CN103524810B - A kind of modified rubber masterbatch and preparation method and a kind of preparation method and a vulcanized rubber thereof - Google Patents
A kind of modified rubber masterbatch and preparation method and a kind of preparation method and a vulcanized rubber thereof Download PDFInfo
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Abstract
The invention provides a kind of modified rubber masterbatch and preparation method and a kind of preparation method and a vulcanized rubber thereof.Described modified rubber masterbatch comprises uncrosslinked rubber and the nitrile rubber particle with cross-linked structure being dispersed therein；Described nitrile rubber particle, mean diameter is 50～200nm, and gel content is 60% weight or higher；Uncrosslinked rubber is butadiene-styrene rubber；Described crosslinking acrylonitrile butadiene particle is more than 20 80, less than or equal to 80 20 with the weight ratio of uncrosslinked rubber.Described oil-filled emulsion polymerized styrene butadiene rubber compositions includes blended above-mentioned modified rubber masterbatch and oil-filled emulsion polymerized styrene butadiene rubber；Being in terms of 100 weight portions by oil-filled emulsion polymerized styrene butadiene rubber, modified rubber masterbatch is 1 ~ 70 part.The wet and slippery performance of vulcanizate of described oil-filled emulsion polymerized styrene butadiene rubber compositions, anti-wear performance can be improved simultaneously, and reduce resistance to rolling simultaneously, 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 preparation method, and by oil-filled emulsion polymerized styrene butadiene rubber compositions of modified rubber masterbatch modification and preparation method thereof and its vulcanizate.
Background technology
Automobile increasingly becomes the instrument that the modern life is indispensable, and the power used by automobile is substantially from oil, petroleum resources are limited, and the fast development of auto industry simultaneously also faces CO2 emission decrement pressure, how to reduce vehicle fuel consumption and become more and more urgent.Reduce fuel oil consumption, be possible not only to reduce automobilism cost, and CO2 emissions can be reduced and alleviate the pressure of petroleum resources.Vehicle fuel consumption is in addition to being affected by automobile self design factor, tire drag is also one of key factor, tire drag fuel oil consumption accounts for 14～17% that vehicle fuel consumes, and tire drag often reduces by 10%, generally can reduce fuel oil and consume 1～2%.Therefore, tire drag is reduced by as one of important measures reducing fuel oil consumption.
But in reducing tyre stock (mainly tread rubber) resistance to rolling research, encounter very stubborn problem.So-called " Magic triangle " problem that i.e. resistance to rolling, wet and slippery performance, anti-wear performance are conflicting.Simple increase softening agent consumption, can improve the anti-slippery of tire, but its wearability reduces and resistance to rolling increases.Improve the consumption of reinforced filling (white carbon black or white carbon), resistance to rolling can be reduced to a certain extent, but make reinforced filling be difficult to be uniformly dispersed in sizing material, and make anti-slippery reduce.Strengthen the consumption of vulcanizing agent, i.e. improve crosslink density, the same with the effect increasing reinforced filling consumption, reduce resistance to rolling and make anti-slippery be deteriorated simultaneously.In order to realize the balance of three aspect performances, in addition to Design of Tire Structure is optimized, the most also sizing material (based on tread rubber) formula is carried out research extensively and profoundly.On the one hand the rubber raw materials (such as solution polymerized butadiene styrene rubber SSBR, trans-polyisoprene TPI, butadiene-isoprene-styrene integrated rubber SIBR, high-vinyl butadiene rubber HVBR etc.) that synthesis is suitable for, on the other hand sets about modifying agent and the practical formulation seeking have preferable combination property.Some progress have been obtained in formulating, relatively more representational: solution polymerized butadiene styrene rubber (SSBR) etc. and white carbon black and white carbon and with or reciprocal (reversion) white carbon black system, system feature is that main formula is basically unchanged, the most different on reinforced filling, the most industrially realizes；Its shortcoming is that when needing to use more silane coupler and refining glue, machine utilization is big, and the wearability of vulcanizate is the most undesirable.
Use rubber gels prepared by the Chemical Crosslinking Methods such as direct polymerization method or peroxide when formula is suitable, the performance of vulcanizate can be improved.Such as, European patent EP 405216 and German patent DE 4220563 report wearability and fatigue temperature rise respectively that be separately added into neoprene gel and butadiene rubber gel in rubber composition to improve vulcanizate, but have lost resistance to wet skidding performance.
So a lot of patents begin with the rubber gels of modification to improve the performance of vulcanization of rubber glue, such as United States Patent (USP) US6184296 uses through the suitable fourth of surface modification and butadiene-styrene rubber gel (latex particle swelling index 4～5 in gel, particle diameter 60～450nm), the resistance to rolling making natural rubber (NR) formula system vulcanizate reduces, and strength property is uninfluenced.
In United States Patent (USP) US6133364,1-chloro-4-methyl-benzene is grafted in butadiene-styrene rubber gel surface, then uses it in NR formula system, make the resistance to rolling of vulcanizate reduce, and anti-slippery improves.
The butadiene-styrene rubber gel of United States Patent (USP) US6207757 1-chloro-4-methyl-benzene modification has reached to reduce the effect of NR formula system vulcanizate resistance to rolling, improves hauling ability and the ruggedness of tire simultaneously.
United States Patent (USP) US6242534 in the lump for NR formula system, not only reduces the butadiene-styrene rubber gel containing carboxyl and amino the resistance to rolling of system vulcanizate, improves anti-slippery, and significantly improve stress at definite elongation.
European patent EP 1431075 butadiene-styrene rubber gel and plasticized starch improve the performance of butadiene-styrene rubber (SBR) and the white carbon system of butadiene rubber (BR), and result wearability is improved, and resistance to rolling reduces, and the proportion of vulcanizate is the least.
United States Patent (USP) US6699935 modification by copolymerization butadiene-styrene rubber gel makes modified styrene butadiene rubber formula system have low-rolling-resistance and has outstanding anti-slippery and wearability concurrently.
The rubber gels that above-mentioned patent documentation is mentioned all uses Chemical Crosslinking Methods to cross-link, this method needs to use the higher cross-linking monomer of price and energy consumption relatively big, and relates generally to white carbon system and the modified styrene butadiene rubber formula system of natural rubber formulations system or butadiene-styrene rubber.And it is important that improve while the rubber gels obtained after crosslinking just can must be reached resistance to rolling, anti-slippery and wearability after being modified.Although having been reported that the particle diameter of rubber gels in these patents, but when these rubber gels are distributed in vulcanizate, the dispersion of initial stage particle diameter can be reached, can really play the modifying function of nano-rubber gel, not report in any patent.
Summary of the invention
For problem of the prior art, an object of the present invention is to provide a kind of modified rubber masterbatch, it is possible to be referred to as modified rubber component.The vulcanizate anti-slippery of oil-filled emulsion polymerized styrene butadiene rubber compositions, the wearability prepared by this masterbatch are improved simultaneously, and resistance to rolling is reduced, and can use as excellent automobile tread rubber.
It is a further object of the present invention to provide the preparation method of described modified rubber masterbatch.
It is also another object of the present invention to provide a kind of oil-filled emulsion polymerized styrene butadiene rubber compositions, include described modified rubber masterbatch.
Fourth object of the present invention is to provide the preparation method of described rubber composition.
5th purpose of the present invention is to provide the vulcanizate of described rubber composition.
The international patent application WO01/40356(priority date that the applicant submits in JIUYUE in 2000 on the 18th December in 1999 3 days) 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.Proposing when using irradiance method to cross-link after rubber latex, owing to cross-linking radiation makes the latex particle (rubber particles) in rubber latex reach certain gel content, the particle diameter of its latex particle is fixed up, will not adhesion or coalescence in dry run later.Inventor finds under study for action, the nitrile rubber latex after this cross-linking radiation and uncrosslinked styrene butadiene rubber latex is mixed, and coalescence obtains the rubber composition of the particle modified butadiene-styrene rubber of nitrile rubber of a kind of crosslinking the most altogether.Wherein due to will not adhesion and coalescence between the nitrile rubber particle with cross-linked structure of cross-linking radiation, and the latex particle meeting coalescence of common uncrosslinked styrene butadiene rubber latex, therefore have in the rubber matrix that the nitrile rubber particle of cross-linked structure will obtain with the particle size dispersion of its predecessor after uncrosslinked styrene butadiene rubber latex coalescence, and the degree that is uniformly dispersed than directly by much better in mixing to fully vulcanized powder rubber and the rubber mixture obtained.Thus obtain a kind of modified rubber masterbatch.
Using this modified rubber component as solid rubber master batch, then obtain elastomeric compound with the uncrosslinked oil-filled emulsion polymerized styrene butadiene rubber of bulk by blending technologies such as banbury, end runner mill, screw extruders.So obtained elastomeric compound, it is also ensured that the rubber particles with cross-linked structure of cross-linking radiation reaches the dispersion situation in described particle size range in uncrosslinked oil-filled emulsion polymerized styrene butadiene rubber matrix.This compositions adds conventional rubber processing aids mixing, sulfuration after obtain vulcanizate.Owing to the nitrile rubber particle after cross-linking radiation has had cross-linked structure, it is not necessary to consider the sulfuration of dispersion phase, this addresses the problem the co-vulcanization problem of the compositions of different rubber composition；The nitrile rubber particle with cross-linked structure of cross-linking radiation is still fairly evenly dispersed in the vulcanite with oil-filled emulsion polymerized styrene butadiene rubber as matrix with the least initial size simultaneously, so the anti-slippery of the vulcanizate finally given, wearability can obtain raising simultaneously, and resistance to rolling is reduced simultaneously.
Specifically, a kind of modified rubber masterbatch of the present invention, comprise uncrosslinked rubber and the rubber particles with cross-linked structure being dispersed therein.Uncrosslinked rubber is continuous phase, and the rubber particles with cross-linked structure is dispersion phase.Described have the rubber particles of cross-linked structure with the weight ratio of uncrosslinked rubber more than 20 80, less than or equal to 80 20；Preferred weight ratio is 30 70-80 20, more preferably 40 60-80 20.
The described rubber particles with cross-linked structure is nitrile rubber particle, and mean diameter is 50～200nm, preferably 70 ~ 200nm, more preferably 80 ~ 180nm；Gel content is 60% weight or higher, preferably 75% weight or higher.The rubber particles in the above modified rubber masterbatch with cross-linked structure is equal phase structure.And do not carry out any graft modification, surface modification.Described uncrosslinked rubber is various butadiene-styrene rubber in prior art, emulsion polymerized styrene butadiene rubber the most of the prior art, the styrene/butadiene copolymers that i.e. prepared by emulsion polymerisation process (newborn poly-method).
The preparation method of modified rubber masterbatch of the present invention, be after uncrosslinked rubber latex is mixed homogeneously with the component including the latex of the rubber particles with cross-linked structure coalescence and obtain: the latex of the rubber particles wherein with cross-linked structure is the rubber latex obtained after cross-linking radiation.
Specifically, the preparation method of described modified rubber masterbatch, comprise the following steps:
(1) by nitrile rubber latex through cross-linking radiation, make the nitrile rubber particle in latex have cross-linked structure, reach described gel content, and make the nitrile rubber particle in latex be fixed in described average particle size range；
(2) then by the described rubber particles with cross-linked structure and the mass ratio range of described uncrosslinked rubber, the latex of the nitrile rubber latex and described uncrosslinked rubber that take above-mentioned cross-linking radiation carries out mixing to uniformly；
(3) mixing latex obtained as above is carried out common coalescence and obtain described modified rubber masterbatch.
The preparation method of above-described modified rubber masterbatch, the latex of the most uncrosslinked rubber is styrene butadiene rubber latex.Nitrile rubber latex before described styrene butadiene rubber latex and non-irradiated crosslinking is synthetic rubber latex common in the art.Described styrene butadiene rubber latex includes the poly-styrene-butadiene latex of breast that in prior art, emulsion polymerisation process is directly prepared and the latex that will obtain after butylbenzene bulk latex prepared by any existing method；It is preferably the latex of emulsion polymerized styrene butadiene rubber in prior art.Wherein the solid content of nitrile rubber latex and the weight ratio of the solid content of styrene butadiene rubber latex are more than 20 80, less than or equal to 80 20；Preferred weight ratio is 30 70-80 20, more preferably 40 60-80 20.
In the above step (1), the cross-linking radiation of nitrile rubber latex picks up from according to international patent application WO01/40356(priority date December in 1999 3 days) disclosed in fully vulcanized powder rubber preparation method in the method for identical cross-linking radiation rubber latex.Nitrile rubber latex after the cross-linking radiation of gained is also with the rubber latex before unseasoned after irradiation in WO01/40356.
Specifically, crosslinking coagent can not be used at nitrile rubber latex, it is possible to 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 combination in any thereof.The example of described simple function group crosslinking coagent includes, but is not limited to: (methyl) 1-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-butanediol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, divinylbenzene；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 methacrylate.These crosslinking coagents can use in the way of in any combination, as long as they contribute to cross-linking under irradiation.
The addition of the above crosslinking coagent is generally 0.1 ~ 10% weight of dry glue weight in latex.It is preferably 0.5 ~ 9% weight, more preferably 0.7 ~ 7% weight.
The high-energy ray source of described irradiation is selected from cobalt source, ultraviolet or high-energy electron accelerator, preferably 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, by the nitrile rubber latex after this kind of cross-linking radiation with in modified rubber masterbatch obtained by coalescence after common uncrosslinked styrene butadiene rubber latex mixing, it is dispersed in the nitrile rubber particle dispersion phase in the continuous phase that uncrosslinked butylbenzene rubber is constituted, it may have the characteristic of the full vulcanised nitrile powdered rubber disclosed in WO01/40356.I.e. this kind has the rubber particles of cross-linked structure is that gel content reaches 60% weight or higher, and more excellent is 75% weight or higher rubber particles.Each microgranule that this kind has in the nitrile rubber particle of cross-linked structure is homogeneous, and the most single microgranule is the most all homogenizing, does not find the most homogeneous phenomenons such as layering, split-phase under the observation of existing microtechnique in microgranule.This has the nitrile rubber particle of cross-linked structure by being fixed by rubber particles particle diameter by corresponding nitrile rubber latex cross-linking radiation, and its particle diameter is consistent with the particle diameter of the latex particle in original nitrile rubber latex.The mean diameter of the rubber particles (latex particle) in original nitrile rubber latex is generally 50 ~ 200nm, preferably 70 ~ 200nm, more preferably 80 ~ 180nm.The mean diameter of the rubber particles with cross-linked structure after cross-linking radiation is the most also 50 ~ 200nm, preferably 70 ~ 200nm, more preferably 80 ~ 180nm.Owing to the method utilizing two kinds of latex mix homogeneously and coalescence, in nitrile rubber latex after cross-linking radiation, nitrile rubber particle is the most crosslinked, there is certain gel content, will not during latex coalescence adhesion or coalescence, and can be uniformly dispersed in uncrosslinked butadiene-styrene rubber, therefore, in the modified rubber masterbatch finally obtained, wherein as the mean diameter of the rubber particles with cross-linked structure of dispersion phase also at 50 ~ 200nm, it is preferably in the range of 70 ~ 200nm, more preferably 80 ~ 180nm.
The present invention is total to coalescence after being mixed by the nitrile rubber latex after uncrosslinked styrene butadiene rubber latex, cross-linking radiation according to described weight ratio, prepares described modified rubber masterbatch.In its preparation process, it is exactly conventional mixing apparatus at the mixing apparatus used by two kinds of rubber latex blend steps, selected from homogenizer of the prior art, kneader etc. mechanical mixing equipment.The coalescence condition of latex and equipment just use latex coalescence condition conventional in existing rubber industry and equipment.
The one oil-filled emulsion polymerized styrene butadiene rubber compositions of the present invention, includes blended modified rubber masterbatch of the present invention and oil-filled emulsion polymerized styrene butadiene rubber；Being in terms of 100 weight portions by oil-filled emulsion polymerized styrene butadiene rubber, modified rubber masterbatch is 1 ~ 70 part, preferably 1 ~ 40 part, more preferably 1 ~ 20 part.
Described oil-filled emulsion polymerized styrene butadiene rubber be according to the method that rubber industry in prior art is conventional emulsion polymerized styrene butadiene rubber is carried out oil-filled obtained by butadiene-styrene rubber, the oil filled is at least one in high aromatic oil, aromatic naphtha and naphthenic oil.Described emulsion polymerized styrene butadiene rubber is styrene/butadiene copolymers prepared by emulsion polymerisation process in prior art (newborn poly-method).Oil-filled emulsion polymerized styrene butadiene rubber can be by commercially available and obtain.
The preparation of oil-filled emulsion polymerized styrene butadiene rubber compositions of the present invention includes: first prepare described modified rubber masterbatch, the method of irradiation will be used to cross-link by nitrile rubber latex, the rubber particles in latex is made to have cross-linked structure, then by the nitrile rubber latex after cross-linking radiation with after mixing on conventional mixing apparatus with uncrosslinked styrene butadiene rubber latex, the coalescence method coalescence using rubber latex conventional obtains described modified rubber masterbatch；The most again using this modified rubber masterbatch as solid rubber master batch, using in rubber industry conventional method for mixing rubber and uncrosslinked oil-filled niggerhead together with other rubber usual auxiliaries, the most oil-filled emulsion polymerized styrene butadiene rubber block glue carries out mixing obtaining described oil-filled emulsion polymerized styrene butadiene rubber compositions.
Specifically, the preparation method of the oil-filled emulsion polymerized styrene butadiene rubber compositions of the present invention, comprise the following steps:
(1) by nitrile rubber latex through cross-linking radiation, the nitrile rubber particle in latex is made to have cross-linked structure, reach described gel content, and make the nitrile rubber particle in latex be fixed in described average particle size range, as at 50 ~ 200nm, it is preferably in the range of 70 ~ 200nm, more preferably 80 ~ 180nm；
(2) then by the described rubber particles with cross-linked structure and the mass ratio range of uncrosslinked rubber, the nitrile rubber latex taking above-mentioned cross-linking radiation carries out mixing to uniformly with uncrosslinked styrene butadiene rubber latex；Wherein the solid content of nitrile rubber latex and the weight ratio of the solid content of styrene butadiene rubber latex are more than 20 80, less than or equal to 80 20；Preferred weight ratio is 30 70-80 20, more preferably 40 60-80 20.
(3) mixing latex obtained as above 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 compositions obtaining oil-filled emulsion polymerized styrene butadiene rubber of described oil-filled emulsion polymerized styrene butadiene rubber；Being wherein in terms of 100 weight portions by oil-filled emulsion polymerized styrene butadiene rubber, modified rubber masterbatch is 1 ~ 70 part, preferably 1 ~ 40 part, more preferably 1 ~ 20 part.
Oil-filled emulsion polymerized styrene butadiene rubber compositions of the present invention also can be containing filler conventional in rubber processing.Following substances is to prepare the present invention oil-filled emulsion polymerized styrene butadiene rubber compositions elastomeric compound and the particularly suitable filler of vulcanizate, middle a kind of or its mixture such as including white carbon black, white carbon, metal-oxide, silicate, carbonate, sulfate, hydroxide, glass fibre or glass microballoon.At least one in wherein said metal-oxide preferential oxidation titanium, aluminium oxide, magnesium oxide, calcium oxide, Barium monoxide and zinc oxide etc..Can also be containing auxiliary agent conventional in the rubber processing sulfidations such as such as cross-linking agent, vulcanization accelerator, antioxidant, heat stabilizer, light stabilizer, ozone stabilizers, processing aid, plasticizer, softening agent, anti-blocking agent, foaming agent, dyestuff, pigment, wax, extender, organic acid, fire retardant and coupling agent in the rubber composition of the present invention.Adjuvant used consumption is conventional amount used, or is adjusted according to the requirement of practical situation.
The addition of above-described various auxiliary agent can modified rubber masterbatch as solid rubber master batch and oil-filled emulsion polymerized styrene butadiene rubber block glue mixing when add, i.e. added by the common calendering process of rubber, equipment can use method conventional in rubber industry and conventional mixing facilities, can make mill, banbury, single screw extrusion machine or double screw extruder etc..
The vulcanizate prepared by oil-filled emulsion polymerized styrene butadiene rubber compositions of the present invention, is vulcanizing system conventional for the emulsion polymerized styrene butadiene rubber compositions employing rubber materials of invention described above and technique to be carried out mixing and vulcanize the vulcanizate obtained.
The present invention oil-filled emulsion polymerized styrene butadiene rubber compositions prepares vulcanizate not to be affected by vulcanizing system, can vulcanize in conventional sulfur cross-linking system or non-sulfur cross-linking system.Vulcanizate prepared by rubber composition of the present invention is not affected by sulfuration process, can be with compression molding, injection sulfurization, sulfurizing pot vulcanization, individual vulcanizer sulfuration, the sulfuration of congruent melting salt, fluidized bed vulcanization, microwave vulcanization and high-energy ray sulfuration etc..
Prepared the mixing of vulcanizate by rubber composition of the present invention and sulfidation uses method conventional in rubber industry and conventional mixing facilities, mill, banbury, single screw extrusion machine or double screw extruder etc. can be made.
Specifically, the Micro of modified rubber masterbatch the most of the present invention is: described uncrosslinked butadiene-styrene rubber is continuous phase, and the described nitrile rubber particle with cross-linked structure is dispersion phase, and disperses with the fine particle size of 50 ~ 200nm.The vulcanizate that the oil-filled emulsion polymerized styrene butadiene rubber compositions obtained after mixing by modified rubber masterbatch and oil-filled emulsion polymerized styrene butadiene rubber prepares, the nitrile rubber particle with cross-linked structure still having in identical microstructure, i.e. modified rubber masterbatch is still dispersed in butadiene-styrene rubber matrix with the fine particle size of 50 ~ 200nm.
Modified rubber masterbatch in rubber composition of the present invention, owing to being made the rubber particles in nitrile rubber latex be fixed up with the particle diameter of original latex particle by cross-linking radiation, so the nitrile rubber particle of cross-linking radiation is as dispersion phase during coalescence, it is dispersed in the uncrosslinked butadiene-styrene rubber of continuous phase using the fine particle size of 50 ~ 200nm.This modified rubber masterbatch is mixing with oil-filled emulsion polymerized styrene butadiene rubber as rubber master batch, obtain oil-filled emulsion polymerized styrene butadiene rubber compositions, the vulcanizate prepared by this rubber composition again, the nitrile rubber particle with cross-linked structure still having in identical microstructure, i.e. modified rubber masterbatch is still dispersed in rubber matrix with the fine particle size of 50 ~ 200nm.So just having such microscopic pattern, the nitrile rubber particle with cross-linked structure just can be made to play nano effect, solve different rubber co-vulcanization problem present in the sulfidation simultaneously, while the vulcanizate anti-slippery of the rubber composition of the present invention, wearability can be improved together, resistance to rolling is also reduced.
Say by the vulcanite prepared by the rubber composition of the present invention, not only there is low resistance to rolling and excellent resistance to wet skidding performance, there is the wearability of excellence simultaneously, can use as high-performance car tread rubber further.
The rubber composition of the present invention and the preparation method of vulcanizate thereof are simple, and processing ease, process conditions are usual conditions, it is easy to extensively apply.
Specific implementation method:
Further describe the present invention by embodiment below, but the scope of the present invention is not restricted by the embodiments.The scope of the present invention is determined by appended claims.
(1) in embodiment, experimental data following instrument and equipment and assay method measure:
(1) resistance to rolling: use RSS-II rubber rolling resistance test machine (Beijing all things on earth Yifang Technology Co., Ltd.) to measure and roll power loss.
Under given load, the garden colyliform rubbery sample of constant motion performs relative motion with wheel hub close contact.The surface that rubbery sample contacts with wheel hub is deformed under pressure load, deforms and is a little gradually increased to intermediate point from coming into contact with；Zero a little it is gradually reduced to leaving again from intermediate point.Due to the viscous-elastic behaviour of various rubber compoundings, rubbery sample is coming into contact with making a concerted effort higher to leave during a recovery than intermediate point during a little deforming to intermediate point, and this power parallel with load forces is the power attenuation value (J/r) of rubbery sample.The resistance to rolling of this rubber compounding can be characterized accordingly.
Rolling resistance index (%): be radix by the rolling resistance measurement value of gum, the measured value of other modified adhesive accounts for the percent of gum rolling resistance measurement value and is rolling resistance index.
(2) anti-wear performance test: according to GB/T1689-1998, uses WML-76 type Akron abrasion machine to measure the wearing valve of vulcanizate.
Principle is: is rubbed under certain angle of inclination and certain load effect with emery wheel by sample, measures the wear volume of certain mileage.Wear volume is calculated as follows:
V sample abrasion volume, cm3
m1Quality before sample abrasion, g
m2Quality after sample abrasion, g
ρ sample density, cm3
Sample abrasion Index for Calculation:
Vs--the wear volume of standard recipe rubber.
Vt--the wear volume of modified rubber.
Abrasion index (%): be radix by the wear volume measured value of gum, the wear volume measured value of other modified adhesive accounts for the percent of gum measured value and is abrasion index.
(3) dynamic mechanical test (measuring wet and slippery): use the DMTAIV(dynamic mechanical analysis instrument that RheometricScientific company of the U.S. produces) test, experimental condition is 10Hz, 0.5% strain, 2 DEG C/min of programming rate.
Sizing material friction on wet structure is relevant with hysteresis loss, and the tan δ at generally using 0 DEG C characterizes wet-sliding resistant performance.Tan δ-value at 0 DEG C is the biggest, and tire hauling ability on wet road surface is the best.
Anti-slippery index (%): be radix by the anti-slippery measured value tan δ of gum, the anti-slippery measured value of other modified adhesive accounts for the percent of the anti-slippery measured value of gum and is anti-slippery index.
(4) mechanical property: measure by relevant standard-required.
(5) mensuration of the gel content of cross-linking radiation rubber latex: after NBR latex is carried out cross-linking radiation according to certain condition, it is spray-dried, obtain full vulcanised nitrile powdered rubber, then according to international patent application WO01/40356(priority date December in 1999 3 days) disclosed in method measure gel content and the mean diameter of full vulcanised nitrile powdered rubber, it is simply that the gel content of nitrile rubber latex and mean diameter after this cross-linking radiation.
(2) raw material used in embodiment and comparative example:
Emulsion polymerized styrene butadiene rubber latex SBR1502: solid content 20wt%, combinated styrene content content 23wt%, Mooney viscosity 50, rubber plant of Qilu Petrochemical Company produces.
Oil-filled emulsion polymerized styrene butadiene rubber: oil-filled block rubber, the trade mark: SBR1712, Sinopec Qilu Petrochemical branch company produces.
Nitrile rubber latex: the trade mark is NBR-26, Tian Yuan Chemical Co., Ltd. of Zhaodong City produces.
White carbon black: N234 Haitun Carbon Black Co., Ltd. Tianjin
Zinc oxide: commercially available
Stearic acid: commercially available
Sulfur: Linyi City Luo Zhuan chemical plant
Accelerator TBBS: the yellow amide of the N-tert-butyl group-2-[4-morpholinodithio time, chemical plant, Kingsoft, Zhengzhou
Calcium chloride: commercially available
Starch: commercially available
Glycerol: commercially available
5% carbolic acid liquid: commercially available
(3) latex coalescence method:
According to the recipe configuration coalescence agent solution of table 1, then according to join in this coalescence agent solution with the rubber latex of coalescence agent solution identical weight, after stirring 15 minutes, filter, wash, be dried, obtain solid rubber (rubber).
Table 1
| Calcium chloride | Starch | Glycerol | 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:
Banbury banbury (Britain's FarrelBridge Products) is carried out, volume 1.57L, rotor speed 80r min-1；Its process is: is individually added into oil-filled emulsion polymerized styrene butadiene rubber rubber or adds modified rubber masterbatch of the present invention, oil-filled emulsion polymerized styrene butadiene rubber rubber, white carbon black and other auxiliary agents (sulfur, accelerator, except) etc., putting down floating weight, mixing 3min.Binder removal (temperature is at 150～160 DEG C).
Two step process:
Lead to the thinnest in XK-160 type mill (Shanghai rubber machinery plant product) after above-mentioned one section of elastomeric compound addition sulfur, accelerator six times, bottom sheet afterwards.Then at 160 DEG C, press sulfurizing time T90Sulfuration, then makes standard batten by vulcanite print, carries out every Mechanics Performance Testing, and its result is as shown in table 3.The formula of elastomeric compound is shown in Table 2, and unit is parts by weight.
Embodiment 1 ~ 2
1, the preparation of modified rubber masterbatch:
(1) preparation of cross-linking radiation nitrile rubber latex:
In nitrile rubber latex (NBR-26) that solid content is 45%wt, after adding crosslinking coagent trimethylolpropane trimethacrylate by the 3%wt of NBR latex solid content, carry out cross-linking radiation, irradiation dose is 3.0Mrad, obtain the nitrile rubber latex of cross-linking radiation, mean diameter 100nm of the nitrile rubber particle of cross-linking radiation in latex, gel content is 91%.
(2) latex mixing and coalescence:
Joining in uncrosslinked emulsion polymerized styrene butadiene rubber latex SBR1502 by the nitrile rubber latex after cross-linking radiation according to certain solid content ratio, wherein nitrile rubber latex solid content and uncrosslinked emulsion polymerized styrene butadiene rubber latex solid content weight ratio after cross-linking radiation are 50:50.After agitator high speed stirs 15 minutes, obtain the modified rubber masterbatch A of solid-state according to aforementioned latex coalescence method coalescence.Wherein the composition of coalescence agent solution is with table 1.
2, prepared by oil-filled emulsion polymerized styrene butadiene rubber compositions and vulcanizate thereof:
Using above-mentioned gained modified rubber masterbatch A as rubber master batch, and add to other related auxiliaries block rubber (oil-filled emulsion polymerized styrene butadiene rubber SBR1712) is carried out mixing, obtaining elastomeric compound, its formula composition is shown in Table 2 in terms of parts by weight, and the preparation of elastomeric compound and vulcanization process are ditto described.Then vulcanite print being made standard batten, carry out every Mechanics Performance Testing, its result is as shown in table 3.
Embodiment 3 ~ 4
1, the preparation of modified rubber masterbatch:
The preparation of cross-linking radiation nitrile rubber latex and latex mixing and coalescence is carried out according to the method identical with embodiment 1, simply nitrile rubber latex solid content and uncrosslinked emulsion polymerized styrene butadiene rubber latex solid content weight ratio after cross-linking radiation become 80:20, obtain the modified rubber masterbatch B of solid-state.
2, prepared by oil-filled emulsion polymerized styrene butadiene rubber compositions and vulcanizate thereof:
Using above-mentioned gained modified rubber masterbatch B as rubber master batch, and add to other related auxiliaries block rubber (oil-filled emulsion polymerized styrene butadiene rubber SBR1712) is carried out mixing, obtaining elastomeric compound, its formula composition is shown in Table 2 in terms of parts by weight, and the preparation of elastomeric compound and vulcanization process are ditto described.Then vulcanite print being made standard batten, carry out every Mechanics Performance Testing, its result is as shown in table 3.
Comparative example 1
Simple oil-filled emulsion polymerized styrene butadiene rubber rubber (oil-filled emulsion polymerized styrene butadiene rubber SBR1712) is used with identical mixing and sulfuration process in embodiment 1 step 2, carries out mixing and sulfuration.The elastomeric compound formula composition of concrete rubber composition is listed in table 2.Cured properties is shown in Table 3.
Table 2 comparative example and Example formulations
| Title material | Comparative example 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| *SBR1500 | 100 | 100 | 100 | 100 | 100 |
| Modified rubber masterbatch A | —— | 11 | 16 | —— | —— |
| Modified rubber masterbatch B | —— | —— | —— | 7 | 10 |
| 3#White carbon black | 50 | 50 | 50 | 50 | 50 |
| Zinc oxide | 3 | 3 | 3 | 3 | 3 |
| Stearic acid | 1 | 1 | 1 | 1 | 1 |
| Sulfur | 1.75 | 1.75 | 1.75 | 1.75 | 1.75 |
| TBBS | 1 | 1 | 1 | 1 | 1 |
| Add up to | 156.75 | 156.75 | 156.75 | 156.75 | 156.75 |
Table 3 comparative example and the main performance of embodiment
As can be seen from Table 3, use the rolling resistance index of its vulcanizate of rubber composition of the present invention, abrasion index, anti-slippery index to be improved simultaneously, and effect is obvious.Its reason is exactly that the nitrile rubber particle with cross-linked structure after cross-linking radiation is dispersed in the butadiene-styrene rubber matrix of continuous phase with the fine particle size of 50 ~ 200nm.This characteristic of the rubber composition of the present invention is especially suitable for use as automobile tread rubber.Owing to three parameters of the rubber composition " Magic triangle " of the present invention are all improved, the specific requirement to these three parameter when can apply according to reality, carried other auxiliary agents of interpolation to regulate the overall synthetic performance of rubber composition, thus give and prepare the tread rubber of different performance demand and bring bigger regulation leeway.
Claims (13)
1. an oil-filled emulsion polymerized styrene butadiene rubber compositions, includes blended oil-filled emulsion polymerized styrene butadiene rubber and modified rubber masterbatch；Being in terms of 100 weight portions by oil-filled emulsion polymerized styrene butadiene 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 cross-linked structure being dispersed therein；The rubber particles wherein with cross-linked structure is nitrile rubber particle, and mean diameter is 50～200nm, and gel content is 60% weight or higher；The most uncrosslinked rubber is butadiene-styrene rubber；Described have the rubber particles of cross-linked structure with the weight ratio of uncrosslinked rubber more than 20 80, less than or equal to 80 20.
Oil-filled emulsion polymerized styrene butadiene rubber compositions the most according to claim 1, it is characterised in that gel content is 75% weight or higher.
Oil-filled emulsion polymerized styrene butadiene rubber compositions the most according to claim 1, it is characterised in that described in have the rubber particles of cross-linked structure be equal phase structure.
Oil-filled emulsion polymerized styrene butadiene rubber compositions the most according to claim 1, it is characterised in that described in there is cross-linked structure the mean diameter of rubber particles be 70～200nm.
Oil-filled emulsion polymerized styrene butadiene rubber compositions the most according to claim 1, it is characterised in that described in there is cross-linked structure the weight ratio of rubber particles and uncrosslinked rubber be 30 70-80 20.
Oil-filled emulsion polymerized styrene butadiene rubber compositions the most according to claim 5, it is characterised in that described in there is cross-linked structure the weight ratio of rubber particles and uncrosslinked rubber be 40 60-80 20.
7. according to the oil-filled emulsion polymerized styrene butadiene rubber compositions described in any one of claim 1～6, it is characterised in that described modified rubber masterbatch is obtained by coalescence after being mixed homogeneously with the component including the latex of the rubber particles with cross-linked structure by uncrosslinked rubber latex；The latex of the rubber particles wherein with cross-linked structure is the rubber latex obtained after cross-linking radiation.
8. an oil-filled emulsion polymerized styrene butadiene rubber compositions according to claim 7, it is characterised in that the preparation method of described modified rubber masterbatch, comprises the following steps:
(1) by nitrile rubber latex through cross-linking radiation, make the nitrile rubber particle in latex have cross-linked structure, reach described gel content, and make the nitrile rubber particle in latex be fixed in described average particle size range；
(2) then by the described rubber particles with cross-linked structure and the mass ratio range of described uncrosslinked rubber, the latex of the nitrile rubber latex and described uncrosslinked rubber that take above-mentioned cross-linking radiation carries out mixing to uniformly；
(3) mixing latex obtained as above is carried out common coalescence and obtain described modified rubber masterbatch.
Oil-filled emulsion polymerized styrene butadiene rubber compositions the most according to claim 1, it is characterised in that be in terms of 100 weight portions by oil-filled emulsion polymerized styrene butadiene rubber, described modified rubber masterbatch is 1～40 part.
Oil-filled emulsion polymerized styrene butadiene rubber compositions the most according to claim 9, it is characterised in that be in terms of 100 weight portions by oil-filled emulsion polymerized styrene butadiene rubber, described modified rubber masterbatch is 1～20 part.
11. 1 kinds of preparation methoies according to oil-filled emulsion polymerized styrene butadiene rubber compositions described in any one of claim 1～10, obtain oil-filled emulsion polymerized styrene butadiene rubber compositions including by described modified rubber masterbatch by described amount and described oil-filled emulsion polymerized styrene butadiene rubber are mixing.
12. according to the preparation method of emulsion polymerized styrene butadiene rubber compositions oil-filled described in claim 11, it is characterised in that the preparation method of described modified rubber masterbatch comprises the following steps:
(1) by nitrile rubber latex through cross-linking radiation, make the nitrile rubber particle in latex have cross-linked structure, reach described gel content, and make the nitrile rubber particle in latex be fixed in described average particle size range；
(2) then by the described rubber particles with cross-linked structure and the mass ratio range of described uncrosslinked rubber, the latex of the nitrile rubber latex and described uncrosslinked rubber that take above-mentioned cross-linking radiation carries out mixing to uniformly；
(3) mixing latex obtained as above is carried out common coalescence and obtain described modified rubber masterbatch.
13. 1 kinds of vulcanizates prepared according to oil-filled emulsion polymerized styrene butadiene rubber compositions described in any one of claim 1～10.
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| CN201210229516.4A CN103524810B (en) | 2012-07-03 | 2012-07-03 | A kind of modified rubber masterbatch and preparation method and a kind of preparation method and a vulcanized 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. |
| 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 |
| 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 |
| SG11201401845PA SG11201401845PA (en) | 2011-10-26 | 2012-10-26 | Modified rubber masterbatch, rubber composition prepared therewith and vulcanized rubber and preparation method thereof |
| 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 |
| 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 |
| 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 |
| 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 |
| PL12844199T PL2772513T3 (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 | |
| KR1020147013129A KR101698947B1 (en) | 2011-10-26 | 2012-10-26 | Modified rubber masterbatch, rubber composition prepared therewith and vulcanized rubber and preparation method thereof |
| EP12844199.5A EP2772513B1 (en) | 2011-10-26 | 2012-10-26 | Modified rubber masterbatch, rubber composition prepared therewith and vulcanized rubber and preparation method thereof |
| 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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