(SBR) is external phase, and the described paracril particle with crosslinking structure is disperse phase, and disperses with the fine particle size of 50 ~ 200nm.By modified rubber masterbatch and oil-filled solution polymerized butadiene styrene rubber mixing after the obtained cross-linked rubber of the oil-filled solution polymerized butadiene styrene rubber composition that obtains, still have identical microtexture, the paracril particle with crosslinking structure namely in modified rubber masterbatch is still dispersed in styrene-butadiene rubber(SBR) matrix with the fine particle size of 50 ~ 200nm.
Modified rubber masterbatch in rubber combination of the present invention, be fixed up with the particle diameter of original latex particle owing to being made the rubber particles in paracril latex by cross-linking radiation, so the paracril particle of cross-linking radiation, as disperse phase, is dispersed in as in the uncrosslinked styrene-butadiene rubber(SBR) of external phase using the fine particle size of 50 ~ 200nm in coalescence process.Using this modified rubber masterbatch as rubber master batch and oil-filled solution polymerized butadiene styrene rubber mixing, obtain oil-filled solution polymerized butadiene styrene rubber composition, the cross-linked rubber obtained by this rubber combination again, still have identical microtexture, the paracril particle with crosslinking structure namely in modified rubber masterbatch is still dispersed in styrene-butadiene rubber(SBR) matrix with the fine particle size of 50 ~ 200nm.So just have such microscopic pattern, the paracril particle with crosslinking structure just can be made to play nano effect, solve the covulcanization problem that different rubber exists in sulfidation simultaneously, make the raising that the cross-linked rubber anti-slippery of rubber combination of the present invention and wear resistance can obtain simultaneously, and maintain low rolling resistance performance and be not affected substantially.
Say further, the vulcanized rubber prepared by rubber combination of the present invention not only has lower rolling resistance and excellent resistance to wet skidding performance, has excellent wear resistance simultaneously, can use as high-performance car tread rubber.Because three parameters of rubber combination of the present invention " grinding triangular " are all very excellent, can according to the specific requirement to these three parameters during practical application, carried and added other auxiliary agents to regulate the overall synthetic performance of rubber combination, thus brought larger adjustment leeway to the tread rubber preparing different performance demand.
The preparation method of rubber combination of the present invention and cross-linked rubber thereof is simple, and processing ease, processing condition are usual conditions, are easy to widespread use.
Specific implementation method:
Further describe the present invention by embodiment below, but scope of the present invention is not by the restriction of these embodiments.Scope of the present invention is determined by accompanying claims.
(1) in embodiment, experimental data following plant and instrument and measuring method measures:
(1) rolling resistance: use RSS-II rubber rolling resistance test machine (Beijing all things on earth Yifang Technology Co., Ltd.) to measure rolling power loss.
To under constant load, the garden colyliform rubbery sample of constant motion and wheel hub close contact do relative movement.The surface that rubbery sample contacts with wheel hub produces and is out of shape under pressure load, be out of shape from point of contact increase gradually to intermediate point; A little zero is gradually reduced to leaving again from intermediate point.Due to the viscous-elastic behaviour of various rubber compounding, rubbery sample start between point of contact to intermediate point deformation phases make a concerted effort by than intermediate point to the height of making a concerted effort leaving a recovery period, this power parallel with load forces is the power loss value (J/r) of rubbery sample.The rolling resistance of this rubber compounding can be characterized accordingly.
Rolling resistance index (%): be radix by the rolling resistance measurement value of gum, the percentage ratio that the measured value of other modified adhesive accounts for gum rolling resistance measurement value is rolling resistance index.
(2) wear resisting property test: according to GB/T1689-1998, adopts WML-76 type Akron abrasion machine to measure the wear(ing)value of cross-linked rubber.
Principle is: sample and emery wheel are rubbed under certain angle of inclination and certain load effect, measure the wear volume of certain mileage.Wear volume is calculated as follows:
V-sample abrasion volume, cm
3
M
1quality before the wearing and tearing of-sample, g
M
2quality after the wearing and tearing of-sample, g
ρ-sample density, cm
3
Sample abrasion Index for Calculation:
V
s--the wear volume of standard recipe rubber.
V
t--the wear volume of modified rubber.
Wear index (%): be radix by the wear volume measured value of gum, the percentage ratio that the wear volume measured value of other modified adhesive accounts for gum measured value is wear index.
(3) dynamic properties test (measuring wet and slippery): adopt the DMTAIV(dynamic mechanical analysis instrument that RheometricScientific company of the U.S. produces) test, test conditions is 10Hz, 0.5% strain, heat-up rate 2 DEG C/min.
The friction of sizing material on wet structure is relevant with hysteresis loss, and the tan δ at usually adopting 0 DEG C characterizes 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 percentage ratio that the anti-slippery measured value of other modified adhesive accounts for the anti-slippery measured value of gum is anti-slippery index.
(4) mechanical property: measure by related standard requirements.
(5) gel content of cross-linking radiation rubber latex and the mensuration of median size: after nitrile rubber is carried out cross-linking radiation according to certain condition, carry out spraying dry, obtain full vulcanised nitrile powdered rubber, then according to international patent application WO01/40356(priority date on December 3rd, 1999) disclosed in method measure gel content and the median size of full vulcanised nitrile powdered rubber, be exactly gel content and the median size of paracril latex after this cross-linking radiation.
(2) used in embodiment and comparative example raw material:
Emulsion polymerized styrene butadiene rubber latex SBR1502: solid content 20wt%, combined styrene content 23wt%, mooney viscosity 50, rubber plant of Qilu Petrochemical Company produces.
Oil-filled solution polymerized butadiene styrene rubber: block rubber, the trade mark: 2535L, Sinopec Shanghai Gaoqiao petrochemical industry branch office produces
Paracril latex: the trade mark is NBR-26, Tian Yuan Chemical Co., Ltd. of Zhaodong City 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-tertiary butyl-2-[4-morpholinodithio time yellow acid amides, chemical plant, Kingsoft, Zhengzhou
Calcium chloride: commercially available
Starch: commercially available
Glycerine: commercially available
5% PHENOL 99.8 MIN ((CARBOLIC ACID)) liquid: commercially available
(3) latex coalescence method:
According to the recipe configuration coalescence agent solution of table 1, then join in this coalescence agent solution according to the rubber latex with coalescence agent solution identical weight, stir after 15 minutes, filtration, washing, drying, obtain solid rubber (rubber).
Table 1
| Calcium chloride | Starch | Glycerine | 5%wt PHENOL 99.8 MIN ((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 rubber unvulcanizate and the method for sulfuration:
One segment process:
Carry out in Banbury Banbury mixer (Britain FarrelBridge Products), volume 1.57L, rotor speed 80rmin
-1; Its process is: add separately oil-filled solution polymerized butadiene styrene rubber rubber or add modified rubber masterbatch of the present invention, oil-filled solution polymerized butadiene styrene rubber rubber, carbon black and other auxiliary agents (sulphur, promotor, except) etc., put down floating weight, mixing 3min.Binder removal (temperature is at 150 ~ 160 DEG C).
Two step process:
Thin-pass is gone up six times in XK-160 type mill (Shanghai rubber machinery plant product), bottom sheet afterwards after above-mentioned one section of rubber unvulcanizate being added sulphur, promotor.Then at 160 DEG C, sulfurizing time T is pressed
90sulfuration, then makes standard batten by vulcanized rubber print, carries out every Mechanics Performance Testing, and its result is as shown in table 3.The formula of rubber unvulcanizate is in table 2, and unit is parts by weight.
Embodiment 1
1, the preparation of modified rubber masterbatch:
(1) preparation of cross-linking radiation paracril latex:
Be in the paracril latex (NBR-26) of 45%wt at solid content, after adding crosslinking coagent Viscoat 295 by the 3%wt of nitrile rubber solid content, carry out cross-linking radiation, irradiation dose is 3.0Mrad, obtain the paracril latex of cross-linking radiation, the median size 100nm of the paracril particle of cross-linking radiation in latex, gel content is 91%.
(2) latex mixing and coalescence:
Join in uncrosslinked emulsion polymerized styrene butadiene rubber latex SBR1502 by the paracril latex after cross-linking radiation according to certain solid content ratio, the paracril latex solid content wherein after cross-linking radiation and uncrosslinked emulsion polymerized styrene butadiene rubber latex solid content weight ratio are 80:20.After agitator high speed stirs 15 minutes, obtain solid-state modified rubber masterbatch according to aforementioned latex coalescence method coalescence.Wherein the composition of coalescence agent solution is with table 1.
2, oil-filled solution polymerized butadiene styrene rubber composition and cross-linked rubber preparation thereof:
Using above-mentioned gained modified rubber masterbatch as rubber master batch, and with other related auxiliaries add to carry out in block rubber (oil-filled solution polymerized butadiene styrene rubber 2535L) mixing, obtain rubber unvulcanizate, its formula composition with weight parts in table 2, the preparation of rubber unvulcanizate and vulcanization process ditto described in.Then vulcanized rubber print is made standard batten, carry out every Mechanics Performance Testing, its result is as shown in table 3.
Comparative example 1
Pure oil-filled solution polymerized butadiene styrene rubber rubber (oil-filled solution polymerized butadiene styrene rubber 2535L) is adopted with mixing and sulfuration process identical in embodiment 1 step 2, carries out mixing and sulfuration.The rubber unvulcanizate formula composition of concrete rubber combination lists in table 2.Cured properties is in table 3.
Table 2 comparative example and Example formulations
| Title material | Comparative example 1 | Embodiment 1 |
| Oil-filled solution polymerized butadiene styrene rubber | 100 | 91.25 |
| Modified rubber masterbatch | 8.75 | |
| 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 salient features of table 3 comparative example and embodiment
| Project | Comparative example 1 | Embodiment 1 | Testing standard |
| Hardness (Shao Er A) | 63 | 65 | GB/T531.1-2008 |
| 300% stress at definite elongation/MPa | 11.6 | 12.8 | GB/T528-1998 |
| Tensile strength/MPa | 16.4 | 18.4 | GB/T528-1998 |
| Elongation rate of tensile failure/% | 395 | 418 | GB/T528 |
| Tension set/% | 8 | 8 | GB/T528 |
| Compression fatigue temperature rise/DEG C | 33.4 | 34.6 | GB/T1687-1993 |
| Rebound resilience/% | 44 | 42 | GB/T1681-2009 |
| Wear index/% | 100 | 93.2 | GB/T1689-1998 |
| Anti-slippery index/% | 100 | 116 | ___________ |
| Rolling resistance index/% | 100 | 107 | ___________ |
As can be seen from Table 3, adopt the wear index of oil-filled its cross-linked rubber of solution polymerized butadiene styrene rubber composition of modified rubber master batch processing of the present invention, anti-slippery index can improve simultaneously, its reason is exactly that the paracril particle with crosslinking structure after cross-linking radiation is dispersed in the oil-filled solution polymerized butadiene styrene rubber matrix of external phase with the fine particle size of 50 ~ 200nm.This characteristic of rubber combination of the present invention is especially suitable for use as automobile tread rubber.The feature of oil-filled solution polymerized butadiene styrene rubber itself is exactly that rolling resistance performance is good, rubber combination of the present invention is when maintaining lower rolling resistance, wear index can also be reduced, improve anti-slippery index, thus the wear resistance of cross-linked rubber and anti-slippery are improved simultaneously.Therefore according to the specific requirement to these three parameters during practical application, can carry and added other auxiliary agents to regulate the overall synthetic performance of rubber combination, thus brought larger adjustment leeway to the tread rubber preparing different performance demand.
Claims (13)
1. an oil-filled solution polymerized butadiene styrene rubber composition, includes blended oil-filled solution polymerized butadiene styrene rubber and modified rubber masterbatch; Be 100 parts by weight with oil-filled solution polymerized butadiene styrene rubber, described modified rubber masterbatch is 1 ~ 70 part; Wherein, described modified rubber masterbatch is made up of uncrosslinked rubber and the rubber particles with crosslinking structure be dispersed in wherein; The rubber particles wherein with crosslinking structure is paracril particle, and median size is 50 ~ 200nm, and gel content is 60% weight or higher; Wherein uncrosslinked rubber is styrene-butadiene rubber(SBR); The weight ratio of the described rubber particles and uncrosslinked rubber with crosslinking structure is greater than 20 ︰ 80, is less than or equal to 80 ︰ 20.
2. oil-filled solution polymerized butadiene styrene rubber composition according to claim 1, is characterized in that gel content is 75% weight or higher.
3. oil-filled solution polymerized butadiene styrene rubber composition according to claim 1, the rubber particles described in it is characterized in that with crosslinking structure is equal phase structure.
4. oil-filled solution polymerized butadiene styrene rubber composition according to claim 1, the median size described in it is characterized in that with the rubber particles of crosslinking structure is 70 ~ 200nm.
5. oil-filled solution polymerized butadiene styrene rubber composition according to claim 1, the weight ratio of the rubber particles and uncrosslinked rubber described in it is characterized in that with crosslinking structure is 30 ︰ 70-80 ︰ 20.
6. oil-filled solution polymerized butadiene styrene rubber composition according to claim 5, the weight ratio of the rubber particles and uncrosslinked rubber described in it is characterized in that with crosslinking structure is 40 ︰ 60-80 ︰ 20.
7. the oil-filled solution polymerized butadiene styrene rubber composition according to any one of claim 1 ~ 6, it is characterized in that described modified rubber masterbatch by comprise uncrosslinked rubber latex is mixed with the component of latex of the rubber particles with crosslinking structure after coalescence and obtaining; The latex wherein with the rubber particles of crosslinking structure is the rubber latex obtained after cross-linking radiation.
8. an oil-filled solution polymerized butadiene styrene rubber composition according to claim 7, the method for making of wherein said modified rubber masterbatch, comprises the following steps:
(1) by paracril latex through cross-linking radiation, make the paracril particle in latex have crosslinking structure, reach described gel content, and make the paracril particle in latex be fixed in described average particle size range;
(2) then have the rubber particles of crosslinking structure and the mass ratio range of described uncrosslinked rubber by described, the latex of the paracril latex and described uncrosslinked rubber of getting above-mentioned cross-linking radiation carries out being mixed to evenly;
(3) above gained mixing latex is carried out common coalescence and obtain described modified rubber masterbatch.
9. oil-filled solution polymerized butadiene styrene rubber composition according to claim 1, it is characterized in that with oil-filled solution polymerized butadiene styrene rubber be 100 parts by weight, described modified rubber masterbatch is 1 ~ 40 part.
10. oil-filled solution polymerized butadiene styrene rubber composition according to claim 9, it is characterized in that with oil-filled solution polymerized butadiene styrene rubber be 100 parts by weight, described modified rubber masterbatch is 1 ~ 30 part.
The preparation method of 11. 1 kinds of oil-filled solution polymerized butadiene styrene rubber compositions according to any one of claim 1 ~ 10, comprises by described amount by described modified rubber masterbatch with described oil-filled solution polymerized butadiene styrene rubber is mixing obtains oil-filled solution polymerized butadiene styrene rubber composition.
12., according to the preparation method of solution polymerized butadiene styrene rubber composition oil-filled described in claim 11, is characterized in that the preparation method of described modified rubber masterbatch comprises the following steps:
(1) by paracril latex through cross-linking radiation, make the paracril particle in latex have crosslinking structure, reach described gel content, and make the paracril particle in latex be fixed in described average particle size range;
(2) then have the rubber particles of crosslinking structure and the mass ratio range of described uncrosslinked rubber by described, the latex of the paracril latex and described uncrosslinked rubber of getting above-mentioned cross-linking radiation carries out being mixed to evenly;
(3) above gained mixing latex is carried out common coalescence and obtain described modified rubber masterbatch.
13. 1 kinds of cross-linked rubbers that according to any one of claim 1 ~ 10 prepared by oil-filled solution polymerized butadiene styrene rubber composition.
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| CN201210229274.9A CN103524813B (en) | 2012-07-03 | 2012-07-03 | A kind of modified rubber masterbatch and method for making and the oil-filled solution polymerized butadiene styrene rubber composition of one and method for making thereof and cross-linked rubber thereof |
| MX2014005050A MX343657B (en) | 2011-10-26 | 2012-10-26 | Modified rubber masterbatch, rubber composition prepared therewith and vulcanized rubber and preparation method thereof. |
| IN3426DEN2014 IN2014DN03426A (en) | 2011-10-26 | 2012-10-26 | |
| PL12844199T PL2772513T3 (en) | 2011-10-26 | 2012-10-26 | Modified rubber masterbatch, rubber composition prepared therewith and vulcanized rubber and preparation method thereof |
| SG11201401845PA SG11201401845PA (en) | 2011-10-26 | 2012-10-26 | Modified rubber masterbatch, rubber composition prepared therewith and vulcanized rubber and preparation method thereof |
| KR1020147013129A KR101698947B1 (en) | 2011-10-26 | 2012-10-26 | Modified rubber masterbatch, rubber composition prepared therewith and vulcanized rubber and preparation method thereof |
| US14/354,233 US9290643B2 (en) | 2011-10-26 | 2012-10-26 | Modified rubber masterbatch, and rubber composition and vulcanized rubber produced therefrom, and the preparation processes for them |
| AU2012327629A AU2012327629B2 (en) | 2011-10-26 | 2012-10-26 | Modified rubber masterbatch, rubber composition prepared therewith and vulcanized rubber and preparation method thereof |
| RU2014121083A RU2608764C2 (en) | 2011-10-26 | 2012-10-26 | Modified rubber mother batch, and rubber mixture and vulcanized rubber made therefrom, and methods of their production |
| PCT/CN2012/083574 WO2013060288A1 (en) | 2011-10-26 | 2012-10-26 | Modified rubber masterbatch, rubber composition prepared therewith and vulcanized rubber and preparation method thereof |
| JP2014537481A JP6091511B2 (en) | 2011-10-26 | 2012-10-26 | Modified rubber masterbatch, rubber composition, vulcanized rubber produced using the same, and method for preparing the same |
| EP12844199.5A EP2772513B1 (en) | 2011-10-26 | 2012-10-26 | Modified rubber masterbatch, rubber composition prepared therewith and vulcanized rubber and preparation method thereof |
| BR112014009912-0A BR112014009912B1 (en) | 2011-10-26 | 2012-10-26 | STANDARD MIXTURE OF MODIFIED RUBBER, STANDARD MIXTURE PROCESS OF MODIFIED RUBBER, RUBBER COMPOSITION, RUBBER COMPOSITION PREPARATION PROCESS AND VOLCANIZED RUBBER |
| CA2853523A CA2853523C (en) | 2011-10-26 | 2012-10-26 | Modified rubber masterbatch, and rubber composition and vulcanized rubber produced therefrom, and the preparation processes for them |
| ZA2014/03789A ZA201403789B (en) | 2011-10-26 | 2014-05-23 | Modified rubber masterbatch, and rubber composition and vulcanized rubber produced therefrom, and the preparation processes for them |
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| CN102050972A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Modified rubber composition 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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| CN102050972A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Modified rubber composition 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 |
| CN103073759A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Solution polymerized styrene-butadiene rubber composition, preparation method thereof, and vulcanized rubber thereof |
| CN103073760A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Emulsion polymerized styrene-butadiene rubber composition, preparation method thereof, and vulcanized rubber thereof |
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