CN103205030A - Application of trans-1,4-polydiene composite rubber in rubber products - Google Patents
Application of trans-1,4-polydiene composite rubber in rubber products Download PDFInfo
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- CN103205030A CN103205030A CN2012100074909A CN201210007490A CN103205030A CN 103205030 A CN103205030 A CN 103205030A CN 2012100074909 A CN2012100074909 A CN 2012100074909A CN 201210007490 A CN201210007490 A CN 201210007490A CN 103205030 A CN103205030 A CN 103205030A
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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 use of a trans-1,4-polydiene composite rubber, and an application formula of the trans-1,4-polydiene composite rubber. The composite rubber is composed of 10-80% by mass of trans-1,4-polyisoprene and 20-90% by mass of a trans-1,4-butadiene-isoprene copolymer, and the copolymer is composed of 0.1-99.9mol% of a butadiene unit and 0.1-99.9mol% by mole of an isoprene unit. The substitution of natural rubber and/or styrene-butadiene rubber and/or butadiene rubber in a tire surface rubber by 5-30 parts of the composite rubber obviously improves the wear resistance of a tire and reduces the rolling resistance. The substitution of natural rubber and/or butadiene rubber in the sidewall rubber of the tire by 5-50 parts of the composite rubber obviously improves the crack increasing resistance of the tire, reduces the rolling resistance and heat generation, and makes the good traction performance of the tire be maintained, so the composite rubber is especially suitable for dynamic use rubber products comprising tires, damping materials and the like, especially tire surface rubber of all-steel radial tires or high duty tires.
Description
Technical field
The invention belongs to the Application Areas of polydiolefin rubber, particularly relate to anti-form-1, the polydiolefin compounded rubber of 4-structure is particularly used in full-steel radial ply or the truck tyre at tire product, belongs to tire material and Rubber processing technical field.
Background technology
The increase day by day of the fast development of motorway and automobile pollution, and people constantly strengthen awareness of safety and the environmental protection ideas of automobile, to doughnut high-performance sizing material, the demand of elastomeric material that particularly has excellent dynamic properties is also more and more stronger.High trans-1,4-polyisoprene (TPI) is though at room temperature be the crystal form plastics, but studies show that, can effectively hang down the crystallization of breaking TPI by sulfuration or with other blend rubber covulcanization, (ZL 95110352.0, ZL200610043556.4) with the elastomerics that obtains to have excellent in resistance flexural property, low-rolling-resistance.This elastomerics dynamic property excellence is suitable for high-performance tire, particularly the tire sidewall glue of low-rolling-resistance, low-heat-generation and fatigue performance excellence and tread rubber elastomeric material.High trans-1 (TPB) has more excellent dynamic properties and wear resistance equally, but because crystallinity is too strong, is difficult to become elastomerics by methods such as above-mentioned blend covulcanization.
Trans butadiene-isoprene copolymer glue has good processing and curability, and with the increase of butadiene structure unit content in the multipolymer, the rebound resilience of copolymer rubber, tensile modulus, tear strength increase gradually, and wear loss reduces.Its cross-linked rubber has low compression heat generation, excellent flex cracking resistance performance and anti-breach increases performance, is the desirable sizing material (China Synthetic Rubber Industry, 2001) of development high-performance tire.
Chinese invention patent (publication number CN102050968A) has been reported a kind of anti-form-1, polydiolefin compounded rubber of 4-structure and preparation method thereof, can fine TPI and TPB homopolymer degree of crystallinity is higher, with problems such as other conventional rubbers and time spent difficult processing.This patent disclosure prepare the anti-form-1 with different The Nomenclature Composition and Structure of Complexes content, the method for the polydiolefin compounded rubber of 4-structure and compounded rubber structure.This compounded rubber is the anti-form-1 of 10-80% by massfraction, and 4-polyisoprene and 20-90% anti-form-1,4-butadiene isoprene copolymer are formed, and the structural unit of all diolefine is trans 1 more than 90% in the compounded rubber, the 4-structure.This compounded rubber is with the low-heat-generation of TPI and the characteristics that rolling resistance is little, life heat is low, wear-resisting, the excellent properties such as antifatigue breach growth property that also have TBIR simultaneously, this patent only performance of, structure synthetic to it and cross-linked rubber is studied, and expection can be used for tread rubber or sidewall rubber, but do not have further its application in tire formulation to be reported.
Anti-form-1, the polydiolefin compounded rubber of 4-structure has possessed various outstanding processing and the use properties of conventional rubber, keep trans poly-diene material excellent dynamic performance and fatigue performance again, in the development high-performance tire, can serve as a kind of novel material of high-quality.
Summary of the invention
The present invention is intended to above-mentioned anti-form-1, the polydiolefin compounded rubber of 4-structure is used for tire tread glue, sidewall rubber and other positions of tire with glue or other rubber items, by reducing rolling resistance and the Sheng Re of tire, improve the fatigue performance of tire, realize energy-saving and emission-reduction and the long lifetime of tire.
Specifically, one of purpose of the present invention is to use anti-form-1 in traditional tire tread glue formulation, the polydiolefin compounded rubber of 4-structure partly substitutes natural rubber (NR) or/and styrene-butadiene rubber(SBR) (SBR) and/or cis-1,4-polybutadiene rubber (BR), on the basis that can satisfy the sizing material basic mechanical performance, improve the wear resistant of sizing material, reduce rolling resistance and Sheng Re, keep hauling ability preferably simultaneously, be applicable to the particularly tread rubber of all-steel radial tyre or truck tyre of rubber tyre;
Two of purpose of the present invention is with anti-form-1 in tire sidewall glue sizing material, the polydiolefin compounded rubber of 4-structure partly substitutes NR and/or BR, can obviously improve the fatigue performance of sizing material and cracking resistance mouth and increase performance, thereby prolong the work-ing life of tire or increase the renovation number of times of tire;
Three of purpose of the present invention is the rest parts at tire, as, add an amount of anti-form-1, the polydiolefin compounded rubber of 4-structure in the sizing materials such as tire shoulder glue, triangle glue, belt glue, hose lining, also can play substituting the part natural rubber and improving some performance, as the effect of flexible resistance etc.
Four of purpose of the present invention is in other rubber items, as adding an amount of anti-form-1 in the goods such as conveying belt, shock spring, the polydiolefin compounded rubber of 4-structure also can play substituting the part natural rubber and improving some performance, as the effect of dynamic fatigue property etc.
Anti-form-1, the polydiolefin compounded rubber of 4-structure adopts the method for description in the aforementioned patent (publication number CN102050968A) to synthesize, the form of compounded rubber is similar to conventional rubber material commonly used in the tire with rerum natura, can carry out blend, also use with conventional rubber material commonly used very easily.
Described anti-form-1, the polydiolefin compounded rubber of 4-structure can with tires such as NR, BR, SBR in conventional rubber carry out blend, and all can adopt Sulfur-accelerator system to vulcanize, anti-form-1 behind the blend covulcanization, the small amount of crystalline of the polydiolefin compounded rubber of 4-structure can be by partial destruction even is destroyed fully, can obtain excellent dynamic properties and flex fatig resistance performance as tire with glue.
Anti-form-1, the polydiolefin compounded rubber of 4-structure is applied to tire tread glue, sidewall rubber and other position glue, as, in the sizing compound formulas such as tire shoulder glue, triangle glue, belt glue, hose lining, except elastomeric material, other conventional auxiliary materials are all identical with original conventional formulation with auxiliary agent.
Described anti-form-1, the polydiolefin compounded rubber of 4-structure is used for tire tread glue formulation, substitute NR or/and SBR and/or BR with this composite gum of 5～30 mass parts, can be on the basis of satisfying the sizing material basic mechanical performance, obviously improve the wear resistant of sizing material, reduce rolling resistance, be applicable to the particularly tread rubber of all-steel radial tyre or truck tyre of rubber tyre.
Described anti-form-1, the polydiolefin compounded rubber of 4-structure is used for tire tread glue formulation, and tread rubber is 100 parts in rubber quality, and its prescription is:
(1) anti-form-1, the polydiolefin compounded rubber of 4-structure is 5～30 mass parts,
(2) all the other rubber are one or both or three kinds in natural rubber, styrene-butadiene rubber(SBR), the cis-1,4-polybutadiene rubber, and total amount is 70～95 mass parts,
(3) other processing aids, strengthening agent and filler are with former conventional formulation.
Wherein, use the anti-form-1 in the tire tread glue formulation, the polydiolefin compounded rubber of 4-structure is characterized in that, this compounded rubber is the anti-form-1 of 10-80% by massfraction, 4-polyisoprene and 20-90% anti-form-1, the 4-butadiene isoprene copolymer is formed, and the structural unit of all diolefine is trans 1 more than 90% in the compounded rubber, the 4-structure.Multipolymer is that the butadiene unit of 0.1-99.9% and the isoprene unit of 0.1-99.9% are formed by molar fraction.
Described anti-form-1, the polydiolefin compounded rubber of 4-structure is used for tire sidewall glue prescription, substitute natural rubber and/or cis-1,4-polybutadiene rubber with this composite gum of 5～50 mass parts, can obviously improve the fatigue performance of sizing material and cracking resistance mouth and increase performance, thereby prolong the work-ing life of tire or increase the renovation number of times of tire.
Described anti-form-1, the polydiolefin compounded rubber of 4-structure are used for tire sidewall glue prescription, and sidewall rubber is 100 parts in rubber quality, and its prescription is:
(1) anti-form-1, the polydiolefin compounded rubber of 4-structure is 5～50 mass parts,
(2) all the other rubber are one or both in natural rubber, the cis-1,4-polybutadiene rubber, and total amount is 50～95 mass parts,
(3) other processing aids, strengthening agent and filler are with former conventional formulation.
Wherein, use the anti-form-1 in the tire sidewall glue prescription, the polydiolefin compounded rubber of 4-structure is characterized in that, this compounded rubber is the anti-form-1 of 10-80% by massfraction, 4-polyisoprene and 20-90% anti-form-1, the 4-butadiene isoprene copolymer is formed, and the structural unit of all diolefine is trans 1 more than 90% in the compounded rubber, the 4-structure.Multipolymer is that the butadiene unit of 0.1-99.9% and the isoprene unit of 0.1-99.9% are formed by molar fraction.
Described anti-form-1, the polydiolefin compounded rubber of 4-structure is applied to other parts of tire, as, add an amount of anti-form-1 in the sizing materials such as tire shoulder glue, triangle glue, belt glue, hose lining, the polydiolefin compounded rubber of 4-structure also can play the effect that substitutes the part natural rubber and improve some performance.
Anti-form-1, the polydiolefin compounded rubber of 4-structure are applied in other rubber items except tire, as, rubber conveyer belt in the sizing materials such as rubber damper, also can play the effect that substitutes the part natural rubber and improve some performance.
Specific embodiment
Utilize embodiment that excellent results of the present invention is described, under the situation that does not exceed purport of the present invention, these embodiment do not constitute any restriction to the present invention.
Anti-form-1, the polydiolefin compounded rubber of 4-structure adopts the method for description in the aforementioned patent (publication number CN102050968A) to synthesize, and the monomer structure unit content that its physical index sees Table in 1. these rubber can carry out the technology regulation and control by needs with colloidality according to the tire different sites.
Table 1 anti-form-1, the polydiolefin compounded rubber physical and mechanical property of 4-structure
Comparative Examples 1
100 parts of NR are opened refining in two roller mills, according to tire tread glue tradition basic components, other auxiliary agents are: 55 parts of carbon black N220,3.5 parts in zinc oxide, 2 parts of stearic acid, 1.2 parts of accelerator NSs, 1.2 parts of Sulfurs, 1.5 parts of antioxidant 4010s, 1.5 parts of anti-aging agent RE, 5 parts of aromatic hydrocarbon oil, 0.2 part of anti-scorching agent CTP.The physical and mechanical property of cross-linked rubber is measured in following sheet and sulfuration back, lists in table 2.
Embodiment 1～4
With 95 parts of NR and 5 parts of different anti-form-1s, the polydiolefin compounded rubber of 4-structure mixes in two roller mills, and according to tire tread glue tradition basic components, other auxiliary agents are: 55 parts of carbon black N220,3.5 parts in zinc oxide, 2 parts of stearic acid, 1.2 parts of accelerator NSs, 1.2 parts of Sulfurs, 1.5 parts of antioxidant 4010s, 1.5 parts of anti-aging agent RE, 5 parts of aromatic hydrocarbon oil, 0.2 part of anti-scorching agent CTP.The physical and mechanical property of cross-linked rubber is measured in following sheet and sulfuration back, lists in table 2.
Embodiment 5～8
With 90 parts of NR and 10 parts of different anti-form-1s, the polydiolefin compounded rubber of 4-structure mixes in two roller mills, and according to tire tread glue tradition basic components, other auxiliary agents are: 55 parts of carbon black N220,3.5 parts in zinc oxide, 2 parts of stearic acid, 1.2 parts of accelerator NSs, 1.2 parts of Sulfurs, 1.5 parts of antioxidant 4010s, 1.5 parts of anti-aging agent RE, 5 parts of aromatic hydrocarbon oil, 0.2 part of anti-scorching agent CTP.The physical and mechanical property of cross-linked rubber is measured in following sheet and sulfuration back, lists in table 2.
Table 2 anti-form-1, the polydiolefin compounded rubber of 4-structure and NR are also with blend sulfurized colloidality energy
As can be seen from Table 2, use anti-form-1, the polydiolefin compounded rubber of 4-structure partly substitutes the NR in the tread glue formula, and blended rubber 100% stretches surely, 300% stretch surely and tensile strength all improves than Comparative Examples, and the tear strength of part embodiment improves than Comparative Examples 1.It is highly important that the DN of embodiment abrasion all reduce than Comparative Examples 1, show and with behind the compounded rubber, the wear resistance of cross-linked rubber improves, can prolong the work-ing life of goods.
Comparative Examples 2
NR and BR mix in two roller mills by mass ratio 50: 50, and according to tire sidewall glue tradition basic components, other auxiliary agents are: 50 parts of carbon black N330,5 parts in zinc oxide, 2.5 parts of stearic acid, 0.9 part of accelerant CZ, 1 part of Microcrystalline Wax, 2 parts of Sulfurs, 2 parts of antioxidant 4010s, 4,020 1 parts in anti-aging agent, 1 part of anti-aging agent RE, 7 parts of aromatic hydrocarbon oil, 0.2 part of anti-scorching agent CTP.The physical and mechanical property of cross-linked rubber is measured in following sheet and sulfuration back, lists in table 3.
Embodiment 9～11
NR, BR and anti-form-1, the polydiolefin compounded rubber of 4-structure mixes in two roller mills, according to tire sidewall glue tradition basic components, other auxiliary agents are: 50 parts of carbon black N330,5 parts in zinc oxide, 2.5 parts of stearic acid, 0.9 part of accelerant CZ, 1 part of Microcrystalline Wax, 2 parts of Sulfurs, 2 parts of antioxidant 4010s, 4,020 1 parts in anti-aging agent, 1 part of anti-aging agent RE, 7 parts of aromatic hydrocarbon oil, 0.2 part of anti-scorching agent CTP.The physical and mechanical property of cross-linked rubber is measured in following sheet and sulfuration back, lists in table 3.
Table 3 anti-form-1, the polydiolefin compounded rubber of 4-structure and NR, BR are also with blend sulfurized colloidality energy
As can be seen from Table 3, use anti-form-1, the polydiolefin compounded rubber of 4-structure partly substitutes NR and the BR in the sidewall rubber prescription, blended rubber 100% stretches surely, 300% stretch surely and tensile strength does not have notable difference than Comparative Examples, still keep level preferably, and use anti-form-1, the cross-linked rubber of the polydiolefin compounded rubber of 4-structure has better flexing fatigue performance, compresses permanentset simultaneously and also reduces.
Claims (8)
1. anti-form-1, the polydiolefin compounded rubber of 4-structure, it is characterized in that, this compounded rubber is the anti-form-1 of 10-80% by massfraction, 4-polyisoprene and 20-90% anti-form-1, the 4-butadiene isoprene copolymer is formed, and the structural unit of all diolefine is trans 1 more than 90% in the compounded rubber, the 4-structure.Multipolymer is that the butadiene unit of 0.1-99.9% and the isoprene unit of 0.1-99.9% are formed by molar fraction.
2. anti-form-1, the polydiolefin compounded rubber of 4-structure, it is characterized in that, the antifatigue of the existing trans butadiene isoprene copolymer excellence of this composite gum and cracking resistance mouth increase performance, anti-form-1 is arranged again, 4-polyisoprene and anti-form-1, characteristics such as the rolling resistance of 4-polybutadiene homopolymer is low, wear resistance is good.This composite gum is owing to contain anti-form-1 simultaneously, the 4-butadiene isoprene copolymer, and degree of crystallinity reduces, and processing characteristics is than anti-form-1,4-polyisoprene and anti-form-1, the 4-polybutadiene homopolymer is obviously improved, and makes it be easy to refine glue and dispersion.Therefore be suitable for the high-performance tire preparation.
3. according to claim 1 and 2 described a kind of anti-form-1s, the polydiolefin compounded rubber of 4-structure, it is characterized in that, this compounded rubber can be applicable in the tire tread glue, on the basis of satisfying the sizing material basic mechanical performance, obviously improve the wear resistant of sizing material, reduce rolling resistance, be applicable to the particularly tread rubber of all-steel radial tyre or truck tyre of rubber tyre.
4. according to claim 3, it is characterized in that described tire tread glue, be 100 parts in rubber quality, its prescription is:
(1) anti-form-1, the polydiolefin compounded rubber of 4-structure is 5～30 mass parts,
(2) all the other rubber are one or both or three kinds in natural rubber, styrene-butadiene rubber(SBR), the cis-1,4-polybutadiene rubber, and total amount is 70～95 mass parts,
(3) other processing aids, strengthening agent and filler are with former conventional formulation.
5. according to claim 1 and 2 described any one anti-form-1s, the polydiolefin compounded rubber of 4-structure, it is characterized in that, this compounded rubber can be applicable in the tire sidewall glue, the fatigue performance and the cracking resistance mouth that obviously improve sizing material increase performance, thereby prolong the work-ing life of tire or increase the renovation number of times of tire.
6. according to claim 5, it is characterized in that described tire sidewall glue, be 100 parts in rubber quality, its prescription is:
(1) anti-form-1, the polydiolefin compounded rubber of 4-structure is 5～50 mass parts,
(2) all the other rubber are one or both in natural rubber, the cis-1,4-polybutadiene rubber, and total amount is 50～95 mass parts,
(3) other processing aids, strengthening agent and filler are with former conventional formulation.
7. according to claim 1 and 2 described any one anti-form-1s, the polydiolefin compounded rubber of 4-structure, it is characterized in that, this composite gum can be applicable to the rest part of tire, in sizing materials such as tire shoulder glue, triangle glue, belt glue, hose lining, also can play the effect that substitutes the part natural rubber and improve some performance.
8. according to claim 1 and 2 described any one anti-form-1s, the polydiolefin compounded rubber of 4-structure, it is characterized in that, this composite gum can be applicable in other rubber items except tire, as, rubber conveyer belt in the sizing materials such as rubber damper, plays the effect that substitutes the part natural rubber and improve some performance.
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| CN201210007490.9A CN103205030B (en) | 2012-01-12 | 2012-01-12 | Anti-form-1, the application in rubber of the 4-polydiene compounded rubber |
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| CN201210007490.9A CN103205030B (en) | 2012-01-12 | 2012-01-12 | Anti-form-1, the application in rubber of the 4-polydiene compounded rubber |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910452A (en) * | 2015-05-20 | 2015-09-16 | 青岛科技大学 | Rubber material with high crack growth resistance, and preparation method thereof |
| CN105348586A (en) * | 2015-12-16 | 2016-02-24 | 济南昊泽环保科技有限公司 | Deflection resistant damping rubber |
| CN109181027A (en) * | 2018-09-07 | 2019-01-11 | 山东华聚高分子材料有限公司 | A kind of high-performance tire tread rubber and preparation method thereof |
| US10308792B2 (en) * | 2013-10-08 | 2019-06-04 | The Goodyear Tire & Rubber Company | Rubbery blend containing trans isoprene-butadiene copolymer |
| CN109880198A (en) * | 2019-02-26 | 2019-06-14 | 山东华聚高分子材料有限公司 | A kind of car green tire tread glue formula and preparation method thereof |
| CN109942910A (en) * | 2019-03-21 | 2019-06-28 | 山东华聚高分子材料有限公司 | A kind of high flexing fatigue service life aviation sidewall rubber, preparation method and application |
| CN110157056A (en) * | 2019-07-02 | 2019-08-23 | 江苏通用科技股份有限公司 | A kind of All-steel tire matrix formula and preparation method thereof |
| CN110452426A (en) * | 2019-08-23 | 2019-11-15 | 山东华聚高分子材料有限公司 | A kind of runflat sidewall support glue and preparation method thereof |
| CN112210054A (en) * | 2019-07-09 | 2021-01-12 | 中国石油化工股份有限公司 | Tire sidewall rubber material based on block distribution lithium system BIR and preparation method |
| CN112210040A (en) * | 2019-07-09 | 2021-01-12 | 中国石油化工股份有限公司 | Wide-distribution polybutadiene-isoprene rubber and preparation method thereof |
| CN113667195A (en) * | 2021-08-24 | 2021-11-19 | 青岛科技大学 | High-wear-resistance tire tread rubber and preparation method thereof |
| CN114276588A (en) * | 2021-11-19 | 2022-04-05 | 浙江威格尔传动股份有限公司 | Anti-cracking low-temperature synchronous belt and manufacturing method thereof |
| CN115304827A (en) * | 2022-06-20 | 2022-11-08 | 山东玲珑轮胎股份有限公司 | Trans-butyl-pentyl rubber apex for tire and preparation method thereof |
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| US10308792B2 (en) * | 2013-10-08 | 2019-06-04 | The Goodyear Tire & Rubber Company | Rubbery blend containing trans isoprene-butadiene copolymer |
| CN104910452A (en) * | 2015-05-20 | 2015-09-16 | 青岛科技大学 | Rubber material with high crack growth resistance, and preparation method thereof |
| CN105348586A (en) * | 2015-12-16 | 2016-02-24 | 济南昊泽环保科技有限公司 | Deflection resistant damping rubber |
| CN109181027A (en) * | 2018-09-07 | 2019-01-11 | 山东华聚高分子材料有限公司 | A kind of high-performance tire tread rubber and preparation method thereof |
| CN109880198A (en) * | 2019-02-26 | 2019-06-14 | 山东华聚高分子材料有限公司 | A kind of car green tire tread glue formula and preparation method thereof |
| CN109942910A (en) * | 2019-03-21 | 2019-06-28 | 山东华聚高分子材料有限公司 | A kind of high flexing fatigue service life aviation sidewall rubber, preparation method and application |
| CN109942910B (en) * | 2019-03-21 | 2021-09-24 | 山东华聚高分子材料有限公司 | Aviation sidewall rubber with long flexing fatigue life, and preparation method and application thereof |
| CN110157056A (en) * | 2019-07-02 | 2019-08-23 | 江苏通用科技股份有限公司 | A kind of All-steel tire matrix formula and preparation method thereof |
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| CN112210040A (en) * | 2019-07-09 | 2021-01-12 | 中国石油化工股份有限公司 | Wide-distribution polybutadiene-isoprene rubber and preparation method thereof |
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