CN103524813A - Modified rubber master batch and preparation method thereof, oil-extended solution-polymerized styrene-butadiene rubber composition, and preparation method and vulcanized rubber thereof - Google Patents
Modified rubber master batch and preparation method thereof, oil-extended solution-polymerized styrene-butadiene rubber composition, and preparation method and vulcanized rubber thereof Download PDFInfo
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Abstract
The invention provides a modified rubber master batch and a preparation method thereof, an oil-extended solution-polymerized styrene-butadiene rubber composition, and a preparation method and a vulcanized rubber thereof. The modified rubber master batch comprises an uncrosslinked rubber and crosslinked-structure nitrile-butadiene rubber particles dispersed in the uncrosslinked rubber, wherein the average particle size of the nitrile-butadiene rubber particles is 50-200 nm; the gel content is 60 wt% or higher; the uncrosslinked rubber is styrene-butadiene rubber; and the weight ratio of the crosslinked nitrile-butadiene rubber particles to the uncrosslinked rubber is more than 20:80 and less than or equal to 80:20. The oil-extended solution-polymerized styrene-butadiene rubber composition comprises 100 parts by weight of modified rubber master batch and 1-70 parts by weight of oil-extended solution-polymerized styrene-butadiene rubber which are blended. The vulcanized rubber of the oil-extended solution-polymerized styrene-butadiene rubber composition has the advantages of higher slippery resistance, higher abrasion resistance and lower rolling resistance, and can be used for preparing a 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 can reduce the pressure of CO2 emissions and alleviation petroleum resources.Vehicle fuel consume is except being subject to automobile self design factor affects, tire drag is also one of important factor, tire drag fuel oil consumption accounts for 14～17% of vehicle fuel consume, and the every reduction by 10% of tire drag, can reduce fuel oil consumption 1～2% conventionally.Therefore, reduce tire drag and be used as one of important measures that reduce fuel oil consumption.
But run into very stubborn problem in reducing tyre stock (being mainly tread rubber) rolling resistance research.Be rolling resistance, wet and slippery performance, conflicting so-called " Magic triangle " problem of wear resisting property.Simply increase tenderizer consumption, can improve the anti-slippery of tire, but its wear resistance reduces and rolling resistance increases.The consumption that improves reinforced filling (carbon black or white carbon black), can reduce rolling resistance to a certain extent, but makes reinforced filling in sizing material, be difficult to be uniformly dispersed, and anti-slippery is reduced.The consumption that strengthens vulcanizing agent, improves cross-linking density, the same with the effect that increases reinforced filling consumption, reduces rolling resistance and makes anti-slippery variation simultaneously.In order to realize the balance of three aspects: performance, except Design of Tire Structure is optimized, also sizing material (take tread rubber as main) formula has been carried out to research extensively and profoundly both at home and abroad.Synthesize on the one hand applicable 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.), set about on the other hand seeking to have properties-correcting agent and the practical formulation of better over-all properties.Some progress in formulating, have been obtained, 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 in industrial realization; Its shortcoming is that in the time of need to using more silane coupling agent and refining glue, machine utilization is large, and the wear resistance of cross-linked rubber is also undesirable.
Rubber gels prepared by the Chemical Crosslinking Methods such as employing direct polymerization method or superoxide, when formula is suitable, can improve the performance of cross-linked rubber.For example, in European patent EP 405216 and German patent DE 4220563, report respectively the wear resistance and the fatigue temperature rise that in rubber combination, add respectively chloroprene rubber gel and cis-1,4-polybutadiene rubber gel to improve cross-linked rubber, but lost moisture-proof slip.
So a lot of patents start to adopt the rubber gels of modification to improve the performance of vulcanization of rubber glue, suitable fourth and styrene-butadiene rubber(SBR) gel (latex particle swelling index 4～5 in gel that for example US Patent No. 6184296 is used through surface modification, 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.
The styrene-butadiene rubber(SBR) gel of US Patent No. 6207757 use 1-chloro-4-methyl-benzene modifications has reached the effect that reduces NR formula system cross-linked rubber rolling resistance, has improved hauling ability and the wearing quality of tire simultaneously.
US Patent No. 6242534 containing carboxyl and amino styrene-butadiene rubber(SBR) gel in the lump for NR formula system, not only reduced the rolling resistance of system cross-linked rubber, improved anti-slippery, and obviously improved stress at definite elongation.
European patent EP 1431075 use styrene-butadiene rubber(SBR) gels and plasticized starch improve the performance of the white carbon black system of styrene-butadiene rubber(SBR) (SBR) and cis-1,4-polybutadiene rubber (BR) use, and result wear resistance is improved, and rolling resistance reduces, and the proportion of cross-linked rubber is also less.
US Patent No. 6699935 use modification by copolymerization styrene-butadiene rubber(SBR) gels make modified styrene butadiene rubber formula system have low-rolling-resistance and have outstanding anti-slippery and wear resistance concurrently.
The rubber gels that above-mentioned patent documentation is mentioned all adopts Chemical Crosslinking Methods crosslinked, this method need to be used cross-linking monomer and energy consumption that price is higher larger, 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 improve when importantly the rubber gels obtaining after crosslinked just can must be reached to rolling resistance, anti-slippery and wear resistance after carrying out modification.Although there is the particle diameter of report rubber gels in these patents, but when these rubber gels are distributed in cross-linked rubber, can reach the dispersion of initial stage particle diameter, can really bring into play the modifying function of nano-rubber gel, in any patent, not report.
Summary of the invention
For the problem of prior art, one of object of the present invention is to provide a kind of modified rubber masterbatch, also can be described as modified rubber component.The cross-linked rubber of the oil-filled solution polymerized butadiene styrene rubber composition of being prepared by this masterbatch not only has lower rolling resistance and excellent moisture-proof slip, has excellent wear resistance simultaneously, can be used as good automobile tread rubber and uses.
Another object of the present invention is to provide the method for making of described modified rubber masterbatch.
A further object of the present invention is to provide the oil-filled solution polymerized butadiene styrene rubber composition that includes described modified rubber masterbatch.
The 4th object of the present invention is to provide the preparation method of described rubber combination.
The 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 WO 01/40356(priority date on December 3rd, 1999 that the applicant submitted on September 18th, 2000) and the applicant International Patent Application WO 01/98395(priority date on June 15th, 2000 of submitting June 15 calendar year 2001) in a kind of fully vulcanized powder rubber is disclosed.Propose, after employing irradiance method cross-linked rubber latex, because cross-linking radiation makes the latex particle (rubber particles) in rubber latex, to reach certain gel content, the particle diameter of its latex particle is fixed up, not can after drying process in adhesion or coalescence.Contriver finds under study for action, and the paracril latex after this cross-linking radiation and uncrosslinked styrene butadiene rubber latex are mixed, and is total to afterwards the rubber combination that coalescence obtains a kind of crosslinked particle modified styrene-butadiene rubber(SBR) of paracril.Wherein due to can adhesion and coalescence between the paracril particle with crosslinking structure of cross-linking radiation, and the latex particle of common uncrosslinked styrene butadiene rubber latex meeting coalescence, therefore have in the rubber matrix that the paracril particle of crosslinking structure just can obtain with the particle size dispersion of its progenitor after uncrosslinked styrene butadiene rubber latex coalescence, and the degree that is uniformly dispersed than directly by much better in fully vulcanized powder rubber and the mixing mixture obtaining of rubber.Obtain thus a kind of modified rubber masterbatch.
Using this modified rubber masterbatch as solid rubber master batch, then by blending technologies such as Banbury mixer, end runner mill, screw extrusion presss, obtain rubber unvulcanizate with the uncrosslinked oil-filled solution polymerized butadiene styrene rubber of bulk.The rubber unvulcanizate so obtaining, the rubber particles with crosslinking structure that also can guarantee cross-linking radiation reaches the dispersion situation in described particle size range in uncrosslinked oil-filled solution polymerized butadiene styrene rubber matrix.In this composition, add again conventional rubber processing aids mixing, sulfuration after obtain cross-linked rubber.Because the paracril particle after cross-linking radiation has had crosslinking structure, do not need to consider the sulfuration of disperse phase, so just solved the covulcanization problem of the composition of different rubber compositions; Simultaneously the paracril particle with crosslinking structure of cross-linking radiation is still evenly dispersed in and take in the vulcanized rubber that oil-filled solution polymerized butadiene styrene rubber is matrix with very little initial size very much, so the anti-slippery of the cross-linked rubber finally obtaining and wear resistance can obtain raising simultaneously, can maintain the low-rolling-resistance performance that oil-filled solution polymerized butadiene styrene rubber itself has simultaneously and not be 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.Described have the rubber particles of crosslinking structure and the weight ratio of uncrosslinked rubber is greater than 20 ︰ 80, is 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 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, the styrene/butadiene copolymers that prepared by emulsion polymerisation process (the poly-method of breast).
The method for making of modified rubber masterbatch of the present invention, be comprise uncrosslinked rubber latex is mixed with the component of latex with the rubber particles of crosslinking structure after coalescence and obtaining: the rubber latex of the latex of rubber particles wherein with crosslinking structure for obtaining after cross-linking radiation.
Specifically, the method for making of described modified rubber masterbatch, comprises the following steps:
(1) by paracril latex process cross-linking radiation, make the paracril particle in latex there is crosslinking structure, reach described gel content, and the paracril particle in latex is fixed in described average particle size range;
(2), then by the described weight ratio with rubber particles and the described uncrosslinked rubber of crosslinking structure, get the paracril latex of above-mentioned cross-linking radiation and the latex of described uncrosslinked rubber is mixed to evenly;
(3) above gained mixing latex is carried out to 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 not cross-linking radiation is synthetic rubber latex common in prior art.Described styrene butadiene rubber latex comprise emulsion polymerisation process in prior art directly the poly-styrene-butadiene latex of breast of preparation and any existing method prepare by the latex obtaining after the block latex of butylbenzene; 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, more preferably 40 ︰ 60-80 ︰ 20.
The cross-linking radiation of paracril latex picked up from according to International Patent Application WO 01/40356(priority date on December 3rd, 1999 in the above step (1)) method of identical cross-linking radiation rubber latex in the preparation method of disclosed fully vulcanized powder rubber.Paracril latex after the cross-linking radiation of gained is also with the rubber latex before not dry after irradiation in WO01/40356.
Specifically, at paracril latex, crosslinking coagent can be do not used, also crosslinking coagent can be used.Crosslinking coagent used is selected from simple function group crosslinking coagent ,Er functional group crosslinking coagent, 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 be used in the mode of arbitrary combination, crosslinked as long as they contribute 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, more preferably 0.7 ~ 7% weight.
The energetic ray source that described irradiation is used 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, irradiation dose should make the rubber particles gel content after rubber latex cross-linking radiation reach 60% weight or higher, preferably 75% weight or higher, more preferably 80% weight or higher.
Thus, in the modified rubber masterbatch that mixes rear coalescence by the paracril latex after this kind of cross-linking radiation with common uncrosslinked styrene butadiene rubber latex and obtain, be dispersed in the paracril particle disperse phase in the external phase that uncrosslinked butylbenzene rubber forms, also there is the characteristic of the disclosed full sulfuration powder nbr rubber of WO01/40356.To have the rubber particles of crosslinking structure be that gel content reaches 60% weight or higher to this kind, 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 single particulate is all homogeneous on forming, and does not find layering, minute equates the phenomenon of uneven phase under the observation of existing microtechnique in particulate.This paracril particle with crosslinking structure is by by corresponding paracril latex cross-linking radiation and rubber particles particle diameter is fixing, and its particle diameter is consistent with the particle diameter of 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 of the rubber particles with crosslinking structure after cross-linking radiation is also generally 50 ~ 200nm, is preferably 70 ~ 200nm, more preferably 80 ~ 180nm.Owing to utilizing two kinds of latex to mix and coalescence in the method, in paracril latex after cross-linking radiation, paracril particle is crosslinked, there is certain gel content, can be in latex coalescence process adhesion or coalescence, and can in uncrosslinked styrene-butadiene rubber(SBR), be uniformly dispersed, therefore, in the modified rubber masterbatch finally obtaining, wherein as the median size of the rubber particles with crosslinking structure of disperse phase also at 50 ~ 200nm, be preferably 70 ~ 200nm, more preferably in the scope of 80 ~ 180nm.
The present invention is total to coalescence after the paracril latex after uncrosslinked styrene butadiene rubber latex, cross-linking radiation being mixed according to described weight ratio, prepares described modified rubber masterbatch.In its preparation process, at two kinds of rubber latex mixing step mixing equipment used, be exactly conventional mixing equipment, be selected from homogenizer of the prior art, kneader etc. mechanical mixing equipment.The coalescence condition of latex and equipment just adopt latex coalescence condition and equipment conventional in existing rubber industry.
A kind of oil-filled solution polymerized butadiene styrene rubber composition of the present invention, includes modified rubber masterbatch of the present invention and the oil-filled solution polymerized butadiene styrene rubber of blend; Take oil-filled solution polymerized butadiene styrene rubber as 100 weight parts, and modified rubber masterbatch is 1 ~ 70 part, is preferably 1 ~ 40 part, more preferably 1 ~ 30 part, and most preferably 5 ~ 15 parts.
Described oil-filled solution polymerized butadiene styrene rubber is, according to the conventional method of rubber industry in prior art, solution polymerized butadiene styrene rubber is carried out to styrene-butadiene rubber(SBR) oil-filled and that obtain, and the oil filling is at least one in high aromatic oil, aromatic hydrocarbon oil and naphthenic oil.Described solution polymerized butadiene styrene rubber is styrene/butadiene copolymers prepared by solution polymerization process in prior art (containing intermingle with method).Oil-filled solution polymerized butadiene styrene rubber can pass through commercially available obtaining.
The preparation of oil-filled solution polymerized butadiene styrene rubber composition of the present invention comprises: first prepare described modified rubber masterbatch, being about to paracril latex adopts the method for irradiation crosslinked, make the rubber particles in latex there is crosslinking structure, then, after mixing on conventional mixing equipment by the paracril latex after cross-linking radiation with uncrosslinked styrene butadiene rubber latex, the conventional coalescence method coalescence of employing rubber latex obtains described modified rubber masterbatch; And then using this modified rubber masterbatch as solid rubber master batch, adopt method for mixing rubber conventional in rubber industry and the uncrosslinked oil-filled rubber of bulk together with other rubber usual auxiliaries, uncrosslinked oil-filled solution polymerized butadiene styrene rubber piece glue carries out the mixing described oil-filled solution polymerized butadiene styrene rubber composition that obtains.
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 process cross-linking radiation, make the paracril particle in latex there is crosslinking structure, reach described gel content, and the paracril particle in latex is fixed in described average particle size range, as at 50 ~ 200nm, be preferably 70 ~ 200nm, more preferably in the scope of 80 ~ 180nm;
(2), then by the described weight ratio with rubber particles and the uncrosslinked rubber of crosslinking structure, get the paracril latex of above-mentioned cross-linking radiation and uncrosslinked described styrene butadiene rubber latex and be mixed to evenly; Wherein the weight ratio of the solid content of the solid content of paracril latex and 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, more preferably 40 ︰ 60-80 ︰ 20.
(3) above gained mixing latex is carried out to common coalescence and obtain described modified rubber masterbatch;
(4) by above-mentioned gained modified rubber masterbatch by described amount and the mixing composition that obtains oil-filled solution polymerized butadiene styrene rubber of described oil-filled solution polymerized butadiene styrene rubber; Wherein take oil-filled solution polymerized butadiene styrene rubber as 100 weight parts, and modified rubber masterbatch is 1 ~ 70 part, is preferably 1 ~ 40 part, more preferably 1 ~ 30 part, and most preferably 5 ~ 15 parts.
Oil-filled solution polymerized butadiene styrene rubber composition of the present invention also can contain weighting agent conventional in rubber processing.Following substances is the suitable especially weighting agent of preparation the present invention's oil-filled solution polymerized butadiene styrene rubber composition rubber unvulcanizate and cross-linked rubber, comprises a kind of or its mixture in carbon black, white carbon black, metal oxide, silicate, carbonate, vitriol, oxyhydroxide, glass fibre or glass microballon etc.At least one in wherein said metal oxide preferential oxidation titanium, aluminum oxide, magnesium oxide, calcium oxide, barium oxide and zinc oxide etc.In rubber combination of the present invention, can also contain conventional auxiliary agent in Rubber processing sulfidations such as linking agent, vulcanization accelerator, antioxidant, thermo-stabilizer, photostabilizer, ozone stablizer, processing aid, softening agent, tenderizer, anti blocking agent, whipping agent, dyestuff, pigment, wax, extender, organic acid, fire retardant and coupling agent.Adjuvant used consumption is conventional amount used, or adjusts according to the requirement of practical situation.
Adding of above-described various auxiliary agents can add in mixing as solid rubber master batch and oil-filled solution polymerized butadiene styrene rubber piece glue at modified rubber masterbatch, by the common calendering process of rubber, add, 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 of being prepared by oil-filled solution polymerized butadiene styrene rubber composition of the present invention is to adopt vulcanization system and the technique that rubber materials is conventional to carry out cross-linked rubber mixing and that sulfuration obtains above-described oil-filled solution polymerized butadiene styrene rubber composition of the present invention.
The oil-filled solution polymerized butadiene styrene rubber composition of the present invention is prepared the impact that cross-linked rubber is not subject to vulcanization system, can in conventional sulfur cross-linking system or non-sulfur cross-linking system, vulcanize.Cross-linked rubber prepared by rubber combination of the present invention is not subject to 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.
Mixing and the sulfidation of being prepared cross-linked rubber by rubber combination of the present invention adopts conventional method and conventional mixing facilities in rubber industry, can make mill, Banbury mixer, single screw extrusion machine or twin screw extruder etc.
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 with the tiny particle size dispersion of 50 ~ 200nm.The cross-linked rubber that the oil-filled solution polymerized butadiene styrene rubber composition being obtained after mixing by modified rubber masterbatch and oil-filled solution polymerized butadiene styrene rubber makes, still there is identical microtexture, the paracril particle with crosslinking structure in modified rubber masterbatch still with the tiny particle size dispersion of 50 ~ 200nm in styrene-butadiene rubber(SBR) matrix.
Modified rubber masterbatch in rubber combination of the present invention, because the particle diameter that makes rubber particles in paracril latex with original latex particle by cross-linking radiation is fixed up, so the paracril particle of cross-linking radiation is as disperse phase in coalescence process, the tiny particle diameter of 50 ~ 200nm of usining is dispersed in the uncrosslinked styrene-butadiene rubber(SBR) as external phase.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 being made by this rubber combination again, still there is identical microtexture, the paracril particle with crosslinking structure in modified rubber masterbatch still with the tiny particle size dispersion of 50 ~ 200nm in styrene-butadiene rubber(SBR) matrix.So just there is such microscopic pattern, just can make to have the paracril particle performance nano effect of crosslinking structure, solved the covulcanization problem that different rubber exists in sulfidation simultaneously, make the cross-linked rubber anti-slippery of rubber combination of the present invention and wear resistance can obtain raising, and maintain low rolling resistance performance and be not affected substantially simultaneously.
Say further not only there is lower rolling resistance and excellent moisture-proof slip by the prepared vulcanized rubber of rubber combination of the present invention, there is excellent wear resistance simultaneously, can be used as high-performing car tread rubber and use.Because three parameters of rubber combination of the present invention " grinding triangular " are all very excellent, the specific requirement to these three parameters in the time of can be according to practical application, carried and added the overall synthetic performance that other auxiliary agents regulate rubber combination, thereby bring larger adjusting leeway to the tread rubber of preparing different performance demand.
The preparation method of rubber combination of the present invention and cross-linked rubber thereof is simple, processing ease, and processing condition are usual conditions, are easy to widespread use.
Specific implementation method:
With embodiment, further described the present invention below, but scope of the present invention is not subject to the restriction of these embodiment.Scope of the present invention is determined by accompanying claims.
(1) in embodiment, experimental data is measured with following plant and instrument and measuring method:
(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, garden colyliform rubbery sample and the wheel hub close contact of constant motion are done relative movement.The surface that rubbery sample contacts with wheel hub produces distortion under pressure load, and distortion increases to intermediate point gradually from starting point of contact; From intermediate point, to leaving, be a little gradually reduced to zero again.Due to the viscous-elastic behaviour of various rubber compoundings, rubbery sample start point of contact between intermediate point deformation phases make a concerted effort by than intermediate point to the height with joint efforts that leaves a recovery period, this power parallel with load forces is the power loss value (J/r) of rubbery sample.Can characterize the rolling resistance of this rubber compounding 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, adopt 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 abrasion volume of certain mileage.Abrasion volume calculation is 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 abrasion volume of standard recipe rubber.
V
t--the abrasion volume of modified rubber.
Wear index (%): be radix by the abrasion stereometry value of gum, the percentage ratio that the abrasion stereometry value of other modified adhesive accounts for gum measured value is wear index.
(3) dynamic properties test (measuring wet and slippery): the DMTA IV(dynamic mechanical analysis instrument that adopts U.S. Rheometric Scientific company to produce) test, test conditions is 10Hz, 0.5% strain, 2 ℃/min of heat-up rate.
Sizing material is relevant with hysteresis loss in wet lip-deep friction, conventionally adopts the tan δ at 0 ℃ to characterize wet-sliding resistant performance.Tan δ value at 0 ℃ 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: nitrile rubber is carried out after cross-linking radiation according to certain condition, spray dry, obtain entirely vulcanizing powder nbr rubber, then according to International Patent Application WO 01/40356(priority date on December 3rd, 1999) in disclosed method measure gel content and the median size of full sulfuration powder nbr rubber, be exactly gel content and the median size of paracril latex after this cross-linking radiation.
(2) raw material used in embodiment and comparative example:
Emulsion polymerized styrene butadiene rubber latex SBR1502: solid content 20wt%, combined styrene content 23wt%, rubber plant of mooney viscosity 50， 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, Zhaodong City Tian Yuan Chemical Co., Ltd. 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:
Recipe configuration coalescence agent solution according to table 1, then joins in this coalescence agent solution according to the rubber latex with coalescence agent solution identical weight, stirs after 15 minutes, filters, washs, is dried, and obtains 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: in table 1, be parts by weight
(4) preparation of rubber unvulcanizate and the method for sulfuration:
One segment process:
In Banbury Banbury mixer (Britain Farrel Bridge company product), carry out 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 ℃).
Two step process:
After above-mentioned one section of rubber unvulcanizate is added to sulphur, promotor, in XK-160 type mill (rubber machinery plant, Shanghai product), go up thin-pass six times, descend sheet afterwards.Then at 160 ℃, press sulfurizing time T
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:
In the paracril latex that is 45%wt at solid content (NBR-26), by the 3%wt of nitrile rubber solid content, add after crosslinking coagent Viscoat 295, 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 mixes and coalescence:
Paracril latex after cross-linking radiation is joined in uncrosslinked emulsion polymerized styrene butadiene rubber latex SBR1502 according to certain solid content ratio, and wherein the paracril latex solid content after cross-linking radiation and uncrosslinked emulsion polymerized styrene butadiene rubber latex solid content weight ratio are 80:20.Agitator high speed stirred after 15 minutes, according to aforementioned latex coalescence method coalescence, obtained solid-state modified rubber masterbatch.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 auxiliary agent relevant to other add in block rubber (oil-filled solution polymerized butadiene styrene rubber 2535L), carry out mixing, obtain rubber unvulcanizate, its formula forms in parts by weight in Table 2, the preparation of rubber unvulcanizate and vulcanization process ditto described in.Then vulcanized rubber print is made to standard batten, carry out every Mechanics Performance Testing, its result is as shown in table 3.
Comparative example 1
Pure oil-filled solution polymerized butadiene styrene rubber rubber (oil-filled solution polymerized butadiene styrene rubber 2535L) is adopted with identical mixing and sulfuration process in embodiment 1 step 2, carry out mixing and sulfuration.The rubber unvulcanizate formula of concrete rubber combination forms 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/℃ | 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 | ___________ |
[0110]as can be seen from Table 3, adopt wear index, the anti-slippery index of oil-filled its cross-linked rubber of solution polymerized butadiene styrene rubber composition prepared by modified rubber masterbatch of the present invention to improve, its reason is exactly the paracril particle with crosslinking structure after cross-linking radiation with the tiny particle size dispersion of 50 ~ 200nm in the oil-filled solution polymerized butadiene styrene rubber matrix of external phase simultaneously.This specific character 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 in the situation that maintained lower rolling resistance, can also reduce wear index, improve anti-slippery index, thereby the wear resistance of cross-linked rubber and anti-slippery are improved simultaneously.Therefore the specific requirement to these three parameters in the time of can be according to practical application, carried and added the overall synthetic performance that other auxiliary agents regulate rubber combination, thereby bring larger adjusting leeway to the tread rubber of preparing different performance demand.
Claims (11)
1. a modified rubber masterbatch, comprises uncrosslinked rubber and is dispersed in the rubber particles with crosslinking structure 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, is preferably 75% weight or higher; Wherein uncrosslinked rubber is styrene-butadiene rubber(SBR); Described have the rubber particles of crosslinking structure and the weight ratio of uncrosslinked rubber is greater than 20 ︰ 80, is less than or equal to 80 ︰ 20.
2. modified rubber masterbatch according to claim 1, the rubber particles described in it is characterized in that with crosslinking structure is equal phase structure.
3. modified rubber masterbatch according to claim 1, the median size described in it is characterized in that with the rubber particles of crosslinking structure is 70 ~ 200nm.
4. modified rubber masterbatch according to claim 1, described in it is characterized in that, having the rubber particles of crosslinking structure and the weight ratio of uncrosslinked rubber is 30 ︰ 70-80 ︰ 20, is preferably 40 ︰ 60-80 ︰ 20.
5. according to the modified rubber masterbatch described in any one of claim 1～4, it is characterized in that described modified rubber masterbatch by comprise uncrosslinked rubber latex is mixed with the component of latex with the rubber particles of crosslinking structure after coalescence and obtaining; The latex wherein with the rubber particles of crosslinking structure is the rubber latex obtaining after cross-linking radiation.
6. according to a method for making for the modified rubber masterbatch described in any one of claim 1 ~ 5, comprise the following steps:
(1) by paracril latex process cross-linking radiation, make the paracril particle in latex there is crosslinking structure, reach described gel content, and the paracril particle in latex is fixed in described average particle size range;
(2), then by the described weight ratio with rubber particles and the described uncrosslinked rubber of crosslinking structure, get the paracril latex of above-mentioned cross-linking radiation and the latex of described uncrosslinked rubber is mixed to evenly;
(3) above gained mixing latex is carried out to common coalescence and obtain described modified rubber masterbatch.
7. an oil-filled solution polymerized butadiene styrene rubber composition, includes the modified rubber masterbatch described in the oil-filled solution polymerized butadiene styrene rubber of blend and any one of claim 1 ~ 5; Take oil-filled solution polymerized butadiene styrene rubber as 100 weight parts, and described modified rubber masterbatch is 1 ~ 70 part.
8. composition according to claim 7, is characterized in that take that oil-filled solution polymerized butadiene styrene rubber is as 100 weight parts, and described modified rubber masterbatch is 1 ~ 40 part, is preferably 1 ~ 30 part.
9. according to a preparation method for oil-filled solution polymerized butadiene styrene rubber composition described in claim 7 or 8, comprise by described amount described modified rubber masterbatch and described oil-filled solution polymerized butadiene styrene rubber is mixing obtains oil-filled solution polymerized butadiene styrene rubber composition.
10. the preparation method of oil-filled solution polymerized butadiene styrene rubber composition according to claim 9, is characterized in that the preparation method of described modified rubber masterbatch comprises the following steps:
(1) by paracril latex process cross-linking radiation, make the paracril particle in latex there is crosslinking structure, reach described gel content, and the paracril particle in latex is fixed in described average particle size range;
(2), then by the described weight ratio with rubber particles and the described uncrosslinked rubber of crosslinking structure, get the paracril latex of above-mentioned cross-linking radiation and the latex of described uncrosslinked rubber is mixed to evenly;
(3) above gained mixing latex is carried out to common coalescence and obtain described modified rubber masterbatch.
11. 1 kinds according to cross-linked rubber that described in claim 7 or 8 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 |
| 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 |
| KR1020147013129A KR101698947B1 (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 |
| 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 |
| IN3426DEN2014 IN2014DN03426A (en) | 2011-10-26 | 2012-10-26 | |
| 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 |
| 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 |
| MX2014005050A MX343657B (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 |
| 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 |
| EP12844199.5A EP2772513B1 (en) | 2011-10-26 | 2012-10-26 | Modified rubber masterbatch, rubber composition prepared therewith and vulcanized rubber and preparation method thereof |
| 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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