CN104725684A - Rubber composition used for semi-steel radial tire tread - Google Patents
Rubber composition used for semi-steel radial tire tread Download PDFInfo
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- CN104725684A CN104725684A CN201310704312.6A CN201310704312A CN104725684A CN 104725684 A CN104725684 A CN 104725684A CN 201310704312 A CN201310704312 A CN 201310704312A CN 104725684 A CN104725684 A CN 104725684A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- 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 discloses a rubber composition used in the production of semi-steel radial tire tread rubber, the rubber composition singlely uses emulsion polymerized ternary integrated rubber as a rubber crude rubber component, the prepared tire tread has good wet-skid resistance and low rolling resistance performance, the rubber composition uses operation oil in accordance with requirements of the EU (European Union) labeling regulations, and the composition is in accord with the requirements of green environmental protection. The production of the rubber composition saves time, and the energy consumption is lower. The rubber composition is particularly suitable for making the tire tread of the semi-steel radial tire used in winter.
Description
Technical field
The present invention relates to a kind of rubber combination for making semi-steel radial tire tread rubber, this rubber combination is particularly suitable for the tyre surface of the semi-steel radial tire making use in winter.The invention belongs to rubber and tire industry production technical field.
Background technology
Along with the development of environmental protection tire, and in order to meet the requirement of European Union's tire tag regulation, world rubber circle adopts the rubber combination based on solution polymerized butadiene styrene rubber to make the tread rubber of radial tyre of passenger car one after another, comprising whole scheme using solution polymerized butadiene styrene rubber or also use part cis-1,4-polybutadiene rubber with solution polymerized butadiene styrene rubber.Ye You producer uses solution polymerization process styrene butadiene-synthetic polyisoprene, ie in solution polymerization ternary integrated rubber.According to imagination, ternary integrated rubber had both been similar to the better over-all properties of polyisoprene rubber, had again the wear resisting property that cis-1,4-polybutadiene rubber is equally good, and eliminated the necessary physical blending of different rubber blending, microcosmic can be reached even, and save the consumption of machining period and the energy.But owing to adopting the poly-Measures compare of breast to be difficult to control terpolymer, therefore initial ternary integrated rubber is all solution polymerization process synthesis, to such an extent as to industry is defaulted as addressed ternary integrated rubber is exactly solution polymerization ternary integrated rubber.
Practical application shows, solution polymerization process ternary integrated rubber is slightly poor relative to its physicals of styrene-butadiene rubber(SBR), especially second-order transition temperature is higher, its resistance to low temperature while improving wet-sliding resistant performance is deteriorated, even be difficult to meet tire service requirements in the winter time, therefore need and use part cis-1,4-polybutadiene rubber.It is conflicting that this point and ternary integrated rubber design original intention, and also part has obliterated its technical superiority relative to solution polymerized butadiene styrene rubber.
The poly-method ternary integrated rubber of emulsion polymerization styrene butadiene-synthetic polyisoprene involved in the present invention i.e. breast is the novel tertiary integrated rubber be developed in recent years.This novel synthetic rubber kind is taken the lead in succeeding in developing by DaLian, China Polytechnics professor Li Yang etc., and cooperates to have carried out further productivity research with rubber plant of Qilu Petrochemical Company.Li Yang etc. are patent to the method application of this letex polymerization ternary integrated rubber, and its patent publication No. is CN101463110A(emulsion polymerized styrene alkene-isoprene-butadiene terpolymer and preparation method thereof).Beijing Research & Design Institute of Rubber Industry is commissioned and has carried out evaluation and action oriented research to the fundamental property of this emulsion polymerization ternary integrated rubber, think that breast rational in infrastructure gathers its physicals of method ternary integrated rubber some kind not second to emulsion polymerized styrene butadiene rubber, even can reach close to natural rubber, be better than solution polymerized butadiene styrene rubber and solution polymerization process ternary integrated rubber.Particularly the second-order transition temperature of this rubber is lower than solution method ternary integrated rubber, therefore possesses the possibility used under lower temperature environment.Simultaneously with contain intermingle with the poly-method ternary integrated rubber of breast compared with method ternary integrated rubber and significantly reduce with an organic solvent in synthesis technique, therefore more energy-saving and environmental protection.
Test shows, the poly-method ternary integrated rubber of this breast with the rubber clone such as natural rubber, cis-1,4-polybutadiene rubber and use, and can not make corresponding rubber combination as rubber component separately, is applied to the tyre surface of making semi-steel radial tire.The wet-sliding resistant performance of this rubber combination and rolling resistance performance can be that main tread rubber composition is suitable with solution polymerized butadiene styrene rubber, thus are applicable to the tyre surface making semi-steel radial tire, are particularly suitable for the tyres for passenger cars making use in winter.
In sum, the rubber combination adopting the poly-method ternary integrated rubber of breast to prepare has good application prospect in field of tire production.Due to a kind of novel synthetic rubber kind of the poly-method ternary integrated rubber system of this breast, very limited for its applied research carried out both at home and abroad, through retrieving and inquire about the patent documentation and technology report that do not find to be correlated with.The present invention for semi-steel radial tire field have no especially its application and evaluate relevant report.
Summary of the invention
The present invention is directed to the poly-method ternary integrated rubber of a kind of novel synthetic rubber breast and devise the composition of rubber combination, preparation method and use target especially.That is: be used alone emulsion polymerization ternary integrated rubber and prepare a kind of high performance Tire tread rubber composition; Use the environment-friendly type process oil meeting European Union's tire tag laws and regulations requirement, thus make this tread mix meet the environmental requirement of European Union's green tire completely; The tread rubber composition that the wet-sliding resistant performance of this rubber combination and rolling resistance performance can be master with solution polymerized butadiene styrene rubber matches in excellence or beauty, thus is applicable to the tyre surface making semi-steel radial tire, is particularly suitable for the tyres for passenger cars making use in winter.Owing to being used alone emulsion polymerization ternary integrated rubber, also do not use natural rubber, also not and with the synthetic rubber of other kind, and its complete processing to have reduced in rubber mixing technique the necessary Blending Processes of blend rubber kind in the past, saves the consumption of machining period and the energy.
technical scheme
The present invention is achieved through the following technical solutions:
1, in this rubber combination with percentages, the styrene butadiene that the rubber raw rubber 100% that rubber combination uses synthesizes for emulsion polymerization-isoprene ternary integrated rubber, does not also use natural rubber, also not and with the synthetic rubber of other kind.The molecular structure of the poly-ternary integrated rubber of this breast has following characteristics:
A combined styrene content 23.5% ± 4%,
B in conjunction with 1，2-butadiene content about 10%,
C in conjunction with 1,2-isoprene content not higher than 3%,
D in conjunction with Isosorbide-5-Nitrae-isoprene content not higher than 30%.
2, in this rubber combination, contain the white carbon black of higher proportion.Specifically, add in the every 100 parts of rubber raw rubbers of mass fraction the white carbon black being not less than 40 parts, the highest use number of white carbon black is not higher than 125 parts.Owing to improve the mass fraction of white carbon black, thus in this rubber combination corresponding minimizing carbon black loading, obtain suitable hardness and physical and mechanical properties with control composition.
3, in order to meet the environmental-protecting performance requirement of European Union's label regulation, in this rubber combination, the process oil of environment-friendly type is employed.Concrete usage quantity is with 100 parts of rubber raw rubbers for benchmark, and the process oil mass fraction of interpolation is 3 ~ 50 parts.The type of its process oil comprises:
A environment-friendly aromatic oil TDAE,
B shallow oil pumping MES,
The remaining volatile oil RAE of C,
The heavy naphthenic oil HNAP of D.
4, according to above-mentioned composition, prepare rubber combination, tire tread glue work in-process with the common equipment of tire and Rubber processing and processing condition and prepare semi-steel radial tire.
beneficial effect
Actual detection is learnt, excellent according to rubber combination wet-sliding resistant performance in technical solution of the present invention, rolling resistance value is lower, is suitable for the tyre surface making semi-steel radial tire, is particularly suitable for the tyres for passenger cars making use in winter.
The process oil that this rubber combination uses the environmental-protecting performance meeting European Union's label regulation to require, therefore more close with the requirement of environmental protection tire.This rubber combination takes single breast to gather ternary integrated rubber glue kind, does not also use natural rubber, also not and with the synthetic rubber of other kind.Therefore in rubber mixing process, reduced its complete processing reduced the necessary Blending Processes of blend rubber kind in the past, decreased technological process, improve production efficiency, therefore save machining period and the energy.
This rubber combination with the common equipment of tire and Rubber processing and processing condition preparation, and and then for tire tread glue work in-process, prepare radial with the half steel method of forming.Therefore without the need to increasing specific equipment for implementing this patent.
Embodiment
The present invention is further illustrated below to enumerate embodiment, and claim of the present invention is not by the restriction of embodiment.In embodiment, the component of rubber combination all counts with mass parts.
Tire tread glue rubber combination in embodiments of the invention includes: rubber components, white carbon black, silane coupling agent, environment-friendly type process oil TDAE.
Rubber components and rubber be 100% breast gather method ternary integrated rubber (E-SIBR).The breast that the present embodiment 1 is used gathers its microtexture of method integrated rubber: combined styrene content is 25.8%; Be 46.6 in conjunction with Isosorbide-5-Nitrae-divinyl amount; 1，2-butadiene amount is 10.5%; Be 1.9% in conjunction with 1,2-isoprene amount, Isosorbide-5-Nitrae-isoprene amount is 13.9,3,4-isoprene amount is 1.3%.
White carbon black can be the precipitated silica of dry method or wet-layer preparation, not special restriction.But require its N2 adsorption specific surface area (N
2sA) at 100m
2/ g ~ 300m
2between/g.To make the existing good reinforcing effect of this white carbon black, be unlikely to again dispersity and reduce, and the heat-dissipating of rubber combination is raised, unfavorable to product.
With the rubber components of 100 parts of mass parts for benchmark, the amount adding white carbon black is at least 40 mass parts, and the addition of carbon black is at most 125 parts.White carbon black content very little low heat generation and anti-slippery can fully demonstrate, and the too many processing characteristics of add-on and workability are deteriorated.
Rubber combination in the present invention comprises silane coupling agent.The silane coupling agent be suitable for is any conventional silanes coupling agent that can use together with white carbon black.As two-[γ-(triethoxysilicane) propyl group] tetrasulfide (Si-69), two-(3-triethoxyl silane propyl group)-disulphide (Si-75, Z-6920 or A1589) etc.
In 100 mass parts white carbon blacks, the add-on of silane coupling agent is 5% ~ 20% of white carbon black amount.The dispersion effect of silane coupling agent add-on white carbon black is very little not good enough, and add-on too much can cause high cost, and to strength property and abrasion resistance unfavorable.
Comprise environment-friendly type mineral tenderizer and process oil in the embodiment of the present invention, application type has TDAE, MES, HNAP, RAE etc.In 100 parts of rubber quality parts, the add-on of process oil is between 3 ~ 50 parts.Process oil add-on very little, to rubber plasticizing less effective, is also unfavorable for fillers dispersed.Add-on is too high, poor processability, even may ooze out from rubber combination, affects the use properties of rubber combination.
The Synergist S-421 95 that rubber circle such as carbon black, promoting agent, linking agent, promotor, anti-aging agent are conventional is also used in the embodiment of the present invention.The present invention does not do special restriction to the use of these Synergist S-421 95s.
The rubber used in reference examples contains intermingle with method integrated rubber (S-SIBR) and solution polymerized butadiene styrene rubber (SSBR).The rubber used in reference examples is all oil-extended rubber, and oil product loading level is 37.5%.The equal weight by dry rubber of rubber quality part of mentioning in embodiment and reference examples, namely all deducts the quality of wherein oil product.
Embodiment, reference examples 1, each material of reference examples 2 are carried out mixing according to formula table 1 Suo Shi and prepare rubbery sample.Vulcanized test specimens is sulfuration 20min at 160 DEG C.And carry out each performance test according to relevant criterion.
Table 1
| Component | Embodiment | Reference examples 1 | Reference examples 2 |
| E-SIBR | 100 | 0 | 0 |
| S-SIBR | 0 | 101.3 | 0 |
| SSBR | 0 | 0 | 101.3 |
| BR | 0 | 25 | 25 |
| Process oil | 37.5 | 10 | 10 |
| White carbon black | 75 | 75 | 75 |
| Carbon black | 5 | 5 | 5 |
| Silane coupling agent | 8 | 8 | 8 |
| Anti-aging agent | 3 | 3 | 3 |
| Stearic acid | 3 | 3 | 3 |
| Zinc oxide | 2 | 2 | 2 |
| Sulphur | 1.5 | 1.5 | 1.5 |
| Accelerator CBS (CZ) | 1.7 | 1.7 | 1.7 |
| Vulkacit D PG | 1.5 | 1.5 | 1.5 |
| Test-results | |||
| Mooney Viscosity of Rubber Mix ML(1+4) 100 DEG C | 71 | 67 | 68 |
| Hardness (Shao Er A) | 70 | 68 | 68 |
| 300% stress at definite elongation/MPa | 20.6 | 17.9 | 18.4 |
| Tensile strength/MPa | 23.9 | 20.0 | 20.2 |
| Elongation rate of tensile failure/% | 320 | 327 | 314 |
| Break tension set/% | 8 | 5 | 4 |
| Tear strength/(kN/m) | 52 | 49 | 45 |
| Akron abrasion/(cm 3/1.61km） | 0.099 | 0.110 | 0.096 |
| Tg/℃ | |||
| Tanδ@0℃ | 0.4335 | 0.4338 | 0.4054 |
| tanδ@60℃ | 0.1765 | 0.1837 | 0.1664 |
Comparative example and reference examples 1,2 known, the high-performance tire tread rubber composition prepared with E-SIBR is compared with SSBR or S-SIBR, and mechanical property is more excellent, and dynamic properties is suitable, is the good tread rubber composition of a kind of over-all properties.
It will be understood by those skilled in the art that the present invention can be actually used in the rubber combination manufacturing semi-steel radial tire tyre surface.
Claims (5)
1. a rubber combination, is characterized in that styrene butadiene-isoprene ternary integrated rubber that the rubber raw rubber 100% that this rubber combination uses synthesizes for emulsion polymerization, does not also use natural rubber, also not and with the synthetic rubber of other kind.
2. styrene butadiene-isoprene ternary the integrated rubber of emulsion polymerization synthesis according to claim 1, is characterized in that:
A combined styrene content 23.5% ± 4%,
B in conjunction with 1，2-butadiene content about 10%,
C in conjunction with 1,2-isoprene content not higher than 3%,
D in conjunction with Isosorbide-5-Nitrae-isoprene content not higher than 30%.
3. rubber combination according to claim 1, is characterized in that the white carbon black ratio used in the every 100 parts of rubber raw rubbers of mass fraction is not less than 40 parts, and in every 100 parts of rubber raw rubbers the highest use number of white carbon black not higher than 125 parts.
4. rubber combination according to claim 1, is characterized in that this rubber combination uses the process oil meeting European Union's label laws and regulations requirement, and its amount ranges is that the addition of process oil is 3 ~ 50 parts in mass fraction every 100 parts of rubber raw rubbers; The type of its process oil comprises:
A environment-friendly aromatic oil TDAE,
B shallow oil pumping MES,
The remaining volatile oil RAE of C,
The heavy naphthenic oil HNAP of D.
5. rubber combination according to claim 1, is characterized in that the purposes of this rubber combination is to make the tyre surface of semi-steel radial tire.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310704312.6A CN104725684A (en) | 2013-12-19 | 2013-12-19 | Rubber composition used for semi-steel radial tire tread |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310704312.6A CN104725684A (en) | 2013-12-19 | 2013-12-19 | Rubber composition used for semi-steel radial tire tread |
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| Publication Number | Publication Date |
|---|---|
| CN104725684A true CN104725684A (en) | 2015-06-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310704312.6A Pending CN104725684A (en) | 2013-12-19 | 2013-12-19 | Rubber composition used for semi-steel radial tire tread |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102803370A (en) * | 2009-06-29 | 2012-11-28 | 米其林集团总公司 | Tyre, the tread of which includes a saturated thermoplastic elastomer |
| CN102898584A (en) * | 2012-10-09 | 2013-01-30 | 大连理工大学 | Styrene-butadiene-isoprene terpolymer integrated latex and preparation method thereof |
-
2013
- 2013-12-19 CN CN201310704312.6A patent/CN104725684A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102803370A (en) * | 2009-06-29 | 2012-11-28 | 米其林集团总公司 | Tyre, the tread of which includes a saturated thermoplastic elastomer |
| CN102898584A (en) * | 2012-10-09 | 2013-01-30 | 大连理工大学 | Styrene-butadiene-isoprene terpolymer integrated latex and preparation method thereof |
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Application publication date: 20150624 |