CN102432927A - Butadiene styrene rubber composition with wear-resisting characteristic and preparation method thereof - Google Patents
Butadiene styrene rubber composition with wear-resisting characteristic and preparation method thereof Download PDFInfo
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Abstract
The invention provides a butadiene styrene rubber composition with a wear-resisting characteristic and a preparation method thereof. The butadiene styrene rubber composition comprises the following components in parts by weight: 100 parts of butadiene styrene rubber, 1-30 parts of modified butylbenzene powdered rubber and can also comprise 1-30 parts of hydroxyl-terminated liquid butadiene styrene rubber and the like. In the butadiene styrene rubber, the content of the bound styrene is 15-50%, and the Mooney viscosity is 30-90; the modified butylbenzene powdered rubber is obtained by modifying the surface of the butylbenzene powdered rubber prepared by a radiation crosslinking method by using ethanthiol and potassium persulfate under the existence of polyethylene glycol, wherein the content of the bound styrene is 15-60% and the average particle size is 50-300nm; and the content of gel is 70-98%. The butylbenzene vulcanized rubber can well achieve the balance among the rolling resistance, the slippery resistance and the wear resistance, and is suitably used for tread rubber.
Description
Technical field
The present invention relates to rubber materials, say further, relate to a kind of styrene-butadiene rubber(SBR) composition and method of making the same.
Background technology
How in short supply day by day along with the increasingly stringent of reducing emission of carbon dioxide policies and regulations and petroleum resources reduces fuel oil consumption and becomes the focus that automobile industry and user pay close attention to, and the rolling resistance that reduces tire is one of important measures that reduce vehicle fuel consume.
In reducing tyre stock (mainly being tread rubber) rolling resistance research, very thorny rolling resistance, wet and slippery performance, conflicting so-called " Magic triangle " problem of wear resisting property have been run into.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 rolling resistance to a certain extent, but make reinforced filling in sizing material, be difficult to be uniformly dispersed, and anti-slippery is reduced.Strengthen the consumption of vulcanizing agent, promptly improve cross-linking density, the same with the effect that increases the reinforced filling consumption, reduce rolling resistance and make the anti-slippery variation simultaneously.In order to realize the balance of three aspect performances, except design is optimized to tire construction, also sizing material (is main with tread rubber) prescription has been carried out research extensively and profoundly both at home and abroad.The synthetic on the one hand rubber raw materials (like solution polymerized butadiene styrene rubber SSBR, using trans-polyisoprene TPI, butadiene-isoprene-vinylbenzene integrated rubber SIBR, high-vinyl cis-1,4-polybutadiene rubber HVBR etc.) that is suitable for, the properties-correcting agent and the practical formulation of setting about seeking to have better over-all properties on the other hand.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 usefulness or reciprocal (counter-rotating) carbon black system; The system characteristics are that main formula is constant basically, and are just different on reinforced filling, in industry, realize easily; Its shortcoming is that machine utilization is big when needing to use more silane coupling agent and refining glue, and the wear resistance of cross-linked rubber is also undesirable.
Meanwhile, the researchist finds that crosslinked powdered rubber can reduce the rolling resistance of cross-linked rubber when prescription is suitable.(swelling index 4～5, particle diameter 60～450nm) rolling resistance of tree elastomer (NR) formula system cross-linked rubber is reduced, and strength property are uninfluenced for the crosslinked suitable fourth of patent US6184296 use process surface-treated and butylbenzene powdered rubber.In patent US6133364, be grafted to 1-chloro-4-methyl-benzene on the crosslinked butylbenzene powdered rubber surface, use it for then in the NR formula system, the rolling resistance of cross-linked rubber is reduced, and anti-slippery improve.
Patent US6207757 has reached the effect that reduces NR formula system cross-linked rubber rolling resistance with the crosslinked butylbenzene powdered rubber of 1-chloro-4-methyl-benzene modification, has improved the hauling ability and the wearing quality of tire simultaneously.
Patent US6242534 is used for the NR formula system containing carboxyl with amino crosslinked butylbenzene powdered rubber in the lump, has not only reduced the rolling resistance of system cross-linked rubber, has improved anti-slippery, and has obviously improved stress at definite elongation.
Patent EP1431075 with butylbenzene powdered rubber and plasticized starch improve styrene-butadiene rubber(SBR) (SBR) and cis-1,4-polybutadiene rubber (BR) and with the performance of WHITE CARBON BLACK system, as a result wear resistance be improved, the rolling resistance reduction, the proportion of cross-linked rubber is also less.
Patent US6699935 makes modification butylbenzene formula system have low-rolling-resistance with the crosslinked butylbenzene powdered rubber of modification by copolymerization and has outstanding anti-slippery and wear resistance concurrently.
The crosslinked butylbenzene powdered rubber that above-mentioned patent documentation is mentioned all adopts Chemical Crosslinking Methods crosslinked; This method need use the higher cross-linking monomer of price and energy consumption bigger, and relates generally to the WHITE CARBON BLACK system and the modification butylbenzene formula system of natural rubber formulations system or styrene-butadiene rubber(SBR).
In sum, seek a kind of styrene-butadiene rubber(SBR) compsn, energy consumption is lower when improving performance, is the present technical issues that need to address.
Summary of the invention
For solving the problem that exists in the prior art, the invention provides a kind of styrene-butadiene rubber(SBR) compsn, its cross-linked rubber is on the basis that anti-slippery improves, and rolling resistance decreases; Perhaps wear resistance is significantly improved.
One of the object of the invention provides a kind of styrene-butadiene rubber(SBR) compsn.
The following component that comprises blend: styrene-butadiene rubber(SBR) and be 100 weight parts in styrene-butadiene rubber(SBR), the modification butylbenzene powdered rubber of 1～30 weight part is preferably 5～15 weight parts.
Said styrene-butadiene rubber(SBR) is various styrene-butadiene rubber(SBR) of the prior art, and wherein combined styrene content 15～50%, and is preferred 20～30%, mooney viscosity 30～90, preferred 40～70.The preferred oil-extended styrene-butadiene rubber of styrene-butadiene rubber(SBR) in the butylbenzene compsn of the present invention.When compsn was selected oil-extended styrene-butadiene rubber for use, the said content of said other each components was 100 weight parts in styrene-butadiene rubber(SBR) in the oil-extended styrene-butadiene rubber still.
The butylbenzene powdered rubber of the radiation crosslinking method preparation that said modification butylbenzene powdered rubber is modification; The butylbenzene powdered rubber of said radiation crosslinking method preparation is specifically prepared with reference to the preparation method of the disclosed fully vulcanized powder rubber of Chinese patent CN 1402752A, or the butylbenzene powdered rubber VP101 that adopts the China Petrochemical Industry Beijing Chemical Research Institute to produce according to this patented technology.The combined styrene content 15～60% of said butylbenzene powdered rubber, preferred 35～55%, median size 50～300nm, preferred 100～200nm; Gel content 70～98%, preferred 85～95%; In the presence of polyoxyethylene glycol, crosslinked butylbenzene powdered rubber is carried out surface-treated with ethanthiol and Potassium Persulphate.
Said modification butylbenzene powdered rubber specifically is by following method preparation:
(1) will be made into suspension-s through the same polyoxyethylene glycol of butylbenzene powdered rubber, ethanthiol and the water that the styrene butadiene rubber latex cross-linking radiation obtains; In 100 parts of butylbenzene powdered rubber weight, the consumption of polyoxyethylene glycol and ethanthiol is respectively 2.0～4.0 parts and 1.5～3.0 parts; Wherein the molecular weight ranges of polyoxyethylene glycol is 200～20000;
(2) be heated to 30 ± 5 ℃, in suspension-s, drip potassium persulfate solution while stirring, be warming up to 70 ± 5 ℃ after all dripping, fully reaction; In order to drip convenient and to be uniformly dispersed, the concentration of potassium persulfate solution is preferably at 1～5%wt; In 100 parts of butylbenzene powdered rubber weight, the consumption of Potassium Persulphate is 1.5～2.5 parts, and is more abundant in order to make modified-reaction, after potassium persulfate solution all drips and is warming up to 70 ± 5 ℃, preferably keeps 0.5～2.0 hour;
(3) temperature is reduced to below 40 ℃, filters, washing, vacuum-drying make said modification butylbenzene powdered rubber.
In order to improve the sooty dispersion effect and to improve rubber and sooty bonding force; Styrene-butadiene rubber(SBR) compsn with antiwear characteristic according to the invention also comprises terminal hydroxy liquid styrene-butadiene rubber(SBR); Its consumption is that 1～30 weight part is preferably 5～15 weight parts in styrene-butadiene rubber(SBR) 100 weight parts.
Said terminal hydroxy liquid styrene-butadiene rubber(SBR) is terminal hydroxy liquid styrene-butadiene rubber(SBR) of the prior art.
In order to improve the bonding force of carbon black and rubber, styrene-butadiene rubber(SBR) compsn according to the invention also comprises silane coupling agent, and its consumption is that 100 weight parts are counted 0.1～5 weight part with styrene-butadiene rubber(SBR).Silane coupling agent is a silane coupler containing sulfur, and commonly used is 3,3 '-two (triethoxy methyl silicane base propyl group) tetrasulfide (Si69).Also have in addition: 3,3 '-two (trimethoxymethylsila,e base propyl group) disulphide, 3; 3 '-two (trimethoxymethylsila,e base propyl group) tetrasulfide, 3,3 '-two (triethoxy methyl silicane base propyl group) disulphide; 3,3 '-two (triethoxy methyl silicane base propyl group) eight sulfide, 3; 3 '-two (three butoxymethyl siloyl group propyl group) disulphide, 3,3 '-two (three butoxymethyl siloyl group propyl group) tetrasulfide etc.
Said styrene-butadiene rubber(SBR) compsn also comprises the processing aid that adopts usually in this area, as: strengthening agent, vulcanizing agent, promotor, promoting agent, anti-aging agent, filling wet goods.
Strengthening agent can be selected carbon black or WHITE CARBON BLACK for use, preferred carbon black.Add-on can be counted 40～120 parts with styrene-butadiene rubber(SBR) 100 weight parts, preferred 70～90 parts.The carbon black trade mark commonly used has: N110, N115, N120, N125, N135, N220, N231, N234, N242, N293, N299, N326, N330, N335, N339, N343, N351, N356, N375, N539, N550, N660, N772, N990 etc.
Vulcanizing agent can be selected sulphur of the prior art or sulfur donor for use, preferred sulphur.With styrene-butadiene rubber(SBR) is 100 weight parts, consumption 0.5～6 weight part of sulphur, preferred 1.2～3 weight parts.
Promotor can be used N tert butyl benzothiazole 2 sulfenamide commonly used, 1,3-diphenylguanidine etc.;
Promoting agent can use traditional zinc oxide and Triple Pressed Stearic Acid;
Anti-aging agent can take anti-RD also to use with anti-4020;
Extending oil can use aromatic hydrocarbon oil, NO;
The consumption of the above promotor, promoting agent, anti-aging agent, extending oil is a common consumption in this area, perhaps suitably adjusts according to practical situation.
When styrene-butadiene rubber(SBR) compsn of the present invention was selected oil-extended styrene-butadiene rubber as base rubber for use, the said content of said other each components was 100 weight parts in styrene-butadiene rubber(SBR) in the oil-extended styrene-butadiene rubber still.
Two of the object of the invention provides said styrene-butadiene rubber(SBR) preparation of compositions method.
Comprise said component mixing in described ratio.
Styrene-butadiene rubber(SBR) compsn of the present invention; Can add the common vulcanization system of styrene-butadiene rubber(SBR); Cure conditions (like temperature, time etc.) and the equipment that uses are institute's employing usually in the styrene-butadiene rubber(SBR) sulfuration processing, and the employed vulcanizing equipment of present method is the general vulcanizing equipment in the Rubber processing already.As: Banbury mixer, mill, vulcanizing press etc.
The present invention is used for the styrene-butadiene rubber(SBR) formula system through the butylbenzene powdered rubber modification, and the processing characteristics of its rubber unvulcanizate is not affected basically as a result, extrudes expansion and also reduces to some extent.The anti-slippery of cross-linked rubber improves, and rolling resistance obviously reduces; After being combined with terminal hydroxy liquid styrene-butadiene rubber(SBR) again in this compsn, terminal hydroxy liquid styrene-butadiene rubber(SBR) and modification butylbenzene powdered rubber produce synergy, and on the improved basis of anti-slippery, wear resistance significantly improves.Even when preferably combination, three performances of Magic triangle all can improve.Styrene-butadiene rubber(SBR) compsn of the present invention is especially suitable for use as the tread rubber of riding tire.
Embodiment
Below in conjunction with embodiment, further specify the present invention.
(1) experimental data is measured with following plant and instrument and measuring method among the embodiment:
(1) mooney viscosity: adopt the test of M200E type mooney's viscosimeter, 100 ℃ of test temperatures.
(2) mooney scorch: adopt the test of M200E type mooney's viscosimeter, 120 ℃ of test temperatures.
(3) vulcanization characteristics: the vulcanization characteristics of rubber unvulcanizate adopts the C200E type not have the test of rotor vulkameter, 160 ℃ of test temperatures, oscillation rate 1.7Hz, 0.5 ° of amplitude.
(4) main Mechanical: (GB/T528-1998, GB/T529-1999, GB/T531-1999) carries out by national standard
(5) rolling resistance: adopt DUNLOP rotary power loss appearance,, experimentize under the 7Hz frequency, be preheating to 38 ℃, measure rolling loss at the 15Kg constant load.Per 10 minutes record one secondary data, the rolling loss (J/r) of result during with 30 minutes represented.
(6) anti-slippery and wear resistance: use LAT 100 indoor wet and slippery abrasion machines to measure the wear hardness and the anti-slippery of sizing material, the wear hardness test has comprehensive and severe condition.Integrated condition is: speed 10km/h, load 75N, 9 ° at inclination angle.The anti-slippery test condition is: speed 6km/h, load 75N, 16 ° at inclination angle, 20 ℃ of temperature.
(2) used raw material in embodiment and the Comparative Examples:
Styrene-butadiene rubber(SBR): oil-filled emulsion polymerized styrene butadiene rubber SBR1712, combined styrene content 23%, mooney viscosity 50, Qilu Petrochemical company produces.Styrene-butadiene rubber(SBR) content 72.7%wt wherein.
Terminal hydroxy liquid styrene-butadiene rubber(SBR): HTBS, the neat imperial chemical industry in Zibo ltd production combined styrene content 18%, hydroxyl value 0.58mmol/g.
Silane coupling agent: Si69 3,3 '-two (triethoxy methyl silicane base propyl group) tetrasulfide, Nanjing really chemical industry ltd difficult to understand
Carbon black: N234 Haitun Carbon Black Co., Ltd. Tianjin
Aromatic hydrocarbon oil is commercially available
Zinc oxide: commercially available
Triple Pressed Stearic Acid: commercially available
The protection wax Microcrystalline Wax, Fushun oil grinds special wax ltd
Anti-RD 2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer, Nanjing chemical industry ltd
Anti-4020 N-(1, Shandong Sheng'Ao Chemical Co., Ltd
Sulphur Linyi City Luo Zhuan chemical plant
The short NS N-tertiary butyl-2-[4-morpholinodithio time yellow acid amides, chemical plant, Kingsoft, Zhengzhou
Short DPG 1,3-diphenylguanidine, Puyang WeiLin chemical engineering Co., Ltd
Modification butylbenzene powdered rubber: self-control
As followsPreparation:
Raw material:
The VP101 (combined styrene content 50%, gel content 89%, median size 100nm) that the butylbenzene powdered rubber selects for use the China Petrochemical Industry Beijing Chemical Research Institute to produce.
Polyoxyethylene glycol (molecular weight 2000) Xingtai blue star auxiliary reagent factory
1,6-ethanthiol and Potassium Persulphate are commercially available.
Process:
Take by weighing 150g butylbenzene powdered rubber and put into the there-necked flask of 1000ml, in bottle, add simultaneously water, the 4.6g of 470ml polyoxyethylene glycol, 3.4g 1, the 6-ethanthiol is mixed with suspension-s.30 ℃ of temperature, stirred suspension limit, limit drips 131g, and the potassium persulfate solution of concentration 2.3%wt after potassium persulfate solution drips, progressively is warming up to 70 ℃.Under this temperature, react 1h.After this, suspension-s is cooled to below 40 ℃, obtains modification butylbenzene powdered rubber through filtration, washing, vacuum drying.
Comparative example 1
The prescription composition of rubber composite is seen table 1, and preparing method's step of rubber unvulcanizate is following:
One segment process:
1.57L the Farril Banbury mixer, 80 ℃, 80 rev/mins.
Add styrene-butadiene rubber(SBR) rubber and modification butylbenzene powdered rubber, put down floating weight, 0.5min plasticates.
Rise floating weight, the carbon black of packing into, and other auxiliary agents (except sulphur, promotor, the aromatic hydrocarbon oil) put down floating weight, mixing 3min.
Rise floating weight, pack into terminal hydroxy liquid styrene-butadiene rubber(SBR) and aromatic hydrocarbon oil put down floating weight, mixing 2.5min.
Binder removal (temperature is at 150～160 ℃).
Two step process:
6 cun mills.
Above-mentioned one section rubber master batch adding sulphur, promotor are approached logical six times, descend sheet afterwards.
Embodiment 1～5
The prescription composition of rubber composite is listed in table 1, and the preparation process of its rubber unvulcanizate is identical with comparative example.Each component is all in parts by weight in the table 1.
Table 1 comparative example and Example formulations
| Title material | Comparative example 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| *SBR1712 | 137.5 | 137.5 | 137.5 | 137.5 | 137.5 | 137.5 |
| Modification VP101 | —— | 10 | 10 | 15 | 5 | 10 |
| HTBS | —— | —— | 20 | —— | 10 | 10 |
| Si69 | —— | —— | —— | —— | 1 | 2 |
| N234 | 75 | 75 | 75 | 75 | 75 | 75 |
| Aromatic hydrocarbon oil | 5 | 5 | 5 | 5 | 5 | 5 |
| Zinc oxide | 3 | 3 | 3 | 3 | 3 | 3 |
| Triple Pressed Stearic Acid | 2 | 2 | 2 | 2 | 2 | 2 |
| Protection wax | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Anti-RD | 1 | 1 | 1 | 1 | 1 | 1 |
| Anti-4020 | 1 | 1 | 1 | 1 | 1 | 1 |
| Sulphur | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Short NS | 1.4 | 1.4 | 1.4 | 1.4 | 1.4 | 1.4 |
| Short DPG | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
Annotate:
*SBR1712 is the mixture of 100 weight part SBR and 37.5 parts of oil
The salient features of comparative example and embodiment is listed in table 2～4.
Table 2 vulcanization characteristics and mooney scorch
Physical and mechanical properties after table 3 sulfuration
Wear-resisting, anti-slippery after table 4 sulfuration and rolling resistance
| Project | Comparative example 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Wear index | 100.0 | 96.7 | 104.3 | 80.5 | 126.0 | 135.0 |
| Anti-slippery | 100.0 | 103.0 | 100.0 | 103.0 | 102.0 | 102.0 |
| Rolling resistance | 100.0 | 95.0 | 122.0 | 91.3 | 102.0 | 96.0 |
Can find out that from the result of table 3 and table 4 be used for the styrene-butadiene rubber(SBR) formula system to the butylbenzene powdered rubber of modification, the anti-slippery of cross-linked rubber improves, rolling resistance obviously reduces, like embodiment 1 and embodiment 3; After being combined with terminal hydroxy liquid styrene-butadiene rubber(SBR) again in this compsn, terminal hydroxy liquid styrene-butadiene rubber(SBR) and modification butylbenzene powdered rubber produce synergy, and on the improved basis of anti-slippery, wear resistance significantly improves, like embodiment 2,4 etc.Even when preferably combination, three performances of Magic triangle all can improve.As embodiment 5 having reached good improvement aspect rolling resistance, anti-slippery and the wear resistance, compare rolling resistance with comparative example 1 and reduced by 4%, anti-slippery slightly improves, wear resistance has improved 35%.
It is thus clear that styrene-butadiene rubber(SBR) compsn of the present invention is balance rolling resistance, wet and slippery performance, conflicting " Magic triangle " problem of wear resisting property well, be especially suitable for use as the tread rubber of riding tire.
Claims (10)
1. styrene-butadiene rubber(SBR) compsn comprises the following component of blend:
Styrene-butadiene rubber(SBR) 100 weight parts
Modification butylbenzene powdered rubber 1～30 weight part
Combined styrene content 15～50% in the wherein said styrene-butadiene rubber(SBR), mooney viscosity 30～90;
Combined styrene content 15～60% in the said modification butylbenzene powdered rubber, median size 50～300nm; Gel content 70～98%;
Said modification butylbenzene powdered rubber is by following method preparation:
(1) will be made into suspension-s through the same polyoxyethylene glycol of butylbenzene powdered rubber, ethanthiol and the water that the styrene butadiene rubber latex cross-linking radiation obtains; In 100 parts of butylbenzene powdered rubber weight, the consumption of polyoxyethylene glycol and ethanthiol is respectively 2.0～4.0 parts and 1.5～3.0 parts;
Wherein the molecular weight ranges of polyoxyethylene glycol is 200～20000;
(2) be heated to 30 ± 5 ℃, in suspension-s, drip potassium persulfate solution while stirring, be warming up to 70 ± 5 ℃ after all dripping, fully reaction; In 100 parts of butylbenzene powdered rubber weight, the consumption of Potassium Persulphate is 1.5～2.5 parts;
(3) temperature is reduced to below 40 ℃, filters, washing, vacuum-drying make said modification butylbenzene powdered rubber.
2. styrene-butadiene rubber(SBR) compsn as claimed in claim 1 is characterized in that:
Combined styrene content 20～30% in the said styrene-butadiene rubber(SBR), mooney viscosity 40～70.
3. styrene-butadiene rubber(SBR) compsn as claimed in claim 1 is characterized in that:
Combined styrene content 35～55% in the said modification butylbenzene powdered rubber, median size 100～200nm, gel content 85～95%.
4. styrene-butadiene rubber(SBR) compsn as claimed in claim 1 is characterized in that:
The consumption of said modification butylbenzene powdered rubber is 5～15 weight parts.
5. styrene-butadiene rubber(SBR) compsn as claimed in claim 1 is characterized in that:
The concentration of potassium persulfate solution is 1～5%wt in said modification butylbenzene powdered rubber preparing method's step (2).
6. styrene-butadiene rubber(SBR) compsn as claimed in claim 1 is characterized in that:
Said styrene-butadiene rubber(SBR) compsn comprises terminal hydroxy liquid styrene-butadiene rubber(SBR), and its consumption is 1～30 weight part.
7. styrene-butadiene rubber(SBR) compsn as claimed in claim 6 is characterized in that:
The consumption of terminal hydroxy liquid styrene-butadiene rubber(SBR) is 5～15 weight parts.
8. styrene-butadiene rubber(SBR) compsn as claimed in claim 1 is characterized in that:
Said styrene-butadiene rubber(SBR) compsn comprises silane coupling agent, and its consumption is 0.1～5 weight part.
9. like the described styrene-butadiene rubber(SBR) compsn of one of claim 1～8, it is characterized in that:
Said styrene-butadiene rubber(SBR) is oil-extended styrene-butadiene rubber.
10. one kind prepares the described a kind of styrene-butadiene rubber(SBR) preparation of compositions method of one of claim 1～9, it is characterized in that comprising with said component mixing in described ratio.
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| CN104292539A (en) * | 2014-09-19 | 2015-01-21 | 明光瑞泰工业有限公司 | Tread rubber of radial tire |
| CN105175832A (en) * | 2015-09-18 | 2015-12-23 | 山东显元化工研究院有限公司 | Granular SBR (styrene butadiene rubber) and preparation method thereof |
| CN105175829A (en) * | 2014-06-23 | 2015-12-23 | 北京橡胶工业研究设计院 | Rubber composition with low rolling resistance and good wet slippery and wear resistance |
| CN105254957A (en) * | 2015-10-14 | 2016-01-20 | 文登市三峰轮胎有限公司 | Off-the-road tire abrasion-resistant formula and preparation method thereof |
| CN105492523A (en) * | 2013-09-17 | 2016-04-13 | 住友橡胶工业株式会社 | Pneumatic tire |
| CN107778590A (en) * | 2016-08-30 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of poly- styrene-butadiene latex blending of breast uses the method for adjusting physical property |
| CN108291059A (en) * | 2016-11-10 | 2018-07-17 | 株式会社Lg化学 | SBR styrene butadiene rubbers compound and the rubber composition for tyre edge core comprising it |
| EP3327042A4 (en) * | 2015-09-01 | 2018-08-22 | Bridgestone Corporation | Emulsion-polymerized styrene-butadiene rubber, rubber composition, and tire |
| US10137733B2 (en) | 2013-11-20 | 2018-11-27 | Sumitomo Rubber Industries, Ltd. | Pneumatic tire |
| CN114437380A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Modified fully-vulcanized powdered rubber, preparation method thereof and epoxy resin composition thereof |
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