Citation: Hao Wang, Ri-Guo Wang, Yun-Sheng Ma, Bo Luan, Ai-Hua He. The Influence of Trans-1,4-poly(butadiene-co-isoprene) Copolymer Rubbers (TBIR) with Different Molecular Weights on the NR/TBIR Blends[J]. Chinese Journal of Polymer Science, ;2019, 37(10): 966-973. doi: 10.1007/s10118-019-2229-9 shu

The Influence of Trans-1,4-poly(butadiene-co-isoprene) Copolymer Rubbers (TBIR) with Different Molecular Weights on the NR/TBIR Blends

Hao Wang ^1,2 ,
Ri-Guo Wang ² ,
Yun-Sheng Ma ² ,
Bo Luan ² ,
Ai-Hua He ^1,,

a.
Shandong Provincial Key Laboratory of Olefin Catalysis and Polymerization, Key Laboratory of Rubber-plastics (Ministry of Education), School of Polymer Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
b.
Shandong Huaju Polymer Material Co., Ltd., Binzhou 256500, China

Corresponding author: Ai-Hua He, aihuahe@iccas.ac.cn;ahhe@qust.edu.cn
Received Date: 21 December 2018
Revised Date: 16 January 2019
Available Online: 7 March 2019

The molecular weight of a polymer is of prime importance and greatly influences the processing and mechanical properties of the polymer. Trans-1,4-poly(butadiene-co-isoprene) multi-block copolymer rubbers (TBIR) exhibit outstanding fatigue resistance, low heat build-up and good abrasion resistance, and are expected to be desirable candidate for high performance tire. Study on the influence of TBIR with different molecular weights on the structure and properties of TBIR and natural rubber (NR)/TBIR blends is essential to understand its contribution to the greatly improved dynamic properties of the rubber vulcanizates. TBIR with different molecular weights characterized by ¹H-NMR, ¹³C-NMR, GPC, and DSC were highly trans-1,4-copolymers with similar chain sequence distribution and crystalline trans-1,4-polyisoprene (TPI) blocks. The green strength and modulus of TBIR increased with the increasing molecular weight. The NR/TBIR compounds filled with 40 phr carbon black were chemically cured by sulfur for the preparation of NR/TBIR vulcanizates. The compatibility between NR and TBIR, filler distribution, crosslinking bond and density, and properties of NR/TBIR vulcanizates were studied. The NR/TBIR vulcanizates showed increasing tensile strength, hardness, modulus, rebound, abrasion resistance, and flexural fatigue properties with increasing molecular weight of TBIR. Furthermore, they presented significant improvement in flexural fatigue resistance when compared with that of NR vulcanizate. The contribution mechanism of TBIR on the NR/TBIR blends was discussed. The TBIR with a wide range of molecular weight are ideal rubbers for high performance tires.
- Trans-1,4-poly(butadiene-co-isoprene) copolymer rubber,
- Nature rubber,
- Blends,
- Molecular weight,
- Fatigue resistance
1. [1]
  Castellano, M.; Conzatti, L.; Costa, G.; Falqui, L.; Turturro, A.; Valenti, B.; Negroni, F. Surface modification of silica: 1. Thermodynamic aspects and effect on elastomer reinforcement. Polymer 2005, 46(3), 695-703. doi: 10.1016/j.polymer.2004.11.010
2. [2]
  Prasertsri, S.; Rattanasom, N. Fumed and precipitated silica reinforced natural rubber composites prepared from latex system: Mechanical and dynamic properties. Polym. Test. 2012, 31(5), 593-605. doi: 10.1016/j.polymertesting.2012.03.003
3. [3]
  Wang, Y. X.; Ma, J. H.; Zhang, L. Q.; Wu, Y. O. Revisiting the correlations between wet skid resistance and viscoelasticity of rubber composites via comparing carbon black and silica fillers. Polym. Test. 2011, 30(5), 557-562. doi: 10.1016/j.polymertesting.2011.04.009
4. [4]
  Ismail, H.; Suzaimah, S. Styrene butadiene rubber/epoxidized natural rubber blends: dynamic properties, curing characteristics and swelling studies. Polym. Test. 2000, 19(8), 879-888. doi: 10.1016/S0142-9418(99)00058-6
5. [5]
  Mathew, N. M.; De, S. K. Scanning electron microscopy studies in abrasion of NR/BR blends under different test conditions. J. Mater. Sci. 1983, 18(2), 515-524. doi: 10.1007/BF00560641
6. [6]
  Wu, W. L.; Chen, D. J. Silica-modified SBR/BR blends. J. Appl. Polym. Sci. 2015, 120(6), 3695-3700.
7. [7]
  Wang, Y. X.; Wu, Y. P.; Li, W. J.; Zhang, L. Q. Influence of filler type on wet skid resistance of SSBR/BR composites: Effects from roughness and micro-hardness of rubber surface. Appl. Surf. Sci. 2011, 257(6), 2058-2065. doi: 10.1016/j.apsusc.2010.08.129
8. [8]
  Rattanasom, N.; Saowapark, T.; Deeprasertkul, C. Reinforcement of natural rubber with silica/carbon black hybrid filler. Polym. Test. 2007, 26(3), 369-377. doi: 10.1016/j.polymertesting.2006.12.003
9. [9]
  Arrighi, V.; Mcewen, I. J.; Qian, H.; Prieto, M. B. S. The glass transition and interfacial layer in styrene-butadiene rubber containing silica nanofiller. Polymer 2003, 44(20), 6259-6266. doi: 10.1016/S0032-3861(03)00667-0
10. [10]
  Stöckelhuber, K. W.; Svistkov, A. S.; Pelevin, A. G.; Heinrich, G. Impact of filler surface modification on large scale mechanics of styrene butadiene/silica rubber composites. Macromolecules 2011, 44(11), 4366-4381. doi: 10.1021/ma1026077
11. [11]
  Yatsuyanagi, F.; Suzuki, N.; Ito, M.; Kaidou, H. Effects of secondary structure of fillers on the mechanical properties of silica filled rubber systems. Polymer 2001, 42(23), 9523-9529. doi: 10.1016/S0032-3861(01)00472-4
12. [12]
  He, A. H.; Huang, B. C.; Jiao, S. K.; Hu, Y. L. Synthesis of a high-trans-1,4-butadiene/isoprene copolymers with supported titanium catalysts. J. Appl. Polym. Sci. 2003, 89(7), 1800-1807. doi: 10.1002/(ISSN)1097-4628
13. [13]
  Jiang, X. B.; Zhang, Q. F.; He, A. H. Synthesis and characterization of trans-1,4-butadiene/isoprene copolymers: determination of sequence distribution and thermal properties. Chinese J. Polym. Sci. 2015, 33(6), 815-822. doi: 10.1007/s10118-015-1626-y
14. [14]
  Zhang, Q. F.; Jiang, X. B.; He, A. H. Synthesis and characterization of trans-1,4-butadiene/isoprene copolymers: determination of monomer reactivity ratios and temperature dependence. Chinese J. Polym. Sci. 2014, 32(8), 1068-1076. doi: 10.1007/s10118-014-1467-0
15. [15]
  He, A. H.; Yao, W.; Huang, B. C.; Huang, Y. Q.; Jiao, S. K. Synthesis of high trans-1,4-butadiene-isoprene copolymers by supported titanium catalysts. Acta Polymerica Sinica (in Chinese) 2002, 19-24.
16. [16]
  Niu, Q. T.; Jiang, X. B.; He, A. H. Synthesis of the spherical trans-1,4-polyisoprene/trans-1,4-poly(butadiene-co-isoprene) rubber alloys within reactor, Polymer, 2014, 55, 2146-2152 doi: 10.1016/j.polymer.2014.03.013
17. [17]
  Niu, Q. T.; Zou, C.; Liu, X. Y.; Wang, R. G.; He, A. H. Isothermal crystallization fractionation and fraction characterization of trans-1,4-poly(isoprene-co-butadiene). Polymer 2017, 109, 197-204. doi: 10.1016/j.polymer.2016.12.028
18. [18]
  Wang, H.; Zou, C.; He, A. H. Characterization of trans-1,4-poly(butadiene-co-isoprene) copolymer rubber and its application as hump strip stocks in PCR tires. Acta Polymerica Sinica (in Chinese) 2015, 296-305.
19. [19]
  He, A. H.; Yao, W.; Huang, B. C. Properties of a new synthetic rubber: High-trans-1,4-poly(butadiene-co-isoprene) rubber. J. Appl. Polym. Sci. 2004, 92(5), 2941-2948. doi: 10.1002/(ISSN)1097-4628
20. [20]
  Wang, H.; Cui, H. H.; Ma, Y. S.; Zhang, J. P.; Song, L. Y.; He, A. H. The study of trans-1,4-poly(butadiene-co-isoprene) copolymer rubbers as tire belts stocks. Polym. Bull. 2016, (10), 61-67.
21. [21]
  Wang, H.; Song, L. Y.; Ma, Y. S.; Wang, R. G.; He, A. H. The structures and properties of high performance PCR tire tread stock modified with trans-1,4-poly(butadiene-co-isoprene) copolymer rubber. Acta Polymerica Sinica (in Chinese) 2018, (3), 419-428. doi: 10.11777/j.issn1000-3304.2017.17101
22. [22]
  Zhang, X. P.; Cui, H. H.; Song, L. Y.; Ren, H. C.; Wang, R. G.; He, A. H. Elastomer nanocomposites with superior dynamic mechanical properties via trans-1,4-poly(butadiene-co-isoprene) incorporation. Compos. Sci. Technol. 2018, 158, 156-163. doi: 10.1016/j.compscitech.2018.02.025
23. [23]
  Wang, H.; Zhang, J. P.; Wang, R. G.; He, A. H. Properties of nature rubber/high trans-1,4-poly(butadiene-co-isoprene) rubber blends. China Rubber Ind. 2018, 65(2), 167-172.
24. [24]
  Zhang, Z. P.; Wang, H.; Ren, H. C.; Wang, R. G.; He, A. H. Rubber nanocomposites with nano-scale phase structures and kinetically inhibited filler flocculation for enhanced integrated performances via reactive multi-block copolymer incorporation. Ind. Eng. Chem. Res. 2019, 58, 917−925 doi: 10.1021/acs.iecr.8b04958
25. [25]
  Wang, H.; Zhang, X. P.; Nie, H. R.; Wang, R. G.; He, A. H. Multi-block copolymer as reactive multifunctional compatibilizer for NR/BR blends with desired network structures and dynamical properties: Compatibility, co-vulcanization and filler dispersion. Comps. Part A-Appl. S. 2019, 116, 197-205. doi: 10.1016/j.compositesa.2018.11.001
26. [26]
  Boochathum, P.; Prajudtake, W. Vulcanization of cis- and trans-polyisoprene and their blends: Cure characteristics and crosslink distribution. Eur. Polym. J. 2001, 37(3), 417-427. doi: 10.1016/S0014-3057(00)00137-3
27. [27]
  Niu, Q. T.; Li, W. T.; Liu, X. Y.; He, A. H. Trans-1,4-stereospecific copolymerization of isoprene and butadiene catalyzed by TiCl₄/MgCl₂ type Ziegler-Natta catalyst II. Copolymerization kinetics and mechanism. Polymer 2018, 143, 173-183. doi: 10.1016/j.polymer.2018.04.007
28. [28]
  Li, W. T.; Nie, H. R.; Shao, H. F.; Ren, H. C.; He, A. H. Synthesis, chain structures and phase morphologies of trans-1,4-poly(butadiene-co-isoprene) copolymers. Polymer 2018, 156, 148-161. doi: 10.1016/j.polymer.2018.10.002
29. [29]
  Marigo, A.; Marega, C.; Causin, V.; Ferrari, P. Influence of thermal treatments, molecular weight, and molecular weight distribution on the crystallization of β-isotactic polypropylene. J. Appl. Polym. Sci. 2010, 91(2), 1008-1012.
30. [30]
  Benedetti, E.; D'Alessio, A.; Bertolutti, C.; Vergamini, P.; Fanti, N. D.; Pianca, M. Influence of molecular weight on the crystallization of poly(vinylidene fluoride). Polym. Bull. 1989, 22(5-6), 645-651. doi: 10.1007/BF00718947
31. [31]
  Shao, H.; Wang, S.; He, A. The influence of molecular weight on high shear rate macroscopic rheological properties of polybutene-1 melts through rubber-processing analyzer. Polym. Bull. 2016, 73(11), 3209-3220. doi: 10.1007/s00289-016-1650-2
32. [32]
  Yuan, M.; Galloway, J. A.; Hoffman, R. J. Influence of molecular weight on rheological, thermal, and mechanical properties of PEEK. Polym. Eng. Sci. 2011, 51(1), 94-102. doi: 10.1002/pen.v51.1
33. [33]
  Jordens, K.; Wilkes, G. L.; Janzen, J.; Rohlfing, D. C.; Welch, M. B. The influence of molecular weight and thermal history on the thermal, rheological, and mechanical properties of metallocene-catalyzed linear polyethylenes. Polymer 2000, 41(19), 7175-7192. doi: 10.1016/S0032-3861(00)00073-2
34. [34]
  Zuiderduin, W. C. J.; Homminga, D. S.; Huétink, H. J.; Gaymans, R. J. Influence of molecular weight on the fracture properties of aliphatic polyketone terpolymers. Polymer 2003, 44(20), 6361-6370. doi: 10.1016/S0032-3861(03)00635-9
35. [35]
  Nunes, R. W.; Martin, J. R.; Johnson, J. F. Influence of molecular weight and molecular weight distribution on mechanical properties of polymers. Polym. Eng. Sci. 2010, 22(4), 205-228.
36. [36]
  Ismail, H.; Freakley, P. K.; Sutherland, I.; Sheng, E. Effects of multifunctional additive on mechanical properties of silica filled natural rubber compound. Eur. Polym. J. 1995, 31(11), 1109-1117. doi: 10.1016/0014-3057(95)00066-6
37. [37]
  Liu, X.; Zhao, S. H.; Zhang, X. Y.; Li, X. L.; Bai, Y. Preparation, structure, and properties of solution-polymerized styrene- butadiene rubber with functionalized end-groups and its silica-filled composites. Polymer 2014, 55(8), 1964-1976. doi: 10.1016/j.polymer.2014.02.067
38. [38]
  Huneau, B.; Masquelier, I.; Marco, Y.; Saux, V. L.; Noizet, S.; Schiel, C.; Charrier, P. Fatigue crack initiation in a carbon black-filled natural rubber. Rubber Chem. Technol. 2016, 89, 126-141.
1. [1]
  Yue Ren , Kang Li , Yi-Zi Wang , Shao-Peng Zhao , Shu-Min Pan , Haojie Fu , Mengfan Jing , Yaming Wang , Fengyuan Yang , Chuntai Liu . Swelling and erosion assisted sustained release of tea polyphenol from antibacterial ultrahigh molecular weight polyethylene for joint replacement. Chinese Chemical Letters, 2025, 36(2): 110468-. doi: 10.1016/j.cclet.2024.110468
2. [2]
  Guizhi Zhu , Junrui Tan , Longfei Tan , Qiong Wu , Xiangling Ren , Changhui Fu , Zhihui Chen , Xianwei Meng . Growth of CeCo-MOF in dendritic mesoporous organosilica as highly efficient antioxidant for enhanced thermal stability of silicone rubber. Chinese Chemical Letters, 2025, 36(1): 109669-. doi: 10.1016/j.cclet.2024.109669
3. [3]
  Hualei Xu , Manman Han , Haiqiang Liu , Liang Qin , Lulu Chen , Hao Hu , Ran Wu , Chenyu Yang , Hua Guo , Jinrong Li , Jinxiang Fu , Qichen Hao , Yijun Zhou , Jinchao Feng , Xiaodong Wang . 4-Nitrocatechol as a novel matrix for low-molecular-weight compounds in situ detection and imaging in biological tissues by MALDI-MSI. Chinese Chemical Letters, 2024, 35(6): 109095-. doi: 10.1016/j.cclet.2023.109095
4. [4]
  Yutong Xiong , Ting Meng , Wendi Luo , Bin Tu , Shuai Wang , Qingdao Zeng . Molecular conformational effects on co-assembly systems of low-symmetric carboxylic acids investigated by scanning tunneling microscopy. Chinese Journal of Structural Chemistry, 2025, 44(2): 100511-100511. doi: 10.1016/j.cjsc.2025.100511
5. [5]
  Yong-Dan Zhao , Yidan Wang , Rongrong Wang , Lina Chen , Hengtong Zuo , Xi Wang , Jihong Qiang , Geng Wang , Qingxia Li , Canqi Ping , Shuqiu Zhang , Hao Wang . Reversing artemisinin resistance by leveraging thermo-responsive nanoplatform to downregulating GSH. Chinese Chemical Letters, 2024, 35(6): 108929-. doi: 10.1016/j.cclet.2023.108929
6. [6]
  Yixuan Wang , Jiexin Li , Zhihao Shang , Chengcheng Feng , Jianmin Gu , Maosheng Ye , Ran Zhao , Danna Liu , Jingxin Meng , Shutao Wang . Wettability-driven synergistic resistance of scale and oil on robust superamphiphobic coating. Chinese Chemical Letters, 2024, 35(7): 109623-. doi: 10.1016/j.cclet.2024.109623
7. [7]
  Yuxin Li , Chengbin Liu , Qiuju Li , Shun Mao . Fluorescence analysis of antibiotics and antibiotic-resistance genes in the environment: A mini review. Chinese Chemical Letters, 2024, 35(10): 109541-. doi: 10.1016/j.cclet.2024.109541
8. [8]
  Shaoqing Du , Xinyong Liu , Xueping Hu , Peng Zhan . Targeting novel sites represents an effective strategy for combating drug resistance. Chinese Chemical Letters, 2025, 36(1): 110378-. doi: 10.1016/j.cclet.2024.110378
9. [9]
  Xiaofang Luo , Ye Wu , Xiaokun Zhang , Min Tang , Feiye Ju , Zuodong Qin , Gregory J Duns , Wei-Dong Zhang , Jiang-Jiang Qin , Xin Luan . Peptide-based strategies for overcoming multidrug-resistance in cancer therapy. Chinese Chemical Letters, 2025, 36(1): 109724-. doi: 10.1016/j.cclet.2024.109724
10. [10]
  Fang-Yuan Chen , Wen-Chao Geng , Kang Cai , Dong-Sheng Guo . Molecular recognition of cyclophanes in water. Chinese Chemical Letters, 2024, 35(5): 109161-. doi: 10.1016/j.cclet.2023.109161
11. [11]
  Zhenchun Yang , Bixiao Guo , Zhenyu Hu , Kun Wang , Jiahao Cui , Lina Li , Chun Hu , Yubao Zhao . Molecular engineering towards dual surface local polarization sites on poly(heptazine imide) framework for boosting H₂O₂ photo-production. Chinese Chemical Letters, 2024, 35(8): 109251-. doi: 10.1016/j.cclet.2023.109251
12. [12]
  Liping Zhao , Xixi Guo , Zhimeng Zhang , Xi Lu , Qingxuan Zeng , Tianyun Fan , Xintong Zhang , Fenbei Chen , Mengyi Xu , Min Yuan , Zhenjun Li , Jiandong Jiang , Jing Pang , Xuefu You , Yanxiang Wang , Danqing Song . Novel berberine derivatives as adjuvants in the battle against Acinetobacter baumannii: A promising strategy for combating multi-drug resistance. Chinese Chemical Letters, 2024, 35(10): 109506-. doi: 10.1016/j.cclet.2024.109506
13. [13]
  Caihong Mao , Yanfeng He , Xiaohan Wang , Yan Cai , Xiaobo Hu . Synthesis and molecular recognition characteristics of a tetrapodal benzene cage. Chinese Chemical Letters, 2024, 35(8): 109362-. doi: 10.1016/j.cclet.2023.109362
14. [14]
  Cheng-Da Zhao , Huan Yao , Shi-Yao Li , Fangfang Du , Li-Li Wang , Liu-Pan Yang . Amide naphthotubes: Biomimetic macrocycles for selective molecular recognition. Chinese Chemical Letters, 2024, 35(4): 108879-. doi: 10.1016/j.cclet.2023.108879
15. [15]
  Yanwei Duan , Qing Yang . Molecular targets and their application examples for interrupting chitin biosynthesis. Chinese Chemical Letters, 2025, 36(4): 109905-. doi: 10.1016/j.cclet.2024.109905
16. [16]
  Zhimin Sun , Xin-Hui Guo , Yue Zhao , Qing-Yu Meng , Li-Juan Xing , He-Lue Sun . Dynamically switchable porphyrin-based molecular tweezer for on−off fullerene recognition. Chinese Chemical Letters, 2024, 35(6): 109162-. doi: 10.1016/j.cclet.2023.109162
17. [17]
  Li Lin , Song-Lin Tian , Zhen-Yu Hu , Yu Zhang , Li-Min Chang , Jia-Jun Wang , Wan-Qiang Liu , Qing-Shuang Wang , Fang Wang . Molecular crowding electrolytes for stabilizing Zn metal anode in rechargeable aqueous batteries. Chinese Chemical Letters, 2024, 35(7): 109802-. doi: 10.1016/j.cclet.2024.109802
18. [18]
  Minghao Hu , Tianci Xie , Yuqiang Hu , Longjie Li , Ting Wang , Tongbo Wu . Allosteric DNAzyme-based encoder for molecular information transfer. Chinese Chemical Letters, 2024, 35(7): 109232-. doi: 10.1016/j.cclet.2023.109232
19. [19]
  Chuan-Zhi Ni , Ruo-Ming Li , Fang-Qi Zhang , Qu-Ao-Wei Li , Yuan-Yuan Zhu , Jie Zeng , Shuang-Xi Gu . A chiral fluorescent probe for molecular recognition of basic amino acids in solutions and cells. Chinese Chemical Letters, 2024, 35(10): 109862-. doi: 10.1016/j.cclet.2024.109862
20. [20]
  Wei-Jia Wang , Kaihong Chen . Molecular-based porous polymers with precise sites for photoreduction of carbon dioxide. Chinese Chemical Letters, 2025, 36(1): 109998-. doi: 10.1016/j.cclet.2024.109998

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(742)
HTML views(28)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142