CN103073760A - Emulsion polymerized styrene-butadiene rubber composition, preparation method thereof, and vulcanized rubber thereof - Google Patents
Emulsion polymerized styrene-butadiene rubber composition, preparation method thereof, and vulcanized rubber thereof Download PDFInfo
- Publication number
- CN103073760A CN103073760A CN2011103306049A CN201110330604A CN103073760A CN 103073760 A CN103073760 A CN 103073760A CN 2011103306049 A CN2011103306049 A CN 2011103306049A CN 201110330604 A CN201110330604 A CN 201110330604A CN 103073760 A CN103073760 A CN 103073760A
- Authority
- CN
- China
- Prior art keywords
- rubber
- latex
- emulsion polymerized
- styrene butadiene
- polymerized styrene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Abstract
The invention provides an emulsion polymerized styrene-butadiene rubber composition, a preparation method thereof, and a vulcanized rubber thereof. The emulsion polymerized styrene-butadiene rubber composition comprises blended modified rubber component and emulsion polymerized styrene-butadiene rubber. Calculated according to the weight of emulsion polymerized styrene-butadiene rubber as 100 parts, the composition comprises 1-70 parts of the modified rubber component. The modified rubber component comprises uncrosslinked rubber and rubber particles with crosslinked structures, which are dispersed in the uncrosslinked rubber. The rubber particles with crosslinked structures are nitrile rubber particles with an average particle size of 50-200nm and a gel content of 60wt% or higher. The uncrosslinked rubber is styrene-butadiene rubber. A weight ratio of the rubber particles with crosslinked structures to the uncrosslinked rubber is 80:20-30:70. The rolling resistance, wet skid performance and wear resistance of the vulcanized rubber of the emulsion styrene-butadiene rubber composition can be improved. The vulcanized rubber can be used for preparing high-efficiency automobile tread rubber.
Description
Technical field
The present invention relates to rubber materials, say further, relate to a kind of emulsion polymerized styrene butadiene rubber composition and method of making the same by the modified rubber component modification and its cross-linked rubber.
Background technology
Automobile more and more becomes the indispensable instrument of the modern life, and the used power of automobile comes from oil substantially, petroleum resources are limited, and the simultaneously fast development of automotive industry also faces Carbon emission decrement pressure, how to reduce vehicle fuel consume and becomes more and more urgent.Reduce fuel oil consumes, and not only can reduce the automobilism cost, and can reduce the pressure of CO2 emissions and alleviation petroleum resources.Vehicle fuel consume is except being subjected to automobile self design factor affects, tire drag also is one of important factor, the tire drag fuel oil consumption accounts for 14～17% of vehicle fuel consume, and the every reduction by 10% of tire drag can consume 1～2% by reduce fuel oil usually.Therefore, reduce tire drag and be used as one of important measures of reduce fuel oil consumption.
But in reducing tyre stock (mainly being tread rubber) rolling resistance research, run into very stubborn problem.Be rolling resistance, wet and slippery performance, conflicting so-called " Magic triangle " problem of wear resisting property.Simply increase the tenderizer consumption, can improve the anti-slippery of tire, but its wear resistance reduces and rolling resistance increases.Improve the consumption of reinforced filling (carbon black or white carbon black), can reduce to a certain extent rolling resistance, but make reinforced filling in sizing material, be difficult to be uniformly dispersed, and anti-slippery is reduced.Strengthen the consumption of vulcanizing agent, namely improve cross-linking density, the same with the effect that increases the reinforced filling consumption, reduce rolling resistance and make simultaneously the anti-slippery variation.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) prescription has been carried out research extensively and profoundly both at home and abroad.Synthesize on the one hand applicable rubber raw materials (such 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.), properties-correcting agent and the practical formulation of setting about on the other hand seeking to have better over-all properties.Some progress in formulating, have been obtained, more representationally be: solution polymerized butadiene styrene rubber (SSBR) etc. and carbon black and white carbon black and with or reciprocal (counter-rotating) carbon black system, the system characteristics are that main formula is substantially constant, just different on reinforced filling, easily in industrial realization; Its shortcoming is that machine utilization is large when needing to use more silane coupling agent and refining glue, and the wear resistance of cross-linked rubber is also undesirable.
Adopt the rubber gels of the Chemical Crosslinking Methods preparations such as direct polymerization method or superoxide when prescription is suitable, can improve the performance of cross-linked rubber.For example, reported respectively in European patent EP 405216 and the German patent DE 4220563 in rubber combination, to add respectively wear resistance and the fatigue temperature rise that chloroprene rubber gel and cis-1,4-polybutadiene rubber gel improve cross-linked rubber, but lost the moisture-proof slip.
So a lot of patents begin to adopt the rubber gels of modification to improve the performance of vulcanization of rubber glue, for example US Patent No. 6184296 is used suitable fourth and styrene-butadiene rubber(SBR) gel (the latex particle swelling index 4～5 in the gel of process 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 the US Patent No. 6133364,1-chloro-4-methyl-benzene is grafted on the styrene-butadiene rubber(SBR) gel surface, then uses it in the 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 usefulness 1-chloro-4-methyl-benzene modifications has reached the effect that reduces NR formula system cross-linked rubber rolling resistance, has improved simultaneously hauling ability and the wearing quality of tire.
US Patent No. 6242534 is used for the NR formula system in the lump to the styrene-butadiene rubber(SBR) gel that contains carboxyl and amino, has not only reduced the rolling resistance of system cross-linked rubber, has improved anti-slippery, and has obviously improved stress at definite elongation.
European patent EP 1431075 usefulness 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) and usefulness, wear resistance is improved as a result, rolling resistance reduces, and the proportion of cross-linked rubber is also less.
US Patent No. 6699935 usefulness modification by copolymerization styrene-butadiene rubber(SBR) gels make the 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 use the higher cross-linking monomer of price and energy consumption 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 that obtains after crosslinked just can must be reached rolling resistance, anti-slippery and wear resistance after carrying out modification.Although the particle diameter of report rubber gels is arranged in these patents, but when these rubber gels are distributed in the 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 purpose of the present invention provides a kind of emulsion polymerized styrene butadiene rubber composition.Cross-linked rubber anti-slippery, rolling resistance and the wear resistance of this rubber combination are improved simultaneously, can be used as good automobile tread rubber and use.
Another object of the present invention provides the preparation method of described rubber combination.
A further object of the present invention provides the cross-linked rubber of described rubber combination.
A kind of fully vulcanized powder rubber is disclosed in the International Patent Application WO 01/98395 (priority date on June 15th, 2000) that the International Patent Application WO 01/40356 (priority date on December 3rd, 1999) that the applicant submitted on September 18th, 2000 and the applicant submitted June 15 calendar year 2001.Propose after adopting irradiance method cross-linked rubber latex, because cross-linking radiation is so that the latex particle in the rubber latex (rubber particles) reaches certain gel content, the particle diameter of its latex particle is fixed up, not can after drying process in adhesion or coalescence.The contriver finds under study for action, and the paracril latex behind this cross-linking radiation and uncrosslinked styrene butadiene rubber latex are mixed, and coalescence obtains a kind of rubber combination of the crosslinked particle modified styrene-butadiene rubber(SBR) of paracril altogether afterwards.Wherein because 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 behind uncrosslinked styrene butadiene rubber latex coalescence with the particle size dispersion of its progenitor, and the degree that is uniformly dispersed than directly with much better in fully vulcanized powder rubber and the mixing mixture that obtains of rubber.Obtain thus a kind of modified rubber component.
This modified rubber component as the solid rubber master batch, is obtained rubber unvulcanizate with uncrosslinked block emulsion polymerized styrene butadiene rubber by blending technologies such as Banbury mixer, end runner mill, screw extrusion presss again.The rubber unvulcanizate that so obtains, the rubber particles with crosslinking structure that also can guarantee cross-linking radiation reaches the dispersion situation in the described particle size range in uncrosslinked emulsion polymerized styrene butadiene rubber matrix.Add again in this composition that rubber processing aids commonly used is mixing, obtain cross-linked rubber after the sulfuration.Because the paracril particle behind the cross-linking radiation has had crosslinking structure, does not need to consider the sulfuration of disperse phase, so just solved the covulcanization problem of the composition that different rubber form; Simultaneously the paracril particle with crosslinking structure of cross-linking radiation still is evenly dispersed in the vulcanized rubber take styrene-butadiene rubber(SBR) as matrix, so the anti-slippery of the cross-linked rubber that finally obtains, rolling resistance and wear resistance can obtain raising simultaneously with very little initial size very much.
Specifically, a kind of emulsion polymerized styrene butadiene rubber composition of the present invention includes modified rubber component and the emulsion polymerized styrene butadiene rubber of blend; Take emulsion polymerized styrene butadiene rubber as 100 weight parts, the modified rubber component is 1～70 part, is preferably 1～40 part, more preferably 1～20 part, most preferably is 1-10 part.
Described emulsion polymerized styrene butadiene rubber is the styrene/butadiene copolymers of emulsion polymerisation process in the prior art (the poly-method of breast) preparation.
The preparation method of above-described rubber combination, described modified rubber component comprise uncrosslinked rubber and the rubber particles with crosslinking structure that is dispersed in wherein; Described have the rubber particles of crosslinking structure and the weight ratio of uncrosslinked rubber is 80: 20～30: 70, preferred 80: 20～40: 60.
Wherein uncrosslinked rubber is various styrene-butadiene rubber(SBR) of the prior art, is preferably emulsion polymerized styrene butadiene rubber of the prior art same as above, i.e. the styrene/butadiene copolymers of emulsion polymerisation process (the poly-method of breast) preparation.
The rubber particles that wherein has crosslinking structure is the 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 that has crosslinking structure in the described modified rubber component is equal phase structure, does not carry out any graft modification, surface modification.
The preparation of the modified rubber component in the emulsion polymerized styrene butadiene rubber composition of the present invention, be comprise uncrosslinked rubber latex mixed with the component of the latex of the rubber particles with crosslinking structure after coalescence and get: wherein have the latex of rubber particles of crosslinking structure for passing through the rubber latex that obtains behind the cross-linking radiation.
Specifically, the preparation method of described modified rubber component may further comprise the steps:
(1) with paracril latex process cross-linking radiation, makes the paracril particle in the latex have crosslinking structure, reach described gel content, and the paracril particle in the latex is fixed in the described average particle size range;
(2) then by described weight ratio with rubber particles and described uncrosslinked rubber of crosslinking structure, get the paracril latex of above-mentioned cross-linking radiation and uncrosslinked styrene butadiene rubber latex and be mixed to evenly;
(3) above gained mixing latex is carried out common coalescence and get described modified rubber component.
The preparation method of above-described modified rubber component, wherein styrene butadiene rubber latex and not the paracril latex before the cross-linking radiation be synthetic rubber latex common in the prior art.Wherein styrene butadiene rubber latex comprises that the breast that emulsion polymerisation process directly prepares in the prior art gathers the latex that obtains behind the block latex of butylbenzene of styrene-butadiene latex and any existing method preparation; Be preferably the latex of emulsion polymerized styrene butadiene rubber in the prior art.Wherein the weight ratio of the solid content of the solid content of paracril latex and styrene butadiene rubber latex is 80: 20～30: 70, preferred 80: 20～40: 60.
The cross-linking radiation of paracril latex picks up from the method for cross-linking radiation rubber latex identical among the preparation method according to the disclosed fully vulcanized powder rubber of International Patent Application WO 01/40356 (priority date on December 3rd, 1999) in the above step (1).Paracril latex behind the cross-linking radiation of gained is also with the rubber latex before not dry behind the irradiation among the WO01/40356.
Specifically, crosslinking coagent can be do not used at paracril latex, also crosslinking coagent can be used.Used crosslinking coagent is selected from simple function group crosslinking coagent, two functional group's crosslinking coagents, trifunctional crosslinking coagent, four-functional group crosslinking coagent or polyfunctional group crosslinking coagent and arbitrary combination thereof.The example of described simple function group crosslinking coagent includes, but is not limited to: (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) glycidyl acrylate; The example of described two functional group's crosslinking coagents includes, but is not limited to: 1,4-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, Vinylstyrene; The example of described trifunctional crosslinking coagent includes, but is not limited to: trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate; The example of described four-functional group crosslinking coagent includes, but is not limited to: tetramethylolmethane four (methyl) acrylate, ethoxyquin tetramethylolmethane four (methyl) acrylate; The example of described polyfunctional group crosslinking coagent includes, but is not limited to: Dipentaerythritol five (methyl) acrylate.In this article, " (methyl) acrylate " refers to acrylate or methacrylic ester.These crosslinking coagents can use in the mode of arbitrary combination, as long as they help crosslinked under irradiation.
The add-on of the above crosslinking coagent is generally 0.1～10% weight of dried glue weight in the 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, preferred cobalt source.The dosage of irradiation can be 0.1～30Mrad, preferred 0.5～20Mrad.Generally speaking, irradiation dose should be so that the rubber particles gel content behind the rubber latex cross-linking radiation reaches 60% weight or higher, preferred 75% weight or higher, more preferably 80% weight or higher.
Thus, coalescence after being mixed with common uncrosslinked styrene butadiene rubber latex by the paracril latex behind this kind cross-linking radiation and the modified rubber component in, be dispersed in the paracril particle disperse phase in the external phase that uncrosslinked rubber consists of, also have the characteristic of the disclosed full sulfuration powder nbr rubber of WO01/40356.Namely 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 namely single particulate all is homogeneous on forming, and does not find layering in the particulate under the observation of existing microtechnique, minute equates the phenomenon of uneven phase.This paracril particle with crosslinking structure is by with corresponding paracril latex cross-linking radiation and the rubber particles particle diameter is fixing, and the particle diameter of the latex particle in its particle diameter and the original paracril latex is consistent.The median size of the rubber particles (latex particle) in the original paracril latex is generally 50～200nm, is preferably 70～200nm, more preferably 80～180nm.Median size through the rubber particles with crosslinking structure behind the cross-linking radiation is 50～200nm also generally, is preferably 70～200nm, more preferably 80～180nm.Owing to utilize two kinds of latex to mix and coalescence in the method, the paracril particle is crosslinked in the paracril latex behind the cross-linking radiation, has 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 component that obtains at last, 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.
Coalescence altogether after the present invention mixes according to the paracril latex of described weight ratio after with uncrosslinked styrene butadiene rubber latex, cross-linking radiation prepares described modified rubber component.In its preparation process, be exactly the mixing equipment of commonly using at two kinds of used mixing equipment of rubber latex mixing step, 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 commonly used in the existing rubber industry.
The preparation of emulsion polymerized styrene butadiene rubber composition of the present invention comprises: prepare first described modified rubber component, being about to paracril latex adopts the method for irradiation crosslinked, make the rubber particles in the latex have crosslinking structure, then with the paracril latex behind the cross-linking radiation and with uncrosslinked styrene butadiene rubber latex after mixing equipment commonly used mixes, adopt rubber latex coalescence method coalescence commonly used to obtain described modified rubber component; And then with this modified rubber component as the solid rubber master batch, adopt method for mixing rubber commonly used in the rubber industry and uncrosslinked niggerhead with other rubber usual auxiliaries, namely emulsion polymerized styrene butadiene rubber piece glue carries out the mixing described emulsion polymerized styrene butadiene rubber composition that obtains.
Specifically, the preparation method of emulsion polymerized styrene butadiene rubber composition of the present invention may further comprise the steps:
(1) with paracril latex process cross-linking radiation, make the paracril particle in the latex have crosslinking structure, reach described gel content, and the paracril particle in the latex is fixed in the described average particle size range, as at 50～200nm, be preferably 70～200nm, more preferably in the scope of 80～180nm;
(2) then by described weight ratio with rubber particles and uncrosslinked styrene-butadiene rubber(SBR) of crosslinking structure, get the paracril latex of above-mentioned cross-linking radiation and uncrosslinked 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 styrene butadiene rubber latex is 80: 20～30: 70, preferred 80: 20～40: 60;
(3) above gained mixing latex is carried out common coalescence and get described modified rubber component;
(4) with above-mentioned gained modified rubber component by described amount and the mixing composition that obtains emulsion polymerized styrene butadiene rubber of described emulsion polymerized styrene butadiene rubber; Wherein take emulsion polymerized styrene butadiene rubber as 100 weight parts, the modified rubber component is 1～70 part, is preferably 1～40 part, more preferably 1～20 part, most preferably is 1～10 part.
Emulsion polymerized styrene butadiene rubber composition of the present invention also can contain weighting agent commonly used in the rubber processing.Following substances is the suitable especially weighting agent of preparation emulsion polymerized styrene butadiene rubber composition rubber unvulcanizate of the present invention 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 the glass microballon etc.At least a in wherein said metal oxide preferential oxidation titanium, aluminum oxide, magnesium oxide, calcium oxide, barium oxide and the zinc oxide etc.Can also contain auxiliary agent commonly used in the Rubber processing sulfidations such as linking agent, vulcanization accelerator, antioxidant, thermo-stabilizer, photostabilizer, ozone stablizer, processing aid, softening agent, tenderizer, antiblocking agent, whipping agent, dyestuff, pigment, wax, extender, organic acid, fire retardant and coupling agent in the rubber combination of the present invention.Adjuvant used consumption is conventional amount used, or adjusts according to the requirement of practical situation.
The adding of above-described various auxiliary agents can add when the modified rubber component is mixing as solid rubber master batch and emulsion polymerized styrene butadiene rubber piece glue, namely add by the common calendering process of rubber, equipment can adopt method and mixing facilities commonly used commonly used in the rubber industry, can make mill, Banbury mixer, single screw extrusion machine or twin screw extruder etc.
By the cross-linked rubber of emulsion polymerized styrene butadiene rubber composition preparation of the present invention, be to adopt rubber materials vulcanization system commonly used and technique to carry out cross-linked rubber mixing and that sulfuration obtains above-described emulsion polymerized styrene butadiene rubber composition of the present invention.
Emulsion polymerized styrene butadiene rubber composition of the present invention prepares the impact that cross-linked rubber is not subjected to vulcanization system, can vulcanize in the sulfur cross-linking system of routine or non-sulfur cross-linking system.The cross-linked rubber of rubber combination of the present invention preparation is not subjected 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 that is prepared cross-linked rubber by rubber combination of the present invention adopts method and mixing facilities commonly used commonly used in the rubber industry, can make mill, Banbury mixer, single screw extrusion machine or twin screw extruder etc.
Specifically, the Micro of modified rubber component of the present invention is as previously mentioned: described uncrosslinked styrene-butadiene rubber(SBR) is external phase, and 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 emulsion polymerized styrene butadiene rubber composition that obtains after mixing by modified rubber component and emulsion polymerized styrene butadiene rubber makes, still have identical microtexture, namely the paracril particle with crosslinking structure in the modified rubber component still with the tiny particle size dispersion of 50～200nm in the styrene-butadiene rubber(SBR) matrix.
Modified rubber component in rubber combination of the present invention, because by cross-linking radiation so that the rubber particles in the paracril latex be fixed up with the particle diameter of original latex particle, so the paracril particle of cross-linking radiation is as disperse phase in the coalescence process, be dispersed in the uncrosslinked styrene-butadiene rubber(SBR) as external phase with the tiny particle diameter of 50～200nm.This modified rubber component is mixing as rubber master batch and emulsion polymerized styrene butadiene rubber, obtain the emulsion polymerized styrene butadiene rubber composition, the cross-linked rubber that is made by this rubber combination again, still have identical microtexture, namely the paracril particle with crosslinking structure in the modified rubber component still with the tiny particle size dispersion of 50～200nm in rubber matrix.So just have such microscopic pattern, just can make the paracril particle performance nano effect with crosslinking structure, cross-linked rubber anti-slippery, rolling resistance and the wear resistance of rubber combination of the present invention solved simultaneously the covulcanization problem that different rubber exist in sulfidation, so that can obtain raising simultaneously.
Say further not only have low rolling resistance and excellent moisture-proof slip by the prepared vulcanized rubber of rubber combination of the present invention, have simultaneously excellent wear resistance, can be used as the high-performing car tread rubber and use.
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:
The below has further described the present invention with embodiment, but scope of the present invention is not subjected to the restriction of these embodiment.Scope of the present invention is determined by accompanying claims.
(1) experimental data is measured with following plant and instrument and measuring method among the embodiment:
(1) rolling resistance: use RSS-II rubber rolling resistance test machine (Beijing all things on earth Yifang Technology Co., Ltd.) to measure the rolling power loss.
To under the 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, distortion increases to intermediate point gradually from the beginning point of contact; A little be gradually reduced to zero from intermediate point to leaving again.Because the viscous-elastic behaviour of various rubber compoundings, rubbery sample the beginning point of contact between the intermediate point deformation phases with joint efforts will be than intermediate point to the with joint efforts height that leaves a recovery period, this power parallel with load forces is the power loss value (J/r) of rubbery sample.Can characterize accordingly the rolling resistance of this rubber compounding.
Rolling resistance index (%): be radix with 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/T 1689-1998, 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.The 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
The 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 with the abrasion stereometry value of gum, the percentage ratio that the abrasion stereometry value of other modified adhesive accounts for the gum measured value is wear index.
(3) dynamic properties test (measuring wet and slippery): DMTAIV (dynamic mechanical analysis instrument) test of adopting U.S. Rheometric Scientific company to produce, 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, usually adopts the tan δ under 0 ℃ to characterize wet-sliding resistant performance.Tan δ value under 0 ℃ is larger, and the hauling ability of tire on wet road surface is better.
Anti-slippery index (%): be radix with 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) mensuration of the gel content of cross-linking radiation rubber latex: after nitrile rubber carried out cross-linking radiation according to certain condition, carry out spraying drying, obtain fully vulcanized powder rubber, then measuring the gel content of full sulfuration powder nbr rubber according to disclosed method in the International Patent Application WO 01/40356 (priority date on December 3rd, 1999), is exactly the gel content of paracril latex behind this cross-linking radiation.
(2) used raw material in embodiment and the Comparative Examples:
Emulsion polymerized styrene butadiene rubber latex SBR1502: solid content 20wt%, combined styrene content 23wt%, mooney viscosity 50, Qilu Petrochemical Company rubber plant produces.
Emulsion polymerized styrene butadiene rubber: block rubber, the trade mark: SBR1500, Shen, Nantong China chemical industry company limited produces.
Paracril latex: the trade mark is NBR-26, and source, sky, Zhaodong City chemical industry company limited produces.
Carbon black: N234 Haitun Carbon Black Co., Ltd. Tianjin
Zinc oxide: commercially available
Stearic acid: commercially available
Sulphur: Linyi City Luo Zhuan chemical plant
Accelerator TBBS: the N-tertiary butyl-2-[4-morpholinodithio time yellow acid amides, chemical plant, Kingsoft, Zhengzhou
Calcium chloride: commercially available
Starch: commercially available
Glycerine: commercially available
5% PHENOL 99.8 MIN ((CARBOLIC ACID)) liquid: commercially available
(3) latex coalescence method:
According to the recipe configuration coalescence agent solution of table 1, then join in this coalescence agent solution according to the rubber latex with coalescence agent solution identical weight, stir after 15 minutes, filtration, washing, drying obtain solid rubber (rubber).
Table 1
| Calcium chloride | Starch | Glycerine | 5%wt PHENOL 99.8 MIN ((CARBOLIC ACID)) liquid | Water |
| 8 parts | 0.8 part | 0.3 part | 2 parts | Transferring to coalescence agent solution gross weight is 100 parts |
Annotate: be parts by weight in the table 1
(4) method of the preparation of rubber unvulcanizate and sulfuration:
One segment process:
In Banbury Banbury mixer (Britain Farrel Bridge company product), carry out volume 1.57L, rotor speed 80rmin
-1Its process is: add separately the emulsion polymerized styrene butadiene rubber rubber or add modified rubber component of the present invention, emulsion polymerized styrene butadiene 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:
With going up thin-pass six times in XK-160 type mill (rubber machinery plant, Shanghai product) after above-mentioned one section rubber unvulcanizate adding sulphur, the promotor, descend sheet afterwards.Then at 160 ℃ of lower sulfurizing time T that press
90Then sulfuration makes the standard batten with the vulcanized rubber print, carries out every Mechanics Performance Testing, and its result is as shown in table 3.The prescription of rubber unvulcanizate sees Table 2, and unit is parts by weight.
Embodiment 1
1, the preparation of modified rubber component:
(1) preparation of cross-linking radiation paracril latex:
Be in the paracril latex (NBR-26) of 45%wt at solid content, after pressing the 3%wt adding crosslinking coagent Viscoat 295 of nitrile rubber solid content, carry out cross-linking radiation, irradiation dose is 3.0Mrad, obtain the paracril latex of cross-linking radiation, the median size 100nm of the paracril particle of cross-linking radiation in the latex, gel content is 91%.
(2) latex mixes and coalescence:
Paracril latex behind the cross-linking radiation is joined among the uncrosslinked emulsion polymerized styrene butadiene rubber latex SBR1502 according to certain solid content ratio, and wherein the paracril latex solid content behind the cross-linking radiation and uncrosslinked emulsion polymerized styrene butadiene rubber latex solid content weight ratio are 50: 50.The agitator high speed stirred after 15 minutes, obtained solid-state modified rubber component A according to aforementioned latex coalescence method coalescence.Wherein the composition of coalescence agent solution is with table 1.
2, emulsion polymerized styrene butadiene rubber composition and cross-linked rubber thereof preparation:
With above-mentioned gained modified rubber component A as rubber master batch, and relevant auxiliary agent with other add to carry out in the block rubber (emulsion polymerized styrene butadiene rubber SBR1500) mixing, obtain rubber unvulcanizate, its prescription composition sees Table 2 in parts by weight, and the preparation of rubber unvulcanizate and vulcanization process are ditto described.Then the vulcanized rubber print is made the standard batten, carry out every Mechanics Performance Testing, its result is as shown in table 3.
Embodiment 2
1, the preparation of modified rubber component:
According to carrying out the preparation of cross-linking radiation paracril latex with embodiment 1 identical method and latex mixes and coalescence, just the paracril latex solid content behind the cross-linking radiation and uncrosslinked emulsion polymerized styrene butadiene rubber latex solid content weight ratio become 80: 20, obtain solid-state modified rubber B component.
2, emulsion polymerized styrene butadiene rubber composition and cross-linked rubber thereof preparation:
With above-mentioned gained modified rubber B component as rubber master batch, and relevant auxiliary agent with other add to carry out in the block rubber (emulsion polymerized styrene butadiene rubber SBR1500) mixing, obtain rubber unvulcanizate, its prescription composition sees Table 2 in parts by weight, and the preparation of rubber unvulcanizate and vulcanization process are ditto described.Then the vulcanized rubber print is made the standard batten, carry out every Mechanics Performance Testing, its result is as shown in table 3.
Comparative example 1
Simple emulsion polymerized styrene butadiene rubber rubber (emulsion polymerized styrene butadiene rubber SBR1500) is adopted with identical mixing and sulfuration process in embodiment 1 step 2, carry out mixing and sulfuration.The rubber unvulcanizate prescription of concrete rubber combination forms lists in table 2.Cured properties sees Table 3.
Table 2 comparative example and Example formulations
| Title material | Comparative example 1 | Embodiment 1 | Embodiment 2 |
| *SBR1500 | 100 | 95 | 96.25 |
| Modified rubber component A | —— | 5 | —— |
| The modified rubber B component | —— | —— | 3.75 |
| 3 #Carbon black | 50 | 50 | 50 |
| Zinc oxide | 3 | 3 | 3 |
| Stearic acid | 1 | 1 | 1 |
| Sulphur | 1.75 | 1.75 | 1.75 |
| TBBS | 1 | 1 | 1 |
| Add up to | 156.75 | 156.75 | 156.75 |
The salient features of table 3 comparative example and embodiment
| Project | Comparative example 1 | Embodiment 1 | Embodiment 2 | Testing standard |
| Hardness (Shao Er A) | 70 | 69 | 67 | GB/T531.1-2008 |
| 300% stress at definite elongation/MPa | 18.0 | 18.2 | 17.4 | GB/T528-1998 |
| Tensile strength/MPa | 26.4 | 27.2 | 24.2 | GB/T528-1998 |
| Elongation rate of tensile failure/% | 407 | 422 | 386 | GB/T528 |
| Tension set/% | 3 | -- | 3 | GB/T528 |
| The compression fatigue temperature rise/℃ | 38.25 | 38.7 | 39 | GB/T1687-1993 |
| Rebound resilience/% | 50 | 50 | 50 | GB/T1681-2009 |
| Rolling resistance index/% | 100 | 97.9 | 97.8 | ———— |
| Wear index/% | 100 | 82.1 | 84.9 | GB/T 1689-1998 |
| Anti-slippery index/% | 100 | 106 | 116 | —— |
As can be seen from Table 3, adopt rolling resistance index, wear index, the anti-slippery index of its cross-linked rubber of rubber combination of the present invention can obtain raising simultaneously, its reason be exactly the paracril particle with crosslinking structure behind the cross-linking radiation with the tiny particle size dispersion of 50～200nm in the emulsion polymerized styrene butadiene rubber matrix of external phase.This specific character of rubber combination of the present invention is especially suitable for use as the automobile tread rubber.Because three parameters of rubber combination of the present invention " Magic triangle " all are improved, 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 are regulated rubber combination, thereby bring larger adjusting leeway for the tread rubber of preparation different performance demand.
Claims (10)
1. emulsion polymerized styrene butadiene rubber composition includes modified rubber component and the emulsion polymerized styrene butadiene rubber of blend; Take emulsion polymerized styrene butadiene rubber as 100 weight parts, the modified rubber component is 1～70 part;
Described modified rubber component comprises uncrosslinked rubber and is dispersed in wherein the rubber particles with crosslinking structure, and described have the rubber particles of crosslinking structure and the weight ratio of uncrosslinked rubber is 80: 20～30: 70; The rubber particles that wherein has crosslinking structure is the paracril particle, and median size is 50～200nm, and gel content is 60% weight or higher; Wherein uncrosslinked rubber is styrene-butadiene rubber(SBR).
2. composition according to claim 1 is characterized in that take emulsion polymerized styrene butadiene rubber as 100 weight parts, the modified rubber component is 1～40 part.
3. composition according to claim 2 is characterized in that take emulsion polymerized styrene butadiene rubber as 100 weight parts, the modified rubber component is 1～20 part.
4. composition according to claim 1, the rubber particles that it is characterized in that having in the described modified rubber component crosslinking structure is equal phase structure.
5. composition according to claim 1, the gel content that it is characterized in that having in the described modified rubber component rubber particles of crosslinking structure is 75% weight or higher.
6. composition according to claim 1, the median size that it is characterized in that having in the described modified rubber component rubber particles of crosslinking structure is 70～200nm.
7. composition according to claim 1 is characterized in that having the rubber particles of crosslinking structure in the described modified rubber component and the weight ratio of uncrosslinked rubber is 80: 20～40: 60.
8. the described composition of according to claim 1～7 each, it is characterized in that described modified rubber component comprise latex with described uncrosslinked rubber mix with the component of the latex of the rubber particles with crosslinking structure after coalescence and get: wherein have the latex of rubber particles of crosslinking structure for passing through the rubber latex that obtains behind the cross-linking radiation.
9. the preparation method of the composition of each described emulsion polymerized styrene butadiene rubber according to claim 1～8 may further comprise the steps:
(1) with paracril latex process cross-linking radiation, makes the paracril particle in the latex have crosslinking structure, reach described gel content, and the paracril particle in the latex is fixed in the described average particle size range;
(2) then by described weight ratio with rubber particles and uncrosslinked rubber of crosslinking structure, get the paracril latex of above-mentioned cross-linking radiation and uncrosslinked styrene butadiene rubber latex and be mixed to evenly;
(3) above gained mixing latex is carried out common coalescence and get described modified rubber component;
(4) with above-mentioned gained modified rubber component by described amount and the mixing composition that obtains emulsion polymerized styrene butadiene rubber of described emulsion polymerized styrene butadiene rubber.
10. the cross-linked rubber of the described emulsion polymerized styrene butadiene rubber composition preparation of according to claim 1～8 each.
Priority Applications (15)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110330604.9A CN103073760B (en) | 2011-10-26 | 2011-10-26 | A kind of modified rubber component and method for making and a kind of emulsion polymerized styrene butadiene rubber composition and method for making thereof and its cross-linked rubber |
| 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 |
| IN3426DEN2014 IN2014DN03426A (en) | 2011-10-26 | 2012-10-26 | |
| 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 |
| 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 |
| AU2012327629A AU2012327629B2 (en) | 2011-10-26 | 2012-10-26 | Modified rubber masterbatch, rubber composition prepared therewith and vulcanized rubber and preparation method thereof |
| SG11201401845PA SG11201401845PA (en) | 2011-10-26 | 2012-10-26 | Modified rubber masterbatch, rubber composition prepared therewith and vulcanized rubber and preparation method thereof |
| 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 |
| 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 |
| KR1020147013129A KR101698947B1 (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 |
| MX2014005050A MX343657B (en) | 2011-10-26 | 2012-10-26 | Modified rubber masterbatch, rubber composition prepared therewith and vulcanized rubber and preparation method thereof. |
| BR112014009912-0A BR112014009912B1 (en) | 2011-10-26 | 2012-10-26 | STANDARD MIXTURE OF MODIFIED RUBBER, STANDARD MIXTURE PROCESS OF MODIFIED RUBBER, RUBBER COMPOSITION, RUBBER COMPOSITION PREPARATION PROCESS AND VOLCANIZED RUBBER |
| 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110330604.9A CN103073760B (en) | 2011-10-26 | 2011-10-26 | A kind of modified rubber component and method for making and a kind of emulsion polymerized styrene butadiene rubber composition and method for making thereof and its cross-linked rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103073760A true CN103073760A (en) | 2013-05-01 |
| CN103073760B CN103073760B (en) | 2015-09-16 |
Family
ID=48150472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110330604.9A Active CN103073760B (en) | 2011-10-26 | 2011-10-26 | A kind of modified rubber component and method for making and a kind of emulsion polymerized styrene butadiene rubber composition and method for making thereof and its cross-linked rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103073760B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524814A (en) * | 2012-07-03 | 2014-01-22 | 中国石油化工股份有限公司 | Modified rubber master batch and preparation method thereof, polybutadiene rubber composition, and preparation method and vulcanized rubber thereof |
| CN103524810A (en) * | 2012-07-03 | 2014-01-22 | 中国石油化工股份有限公司 | Modified rubber master batch and preparation method thereof, oil-extended emulsion-polymerized butadiene-styrene rubber composition, and preparation method and vulcanized rubber thereof |
| CN103524813A (en) * | 2012-07-03 | 2014-01-22 | 中国石油化工股份有限公司 | Modified rubber master batch and preparation method thereof, oil-extended solution-polymerized styrene-butadiene rubber composition, and preparation method and vulcanized rubber thereof |
| US9290643B2 (en) | 2011-10-26 | 2016-03-22 | China Petroleum & Chemical Corporation | Modified rubber masterbatch, and rubber composition and vulcanized rubber produced therefrom, and the preparation processes for them |
| CN105778165A (en) * | 2014-12-16 | 2016-07-20 | 北京橡胶工业研究设计院 | Natural rubber/radiation-crosslinked nitrile-butadiene rubber composite material and preparation method therefor |
| CN109153826A (en) * | 2016-05-19 | 2019-01-04 | 横滨橡胶株式会社 | Rubber composition for tire |
| CN112375253A (en) * | 2020-10-26 | 2021-02-19 | 贵州大学 | Preparation method of modified sulfur and white carbon black blend for rubber |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1149867A2 (en) * | 2000-04-27 | 2001-10-31 | JSR Corporation | Crosslinked rubber particles and rubber compositions |
| CN1342183A (en) * | 1999-11-01 | 2002-03-27 | 东海橡胶工业株式会社 | Rubber vibration isolator and method for producing the same |
| WO2002032990A2 (en) * | 2000-10-20 | 2002-04-25 | Bayer Aktiengesellschaft | Rubber gels and rubber mixtures containing phenolic resin educts |
| CN101787148A (en) * | 2009-01-22 | 2010-07-28 | 中国科学院化学研究所 | Green tire material containing amphipathic starch derivant and preparation method thereof |
| 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 |
-
2011
- 2011-10-26 CN CN201110330604.9A patent/CN103073760B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1342183A (en) * | 1999-11-01 | 2002-03-27 | 东海橡胶工业株式会社 | Rubber vibration isolator and method for producing the same |
| EP1149867A2 (en) * | 2000-04-27 | 2001-10-31 | JSR Corporation | Crosslinked rubber particles and rubber compositions |
| WO2002032990A2 (en) * | 2000-10-20 | 2002-04-25 | Bayer Aktiengesellschaft | Rubber gels and rubber mixtures containing phenolic resin educts |
| CN101787148A (en) * | 2009-01-22 | 2010-07-28 | 中国科学院化学研究所 | Green tire material containing amphipathic starch derivant and preparation method thereof |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 王梦蛟: "连续液相混炼工艺生产的NR炭黑母炼胶", 《轮胎工业》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9290643B2 (en) | 2011-10-26 | 2016-03-22 | China Petroleum & Chemical Corporation | Modified rubber masterbatch, and rubber composition and vulcanized rubber produced therefrom, and the preparation processes for them |
| CN103524814A (en) * | 2012-07-03 | 2014-01-22 | 中国石油化工股份有限公司 | Modified rubber master batch and preparation method thereof, polybutadiene rubber composition, and preparation method and vulcanized rubber thereof |
| CN103524810A (en) * | 2012-07-03 | 2014-01-22 | 中国石油化工股份有限公司 | Modified rubber master batch and preparation method thereof, oil-extended emulsion-polymerized butadiene-styrene rubber composition, and preparation method and vulcanized rubber thereof |
| CN103524813A (en) * | 2012-07-03 | 2014-01-22 | 中国石油化工股份有限公司 | Modified rubber master batch and preparation method thereof, oil-extended solution-polymerized styrene-butadiene rubber composition, and preparation method and vulcanized rubber thereof |
| CN103524814B (en) * | 2012-07-03 | 2015-11-25 | 中国石油化工股份有限公司 | A kind of modified rubber masterbatch and method for making and a kind of polybutadiene rubber composite and preparation method thereof and cross-linked rubber thereof |
| CN103524813B (en) * | 2012-07-03 | 2016-03-30 | 中国石油化工股份有限公司 | 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 |
| CN103524810B (en) * | 2012-07-03 | 2016-08-03 | 中国石油化工股份有限公司 | A kind of modified rubber masterbatch and preparation method and a kind of preparation method and a vulcanized rubber thereof |
| CN105778165A (en) * | 2014-12-16 | 2016-07-20 | 北京橡胶工业研究设计院 | Natural rubber/radiation-crosslinked nitrile-butadiene rubber composite material and preparation method therefor |
| CN109153826A (en) * | 2016-05-19 | 2019-01-04 | 横滨橡胶株式会社 | Rubber composition for tire |
| CN109153826B (en) * | 2016-05-19 | 2021-04-30 | 横滨橡胶株式会社 | Rubber composition for tire |
| CN112375253A (en) * | 2020-10-26 | 2021-02-19 | 贵州大学 | Preparation method of modified sulfur and white carbon black blend for rubber |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103073760B (en) | 2015-09-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103073759B (en) | A kind of modified rubber component and method for making and a kind of solution polymerized butadiene styrene rubber composition and method for making thereof and its cross-linked rubber | |
| CN103073760B (en) | A kind of modified rubber component and method for making and a kind of emulsion polymerized styrene butadiene rubber composition and method for making thereof and its cross-linked rubber | |
| KR101698947B1 (en) | Modified rubber masterbatch, rubber composition prepared therewith and vulcanized rubber and preparation method thereof | |
| EP2772512B1 (en) | Rubber composition and preparation method and vulcanized rubber thereof | |
| CN103965530B (en) | A kind of rubber combination and preparation method thereof and its cross-linked rubber | |
| CN102432927B (en) | Butadiene styrene rubber composition with wear-resisting characteristic and preparation method thereof | |
| CN102924761B (en) | Tread rubber of zinc oxide pre-dispersion master colloidal particle and preparation method thereof | |
| CN102977428A (en) | Method for preparing blend composite material by virtue of performing blending modification on kaolin/white carbon black | |
| CN103073758B (en) | A kind of rubber combination and preparation method thereof and its cross-linked rubber | |
| CN103524813B (en) | 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 | |
| CN103524810B (en) | A kind of modified rubber masterbatch and preparation method and a kind of preparation method and a vulcanized rubber thereof | |
| CN103772766B (en) | A kind of rubber combination and preparation method thereof and its cross-linked rubber | |
| CN103524814B (en) | A kind of modified rubber masterbatch and method for making and a kind of polybutadiene rubber composite and preparation method thereof and cross-linked rubber thereof | |
| CN109666195A (en) | A kind of preparation method of rubber composite material | |
| CN103772767B (en) | A kind of rubber composition and preparation method thereof and its vulcanizate | |
| CN108164768A (en) | A kind of preparation method of graphene masterbatch |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |