CN102952296A - High vinyl polybutadiene oil-extended rubber and preparation method thereof - Google Patents
High vinyl polybutadiene oil-extended rubber and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high vinyl polybutadiene oil-extended rubber and a preparation method thereof, relating to the field of synthetic rubber. The preparation method comprises the steps of: adding a branched high vinyl polybutadiene rubber latex and extending oil by using a wet method; after oil extending, stirring for 2-4h; and condensing and drying to prepare the high vinyl polybutadiene oil-extended rubber, wherein the weight ratio of an oil extending amount of extending oil to dry glue is (33-45)g: 100g, and the conversion rate of a polymerizing kettle is not less than 80%; the mooney viscosity ML(1+4) 100 DEG C of the prepared crude rubber is 30-50; the mooney viscosity ML(1+4) 100 DEG C of the vulcanized rubber obtained from the vulcanization formula is 50-80; the tensile strength is (12-18)MPa; the tearing strength is (30-40)MPa; and the elongation at rupture is 350-500%. The high vinyl polybutadiene oil-extended rubber is used in the tread rubber of tires, so that the slip resistance wet, the wear resistance and the aging property of the tires are improved, and the themogenesis of the tread rubber is obviously reduced; meanwhile, the high vinyl polybutadiene oil-extended rubber has excellent processability, and is easily mixed with various compounding agents during processing; and the rubber milling time is shortened, the energy consumption is reduced, and the production capability is improved.
Description
Technical field
High vinyl polybutadiene oil-extended rubber and preparation method thereof, belong to synthesis of polymer material and preparing technical field, relate to the synthetic rubber field, specially referring to the molybdenum that has vinyl group pendant on 1,2-polyhutadiene molecular backbone chain is the oil-filled glue virgin rubber kind that high vinyl polybutadiene rubber carries out oil-filled preparation.
Background technology
Qingdao University of Science and Technology and asphalt in Shenli Refinery rubber plant cooperation contain the novel high vinyl polybutadiene of branched structure.Contain the high vinyl polybutadiene of branched structure by in polymerization system, adding the structure modifier preparation, and do not produce excessive gel＜0.5%; The catalytic activity that keeps simultaneously original catalyst system, the characteristics of the high-vinyl-content of polymerisate 〉=75%.By the branched modification to polymkeric substance, the kinetic viscosity of polyreaction glue reduces and the polymer processing performance improves.Be on the basis of high vinyl polybutadiene at molybdenum, adjust and add the plasticity that an amount of extending oil can improve rubber after prescription improves its mooney viscosity, reduce viscosity and the melting temperature of rubber, power consumption when refining is rolled in saving, reduce hardness and the cost of cross-linked rubber, and can improve dispersion and the mixed effect of other Synergist S-421 95s, improve Rubber Yield.
Along with the development of automotive industry, the tire technology development priority is paid close attention to two aspect problems, the one, REACH rules, the 2nd, tire new logo.The performance of this glue kind meets the at present domestic and international rolling resistance low to riding tyre surface (burning consumes) and the excellent more and more higher requirement of wet-sliding resistant performance (driving safety), by 1, the HVPB new variety of 2 polyhutadiene are used for the optimization of tire tread glue sulfurizing formula, develop the prescription of the tire tread glue of excellent combination property, for applying of this glue kind provides technical support.The oil-filled glue of high vinyl polybutadiene of preparation has the advantages such as anti-slippery is good, ageing-resistant, low-heat-generation, simultaneously also can under the nickel system prerequisite substantially constant along processing condition on the production line of fourth, realize that molybdenum is the production of high vinyl polybutadiene oil-extended rubber.
After the consulting of document data, we find that both at home and abroad the research report that not institution of higher learning, scientific research institutions do not carry out the poly-fourth two oil-filled alkene glue of high-vinyl occurs.More without suitability for industrialized production.Thereby to carry out molybdenum be that the development of oil-extended high vinyl polybutadiene rubber helps to form independent intellectual property right, promotes the capability of independent innovation of rubber new material industry, and the upgrading of traditional material industry is had good pushing effect.
Summary of the invention
The technical problem to be solved in the present invention is: overcome the deficiencies in the prior art, provide a kind of anti-slippery good with ageing-resistant performance, simultaneously life heat is low and have excellent machinability, adds high vinyl polybutadiene oil-extended rubber that easily mixes with various Synergist S-421 95s man-hour and preparation method thereof.
Technical scheme of the present invention is: a kind of high vinyl polybutadiene oil-extended rubber, it is characterized in that: adopt the wet method mode by branched high vinyl polybutadiene rubber glue and extending oil, oil-filled rear stirring 2～4h, make through condensing drying again, oil-filled amount (weight ratio) is the dried glue of (33～45) g extending oil: 100g, makes 100 ℃ of the mooney viscosity ML (1+4) of rubber: 30～50; 100 ℃ of the mooney viscosity ML (1+4) of sulfurizing formula gained cross-linked rubber: 50～80; Tensile strength (12～18) MPa; Tear strength: (30～40) MPa; Tensile yield is 350%～500%.
Described extending oil is selected a kind of in naphthenic oil, high aromatic oil (DAE) or the low condensed-nuclei aromatics content aromatic hydrocarbon oil (TDAE).
Described branched high vinyl polybutadiene rubber glue is preheating to 60 ℃ by the monomer divinyl in the C6 solvent, add again Primary Catalysts and promotor, at polymeric kettle internal reaction 3～5h, make after condensing drying, described Primary Catalysts is for being done the molybdenum series catalyst of part and MoCl5 reaction preparation by tbp again; Promotor is the aluminium agent catalyzer of meta-cresol and the preparation of triisobutyl reactive aluminum.
Described branched high vinyl polybutadiene rubber glue gelatin viscosity (under 40 ℃) is (2～6) * 10
4MPa.S, 100 ℃ of mooney viscosity ML (1+4) they are 90～150,1,2-structural content 〉=70%, and gel content is less than or equal to 1%.
Preferably, in the described branched high vinyl polybutadiene rubber glue 1,2-structural content 〉=75%, gel content 0.3%～0.5%.
The preparation method of this high vinyl polybutadiene oil-extended rubber is characterized in that, comprises following processing step:
1, solution polymerization process prepares the branched high vinyl polybutadiene rubber glue: the monomer divinyl is preheating to 60 ℃ in the C6 solvent, add again Primary Catalysts, promotor and structure modifier, at polymeric kettle internal reaction 3～5h, after condensing drying, make again the single still transformation efficiency of polymerization 〉=80%; Primary Catalysts is that tbp is part and MoCl
5The molybdenum series catalyst of reaction preparation; Promotor is the aluminium agent catalyzer with meta-cresol and the preparation of triisobutyl reactive aluminum;
2, adopt the wet method mode to prepare high vinyl polybutadiene oil-extended rubber glue: ring type filling alkane oil, high aromatic oil or low condensed-nuclei aromatics content aromatic hydrocarbon oil in the branched high vinyl polybutadiene rubber glue, oil-filled rear stirring 2～4h prepares the oil-filled glue of high-vinyl;
3, adopt the elutriation coacervation, make oil-extended rubber through extruding, dehydration, drying.
This high vinyl polybutadiene oil-extended rubber is used for making tire tread.But Effective Raise tire anti-slippery, wear resistance, aging resistance can also make the heat of giving birth to of tread rubber obviously reduce, and have simultaneously good processing characteristics, shorten the refining glue time, reduce energy consumption, improve throughput.
This branched high vinyl polybutadiene rubber glue is characterized in that: gelatin viscosity (under 40 ℃) is (2～6) * 10
4MPa.S, 100 ℃ of mooney viscosity ML (1+4) they are 90～150,1,2-structural content 〉=70%, and gel content is less than or equal to 1%.
Preferably, in the rubber glue 1,2-structural content 〉=75%, gel content 0.3%～0.5%.
The preparation method of this branched high vinyl polybutadiene rubber glue, it is characterized in that: monomer divinyl and branching agent are preheating to 60 ℃ in the C6 solvent, add Primary Catalysts, promotor and structure modifier, at polymeric kettle internal reaction 3～5h, after condensing drying, make again the single still transformation efficiency of polymerization 〉=80%; Primary Catalysts is that tbp is part and MoCl
5The molybdenum series catalyst of reaction preparation; Promotor is the aluminium agent catalyzer with meta-cresol and the preparation of triisobutyl reactive aluminum.Used branching agent and structure modifier are the industry universal product.
Branched high vinyl polybutadiene rubber (BHVPBR) adopts the molybdenum series catalyst preparation.Be the preparation of BHVPBR about molybdenum, the Chinese patent CN1884328A (applicant Qingdao University of Science and Technology) of application discloses concrete preparation technology and technology in detail before the contriver.The present invention from that invent unique different be that the used part of promotor has different.Disclosed Primary Catalysts part N among the patent CN1884328A, N-bipyridine, triphenylphosphine or tetramethyl-diamines, and the part that uses among the present invention is tbp.Used part mainly is based on the consideration of cost before replacing, and usage quantity is consistent, to synthetic the having little significance of BHVPBR, so BHVPBR is not the present invention's main idea place.The present invention focuses in the application of the oil-filled glue of BHVPBR development of new high vinyl polybutadiene.
The parameter of materialss such as the character of side chain, length, distribution, the degree of branching have very close contact in the physical and mechanical properties of branched high vinyl polybutadiene rubber and processing characteristics and ATRP (atom transfer radical polymerization) and coordination composite polymeric parameter and the branch high polymer.Therefore, the polymkeric substance of branched modification can be by the degree of regulating branching and physical and mechanical properties and the processing characteristics that branched structure improves polymkeric substance.About this point, in patent CN1884328A, developing, the present invention will not give unnecessary details at this.
This technology adopts solution polymerization process, and take divinyl as monomer, carbon six oil are solvent, are part and MoCl with phosphorous compound tbp
5The catalyzer of reaction preparation is Primary Catalysts, and preparing aluminium agent catalyzer with meta-cresol and triisobutyl reactive aluminum is promotor, adds the high vinyl polybutadiene basis glue that the structure modifier preparation contains branched structure in polymerization system.For reaching the purpose of reasonable adjustment glue kind performance, the branched high vinyl polybutadiene rubber of selecting (BHVPBR) is characterised in that: the single still transformation efficiency of polymerization: 〉=80%; Gelatin viscosity (40 ℃): (2-6) * 10
4MPa.S; 100 ℃ of mooney viscosity ML (1+4): 90～150; 1,2 structural content: 〉=70%; Gel content: be not higher than 1%.
Basic glue is carried out oil-filled, oil-filled 33～43 grams of oil-filled amount 100 gram glue, 100 ℃ of the crude rubber Mooney viscosity ML (1+4) that makes: 30～50; 100 ℃ of the mooney viscosity ML (1+4) of sulfurizing formula gained cross-linked rubber: 50～80; Tensile strength 12～18MPa; Tear strength: 30～40MPa; Tensile yield is between 350～500%.Gelatin viscosity (40 ℃): (2～6) * 10
4MPa.S; 1,2 structural content: 〉=75%; Gel content: be not higher than 1%.
The basic glue of preparation high vinyl polybutadiene oil-extended rubber is the consumption etc. by adjusting Al/Mo, Mo/Bd, temperature of reaction and branching agent, regulates the prescription preparation.Be to be filled with naphthenic oil, high aromatic oil (DAE), low condensed-nuclei aromatics content aromatic hydrocarbon oil (TDAE) extending oil in the glue of high vinyl polybutadiene basis at molybdenum, adopt the wet method mode, the high-vinyl oil-extended rubber was prepared in oil-filled rear stirring in 4 hours.Owing in polymerization system, adding structure modifier, carry out oil-filled to high vinyl polybutadiene basis glue, effectively reducing molybdenum is the gelatin viscosity of high vinyl polybutadiene oil-extended rubber, reduced wall built-up and the obstruction of glue in mobile or course of conveying, so just can produce along the fourth production equipment in the nickel system of changing a little.
Compared with prior art, the beneficial effect that high vinyl polybutadiene oil-extended rubber of the present invention and preparation method thereof has is: adjust the structure of structure modifier according to prior art, make it realize that along the fourth production equipment molybdenum is the production of oil-extended high vinyl polybutadiene rubber in the nickel system of changing a little.The high vinyl polybutadiene oil-extended rubber is used for tire tread glue, tire anti-slippery, wear resistance and ageing resistance have not only been improved, and the heat of giving birth to of tread rubber obviously reduces, has simultaneously good processing characteristics, add and easily mix with various Synergist S-421 95s man-hour, shorten the refining glue time, reduce energy consumption, improve throughput.Being oil-filled glue and the performance of oil-filled glue kind commonly used for characterizing molybdenum, is the oil-filled glue of high vinyl polybutadiene with BR9053, BR9073 laboratory product performance test result as showing with this molybdenum:
| Project | Molybdenum is oil-filled glue | BR9053 | BR9073 |
| Tensile strength/MPa | 18.7 | 14.5 | 17.1 |
| 300% stress at definite elongation/MPa | 17.9 | 12.6 | |
| Tensile yield/% | 313.0 | 409 | 401 |
| Shao A hardness | 72 | 66 |
As seen from the above table, the virgin rubber kind superior performance take BHVPBR as development of raw materials can satisfy actual needs.
Embodiment
Embodiment 1
The preparation process of this kind high vinyl polybutadiene oil-extended rubber is: adopt the wet method mode oil-filled the naphthenic oil of 100 parts high vinyl polybutadiene glues and 33 parts, oil-filled rear stirring 2～4h cohesion drying makes.Described branched high vinyl polybutadiene rubber (BHVPBR) gelatin viscosity (under 40 ℃) is 4 * 10
4MPa.S, 100 ℃ of mooney viscosity ML (1+4) are 100,1,2-structural content 75%, gel content 1%.
The preparation process of concrete branched high vinyl polybutadiene rubber (BHVPBR) glue is: by the monomer divinyl, add the liquid polybutadiene as branching agent, be preheating to 60 ℃, add by tbp again and be part and MoCl
5The aluminium agent catalyzer of the molybdenum series catalyst of reaction preparation and meta-cresol and the preparation of triisobutyl reactive aluminum makes at polymeric kettle internal reaction 3～5h and after condensing drying.
100 ℃ of the crude rubber Mooney viscosity ML (1+4) of the oil-filled tire tread glue of gained: 40; 100 ℃ of the mooney viscosity ML (1+4) of sulfurizing formula gained cross-linked rubber: 60.The performance of embodiment products obtained therefrom and compare with BR9053 and these two kinds oil-filled glue kinds of BR9073 sees Table 1.
Table 1 embodiment products obtained therefrom performance and with the contrast of existing two kinds of oil-filled glue kinds
By 1 table as can be known, with existing oil-filled glue contrast, the oil-filled glue of producing according to this invention has not only improved tire anti-slippery, wear resistance and ageing resistance for the preparation of tire tread, the heat of giving birth to of tread rubber is obviously reduced, has simultaneously good processing characteristics, shorten the refining glue time, reduce energy consumption, improve throughput.
Embodiment 2～6
The composition of embodiment 2～6 described high vinyl polybutadiene oil-extended rubber and the performance of used BHVPBR see Table 2.
Concrete preparation method is with embodiment 1.
The composition of table 2 embodiment 2～6 high vinyl polybutadiene oil-extended rubber and the performance of BHVPBR
100 ℃ of embodiment 2 gained high vinyl polybutadiene oil-extended rubber crude rubber Mooney viscosity ML (1+4): 50; 100 ℃ of the mooney viscosity ML (1+4) of sulfurizing formula gained cross-linked rubber: 80, tensile strength 18MPa; Tear strength: 30MPa, tensile yield is 350%;
100 ℃ of embodiment 3 gained high vinyl polybutadiene oil-extended rubber crude rubber Mooney viscosity ML (1+4): 45; 100 ℃ of the mooney viscosity ML (1+4) of sulfurizing formula gained cross-linked rubber: 75, tensile strength 15MPa; Tear strength: 32MPa, tensile yield is 350%;
100 ℃ of embodiment 4 gained high vinyl polybutadiene oil-extended rubber crude rubber Mooney viscosity ML (1+4): 40; 100 ℃ of the mooney viscosity ML (1+4) of sulfurizing formula gained cross-linked rubber: 70, tensile strength 15MPa; Tear strength: 32MPa, tensile yield is 400%;
100 ℃ of embodiment 5 gained high vinyl polybutadiene oil-extended rubber crude rubber Mooney viscosity ML (1+4): 35; 100 ℃ of the mooney viscosity ML (1+4) of sulfurizing formula gained cross-linked rubber: 60, tensile strength 13MPa; Tear strength: 35MPa, tensile yield is 450%;
100 ℃ of embodiment 6 gained high vinyl polybutadiene oil-extended rubber crude rubber Mooney viscosity ML (1+4): 30; 100 ℃ of the mooney viscosity ML (1+4) of sulfurizing formula gained cross-linked rubber: 50, tensile strength 12MPa; Tear strength: 40MPa, tensile yield is 500%.
The performance of embodiment 2～6 gained high vinyl polybutadiene oil-extended rubber, comprise that tensile strength, 300% stress at definite elongation, tensile yield, wear loss, wet-sliding resistant performance, rebound performance, compression heat generation etc. are all similar to embodiment 1 products obtained therefrom performance, therefore be not described in detail at this.
The above only is preferred embodiment of the present invention, is not to be the restriction of invention being made other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But every technical solution of the present invention content that do not break away to any simple modification, equivalent variations and remodeling that above embodiment does, still belongs to the protection domain of technical solution of the present invention according to technical spirit of the present invention.
Claims (10)
1. high vinyl polybutadiene oil-extended rubber, it is characterized in that: adopt the wet method mode by branched high vinyl polybutadiene rubber glue and extending oil, oil-filled rear stirring 2～4h, make through condensing drying again, oil-filled amount (weight ratio) is the dried glue of (33～45) g extending oil: 100g, makes 100 ℃ of the mooney viscosity ML (1+4) of rubber: 30～50; 100 ℃ of the mooney viscosity ML (1+4) of sulfurizing formula gained cross-linked rubber: 50～80; Tensile strength (12～18) MPa; Tear strength: (30～40) MPa; Tensile yield is 350%～500%.
2. high vinyl polybutadiene oil-extended rubber according to claim 1 is characterized in that: described extending oil is selected a kind of in naphthenic oil, high aromatic oil (DAE) or the low condensed-nuclei aromatics content aromatic hydrocarbon oil (TDAE).
3. high vinyl polybutadiene oil-extended rubber according to claim 1, it is characterized in that: described branched high vinyl polybutadiene rubber glue is preheating to 60 ℃ by the monomer divinyl in the C6 solvent, add again Primary Catalysts and promotor, at polymeric kettle internal reaction 3～5h, make after condensing drying, described Primary Catalysts is for being done the molybdenum series catalyst of part and MoCl5 reaction preparation by tbp again; Promotor is the aluminium agent catalyzer of meta-cresol and the preparation of triisobutyl reactive aluminum.
4. it is characterized in that according to claim 1 or 3 described high vinyl polybutadiene oil-extended rubber: described branched high vinyl polybutadiene rubber glue gelatin viscosity (under 40 ℃) is (2～6) * 10
4MPa.S, 100 ℃ of mooney viscosity ML (1+4) they are 90～150,1,2-structural content 〉=70%, and gel content is less than or equal to 1%.
5. high vinyl polybutadiene oil-extended rubber according to claim 4 is characterized in that: in the described branched high vinyl polybutadiene rubber glue 1, and 2-structural content 〉=75%, gel content 0.3%～0.5%.
6. the preparation method of high vinyl polybutadiene oil-extended rubber is characterized in that, comprises following processing step:
6.1 the monomer divinyl is preheating to 60 ℃ in the C6 solvent, add again Primary Catalysts, promotor and structure modifier, at polymeric kettle internal reaction 3～5h, after condensing drying, make again; Primary Catalysts is that tbp is part and MoCl
5The molybdenum series catalyst of reaction preparation; Promotor is the aluminium agent catalyzer with meta-cresol and the preparation of triisobutyl reactive aluminum;
6.2 ring type filling alkane oil, high aromatic oil or low condensed-nuclei aromatics content aromatic hydrocarbon oil in the branched high vinyl polybutadiene rubber glue, oil-filled rear stirring 2～4h prepares the oil-filled glue of high-vinyl;
6.3 adopt the elutriation coacervation, make oil-extended rubber through extruding, dehydration, drying.
7. each described high vinyl polybutadiene oil-extended rubber is used for making tire tread according to claim 1～3.
8. branched high vinyl polybutadiene rubber glue is characterized in that: gelatin viscosity (under 40 ℃) is (2～6) * 10
4MPa.S, 100 ℃ of mooney viscosity ML (1+4) they are 90～150,1,2-structural content 〉=70%, and gel content is less than or equal to 1%.
9. branched high vinyl polybutadiene rubber glue according to claim 8 is characterized in that: in the rubber glue 1, and 2-structural content 〉=75%, gel content 0.3%～0.5%.
10. according to claim 8 or the preparation method of 9 described branched high vinyl polybutadiene rubber glues, it is characterized in that: the monomer divinyl is preheating to 60 ℃ in the C6 solvent, add Primary Catalysts, promotor and structure modifier, at polymeric kettle internal reaction 3～5h, after condensing drying, make again, the single still transformation efficiency of polymerization 〉=80%, Primary Catalysts is that tbp is part and MoCl
5The molybdenum series catalyst of reaction preparation; Promotor is the aluminium agent catalyzer with meta-cresol and the preparation of triisobutyl reactive aluminum.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105199028A (en) * | 2015-09-12 | 2015-12-30 | 青岛科技大学 | High vinyl polybutadiene rubber capable of adjusting microstructure and preparation method thereof |
| CN105295128A (en) * | 2014-06-06 | 2016-02-03 | 中国石油化工股份有限公司 | Rubber composition for high-speed energy-saving tire tread |
| CN105324429A (en) * | 2013-07-05 | 2016-02-10 | 住友橡胶工业株式会社 | Tire rubber composition and pneumatic tire |
| CN106317281A (en) * | 2015-06-17 | 2017-01-11 | 中国石油化工股份有限公司 | Production method of thermostable high-vinyl butadiene rubber |
| CN108610457A (en) * | 2018-05-28 | 2018-10-02 | 青岛科技大学 | A kind of preparation method of siliceous high vinyl polybutadiene |
| CN110724317A (en) * | 2018-07-16 | 2020-01-24 | 中国石油化工股份有限公司 | Environment-friendly tire side rubber material |
| CN115806741A (en) * | 2021-09-14 | 2023-03-17 | 中国石油化工股份有限公司 | Filling oil for styrene butadiene rubber and preparation method thereof |
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| US9994699B2 (en) | 2013-07-05 | 2018-06-12 | Sumitomo Rubber Industries, Ltd. | Tire rubber composition and pneumatic tire |
| CN105324429A (en) * | 2013-07-05 | 2016-02-10 | 住友橡胶工业株式会社 | Tire rubber composition and pneumatic tire |
| CN105324429B (en) * | 2013-07-05 | 2018-09-11 | 住友橡胶工业株式会社 | Rubber composition for tire and pneumatic tire |
| CN105295128A (en) * | 2014-06-06 | 2016-02-03 | 中国石油化工股份有限公司 | Rubber composition for high-speed energy-saving tire tread |
| CN105295128B (en) * | 2014-06-06 | 2017-05-31 | 中国石油化工股份有限公司 | High-speed and energy-saving rubber composition for tire tread |
| CN106317281A (en) * | 2015-06-17 | 2017-01-11 | 中国石油化工股份有限公司 | Production method of thermostable high-vinyl butadiene rubber |
| CN106317281B (en) * | 2015-06-17 | 2019-03-08 | 中国石油化工股份有限公司 | A kind of preparation method of heat-staple high-vinyl butadiene rubber |
| CN105199028A (en) * | 2015-09-12 | 2015-12-30 | 青岛科技大学 | High vinyl polybutadiene rubber capable of adjusting microstructure and preparation method thereof |
| CN108610457A (en) * | 2018-05-28 | 2018-10-02 | 青岛科技大学 | A kind of preparation method of siliceous high vinyl polybutadiene |
| CN110724317A (en) * | 2018-07-16 | 2020-01-24 | 中国石油化工股份有限公司 | Environment-friendly tire side rubber material |
| CN110724317B (en) * | 2018-07-16 | 2022-08-12 | 中国石油化工股份有限公司 | Environment-friendly tire side rubber material |
| CN115806741A (en) * | 2021-09-14 | 2023-03-17 | 中国石油化工股份有限公司 | Filling oil for styrene butadiene rubber and preparation method thereof |
| CN115806741B (en) * | 2021-09-14 | 2024-04-09 | 中国石油化工股份有限公司 | Filling oil for styrene butadiene rubber and preparation method thereof |
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