青岛科技大学高分子科学与工程学院 高性能有机光学聚合物与先进制造技术全国重点实验室 橡塑材料与工程教育部重点实验室 山东省高性能聚烯烃材料与循环利用重点实验室 青岛 266042
济宁神州轮胎有限公司 济宁 272100
aihuahe@iccas.ac.cn,ahhe@qust.edu.cn
收稿:2026-03-17,
录用:2026-04-02,
移动端阅览
刘忠光, 王硕, 鲁明诚, 侯雯静, 周丽君, 贺爱华. 交联密度对高填充溶聚丁苯橡胶/顺丁橡胶/白炭黑橡胶复合材料性能及作用机制. 高分子通报, doi: 10.14028/j.cnki.1003-3726.2026.26.100
Liu, Z. G.; Wang, S.; Lu, M. C.; Hou, W. J.; Zhou, L. J.; He, A. H. Properties and mechanism of high-silica filled solution polymerized styrene-butadiene rubber/butadiene rubber/SiO2 rubber composites with varied crosslinking density. Polym. Bull. (in Chinese), doi: 10.14028/j.cnki.1003-3726.2026.26.100
刘忠光, 王硕, 鲁明诚, 侯雯静, 周丽君, 贺爱华. 交联密度对高填充溶聚丁苯橡胶/顺丁橡胶/白炭黑橡胶复合材料性能及作用机制. 高分子通报, doi: 10.14028/j.cnki.1003-3726.2026.26.100 DOI:
Liu, Z. G.; Wang, S.; Lu, M. C.; Hou, W. J.; Zhou, L. J.; He, A. H. Properties and mechanism of high-silica filled solution polymerized styrene-butadiene rubber/butadiene rubber/SiO2 rubber composites with varied crosslinking density. Polym. Bull. (in Chinese), doi: 10.14028/j.cnki.1003-3726.2026.26.100 DOI:
高白炭黑(SiO
2
)填充的溶聚丁苯橡胶(SSBR)/顺丁橡胶(BR)复合材料是发展高耐磨、高抗湿滑绿色轿车轮胎胎面胶的重要方向之一,然而交联密度对高SiO
2
填充复合材料结构与性能的调控规律及作用机制尚不清晰。本工作系统研究了硫磺用量(0.8~2.4 phr)对高填充的SSBR/BR (SiO
2
100 phr)复合材料的加工行为、交联网络及力学性能的影响,并与低填充体系(SiO
2
60 phr)进行了对比。结果表明,随着硫磺用量的增加,高填充SSBR/BR/SiO
2
复合材料的交联密度线性增长,多硫交联键比例增加,单硫与双硫交联键比例降低。适量硫磺的加入提高了硫化胶的拉伸强度、耐磨性及撕裂强度,显著降低60 ℃损耗因子,意味着硫化胶滚动阻力显著降低,与此同时抗湿滑性能基本不变。在相同硫磺用量(1.6 phr)下,高填充体系相较于低填充体系具有更高的交联密度和更优的综合力学性能,在强韧性、耐磨性与动态性能之间达到最佳平衡,有效改善了轮胎“魔三角”性能矛盾。本研究可为绿色轮胎胎面胶配方设计提供实验依据和理论参考。
High silica (SiO
2
) filled solution polymerized styrene-butadiene rubber (SSBR)/butadiene rubber (BR) composites are an important development direction for green car tire stocks with high resistance to wear and wet-skid. However
the influence and mechanism of varied crosslinking densities on the structure and performance of high silica filled rubber stocks remain unclear.This study systematically investigated the effects of sulfur dosages (0.8–2.4 phr) on the processing behavior
crosslinking network
and mechanical properties of high silica filled SSBR/BR (SiO
2
100 phr) composites
which were compared with the low silica filled (SiO
2
60 phr) rubber composites. The results showed that the crosslinking density and ratio of polysulfide bonds of high silica filled SSBR/BR/SiO
2
rubber
composites increased linearly
where as the ratios of mono-sulfide and di-sulfide bonds decreased with increasing sulfur loading. The addition of an appropriate amount of sulfur improved the tensile strength
wear resistance
and tear strength of the vulcanizates and significantly reduced the loss factor at 60 ℃
which means that the rolling resistance of the vulcanizates was significantly reduced
whereas the wet-skid resistance remained basically unchanged. Compared with the low silica filled rubber vulcanizate
the highsilica filled vulcanizate exhibiteda higher crosslinking density and better comprehensive mechanical properties with the same sulfur dosage (1.6 phr)
achieving the best balance among strength and toughness
wear resistance
and dynamic performance
effectively improving the “magic triangle” performance contradiction of the tire. This study provides an experimental basis and theoretical reference for the formulation design of green tire tread rubber.
Deng, S. ; Chen, R. X. ; Duan, S. Y. ; Jia, Q. X. ; Hao, X. M. ; Zhang, L. Q . Research progress on sustainability of key tire materials . SusMat , 2023 , 3 ( 5 ), 581 – 608 .
赵菲 , 黄琪伟 , 高红娜 , 赵树高 . 绿色轮胎原材料的研究发展 . 科学通报 , 2016 , 61 ( 31 ), 3348 – 3358 .
Zhao, Y. H. ; Ren, M. W. ; Zhu, X. D. ; Ren, Z. Y. ; Hu, Y. F. ; Zhao, H. H. ; Wang, W. H. ; Chen, Y. B. ; Gao, K. W. ; Zhou, Y. J . Expanding the “magic triangle” of reinforced rubber using a supramolecular filler strategy . Materials , 2023 , 16 ( 9 ), 3429 .
Kim, D. ; Yeom, G. ; Joo, H. ; Ahn, B. ; Paik, H. J. ; Jeon, H. ; Kim, W . Effect of the functional group position in functionalized liquid butadiene rubbers used as processing aids on the properties of silica-filled rubber compounds . Polymers , 2021 , 13 ( 16 ), 2698 .
Xu, Y. H. ; Liu, Y. D. ; Gao, Y. Y. ; Liu, L. ; Zhang, L. Q . Designing high-performance green tire treads by reinforcing the styrene-butadiene rubber/silica interface with chain difunctionalization . Compos. Part B Eng. , 2025 , 290 , 111887 .
Hou, G. Y. ; Tao, W. ; Liu, J. ; Zhang, X. Y. ; Dong, M. J. ; Zhang, L. Q . Effect of the structural characteristics of solution styrene–butadiene rubber on the properties of rubber composites . J. Appl. Polym. Sci. , 2018 , 135 ( 24 ), 45749 .
Bisschop, R. ; Grunert, F. ; Ilisch, S. ; Stratton, T. ; Blume, A . Influence of molecular properties of SSBR and BR types on composite performance . Polym. Test. , 2021 , 99 , 107219 .
Neethirajan, J. ; Natarajan, T. S. ; Velusamy, R. ; Patel, B. ; Krishnan, R. S. ; Naskar, K . Optimization of mixing parameters on the degree of silanization using Taguchi and response surface method for fuel‐efficient tire tread compound . J. Appl. Polym. Sci. , 2022 , 139 ( 47 ), e53200 .
Joseph, E. ; Swaminathan, N . Investigation of mechanical properties and dispersion in silica/styrene butadiene rubber (SBR) nanocomposites: a ReaxFF molecular dynamics study . Comput. Mater. Sci. , 2021 , 200 , 110751 .
Ge, L. ; Liu, Q . Preparation and characterization of diene rubbers/silica composites via reactions of hydroxyl groups and blocked polyisocyanates . Polymers , 2022 , 14 ( 3 ), 461 .
Zhong, B. C. ; Jia, Z. X. ; Hu, D. C. ; Luo, Y. F. ; Jia, D. M. ; Liu, F . Enhancing interfacial interaction and mechanical properties of styrene-butadiene rubber composites via silica-supported vulcanization accelerator . Compos. Part A Appl. Sci. Manuf. , 2017 , 96 , 129 – 136 .
Dwivedi, C. ; Mohanty, T. R. ; Manjare, S. ; Ramakrishnan, S. ; Amarnath, S. K. P. ; Lorenzetti, D . Advanced carbon-silica hybrid fillers for enhanced rubber compounds in tires . Emergent Mater. , 2025 , 8 ( 3 ), 2241 – 2253 .
蔡晓艺 , 张志 , 陈禹竹 . 绿色轮胎技术创新对经济效益的推动 . 中国轮胎资源综合利用 , 2024 , ( 12 ), 70 – 72 .
Jia, W. J. ; Lin, F. F. ; Li, Z. B. ; Zhang, H. ; Liu, F. ; Yang, Y . Novel experimental approach to evaluate silica–elastomer interactions of vulcanizates . Polym. Eng. Sci. , 2024 , 64 ( 11 ), 5551 – 5565 .
Hayeemasae, N. ; Waesateh, K. ; Soontaranon, S. ; Masa, A . Effect of vulcanization systems and crosslink density on tensile properties and network structures of natural rubber . J. Teknologi , 2022 , 84 ( 6 ), 181 – 187 .
Cui, J. Z. ; Zeng, F. L. ; Wei, D. H. ; Wang, Y. S . Analysis of static and dynamic mechanical properties of carbon black/carbon nanotubes hybrid filled natural rubber nanocomposites using coarse-grained molecular dynamics . Polym. Compos. , 2024 , 45 ( 6 ), 5148 – 5163 .
Ejsmont, J. ; Owczarzak, W . Engineering method of tire rolling resistance evaluation . Measurement , 2019 , 145 , 144 – 149 .
Kratina, O. ; Pöschl, M. ; Stoček, R . The effect of apparent density of sulfidic crosslink and their chemical nature on self-heat build-up in carbon black filled natural rubber under cyclic mechanical loading . Polym. Degrad. Stab. , 2024 , 227 , 110871 .
Aggarwal, A. ; Hackel, N. ; Grunert, F. ; Ilisch, S. ; Beiner, M. ; Blume, A . Investigation of rheological, mechanical, and viscoelastic properties of silica-filled SSBR and BR model compounds . Polymers , 2024 , 16 ( 22 ), 3212 .
Zhang, H. ; Zheng, S. L. ; Zheng, L. N. ; Liu, F. ; Song, Y. D. ; Wang, M. J . Study on volume change and scanning electron microscopy observation of silica-filled solution polymerized styrene-butadiene rubber/ cis -1, 4-polybutadiene rubber blends upon stretching . Microsc. Res. Tech. , 2021 , 84 ( 11 ), 2636 – 2651 .
Liu, W. ; Li, L. ; Han, B. K. ; Zong, C. Z . Studies on mechanical properties and dynamic performance of SSBR/CB/silica composites . Key Eng. Mater. , 2016 , 717 , 52 – 56 .
Wu, T. Y. ; Lai, X. J. ; Li, H. Q. ; Chen, Y. S. ; Wang, Y. L. ; Liu, T. ; Zeng, X. R . Synergistic enhancement of vinyltriethoxysilane and layered Mg–Al double hydroxide on the tracking and erosion resistance of silicone rubber . Polym. Test. , 2020 , 84 , 106373 .
Yuan, X. H. ; Peng, Z. L. ; Zhang, Y. ; Zhang, Y . X. In situ preparation of zinc salts of unsaturated carboxylic acids to reinforce NBR . J. Appl. Polym. Sci. , 2000 , 77 ( 12 ), 2740 – 2748 .
Dileep, P. ; Narayanankutty, S. K . Styrenated phenol modified nanosilica for improved thermo-oxidative and mechanical properties of natural rubber . Polym. Test. , 2020 , 82 , 106302 .
Ahmed, N. M. ; ElNashar, D. E . The effect of zinc oxide-phosphate core-shell pigments on the properties of blend rubber composites . Mater. Des. , 2013 , 44 , 1 – 11 .
钱浙濠 , 王硕 , 宗鑫 , 蔡磊 , 贺爱华 . TBIR对天然橡胶纳米复合材料结构和性能的调控 . 高等学校化学学报 , 2023 , 44 ( 8 ), 28 – 35 .
Zhang, X. P. ; Cai, L. ; Wang, C. W. ; He, A. H . Effect of room-temperature annealing on structures and properties of SSBR/BR blends and SSBR/BR/SiO 2 composites . Compos. Sci. Technol. , 2019 , 184 , 107835 .
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 .
Sun, H. M. ; Liang, K. ; Li, J. ; Guo, S. Y . Real-time monitoring the vulcanization of EPDM rubber with ultrasound: a study on the reaction kinetics . J. Macromol. Sci. Part B , 2013 , 52 ( 10 ), 1341 – 1354 .
Marzocca, A. J. ; Goyanes, S . An analysis of the influence of the accelerator/sulfur ratio in the cure reaction and the uniaxial stress–strain behavior of SBR . J. Appl. Polym. Sci. , 2004 , 91 ( 4 ), 2601 – 2609 .
Blume, A. ; van Elburg, F. ; Grunert, F. ; Talma, A . “Re-think” sulfur curing . Molecules , 2024 , 29 ( 21 ), 5198 .
Kawahara, S. ; Fukushige, K. ; Nghiem Thi, T. ; Phan Trung, N. ; Yamamoto, Y . Accelerated sulfur vulcanization of silica-filled natural rubber analyzed by rubber-state NMR spectroscopy . Polym. Test. , 2025 , 153 , 109037 .
Li, K. ; Li, Z. W. ; Liu, J. ; Wen, S. P. ; Liu, L. ; Zhang, L. Q . Designing the cross-linked network to tailor the mechanical fracture of elastomeric polymer materials . Polymer , 2022 , 252 , 124931 .
Sakaki, Y. ; Usami, R. ; Tohsan, A. ; Junkong, P. ; Ikeda, Y . Dominant formation of disulfidic linkages in the sulfur cross-linking reaction of isoprene rubber by using zinc stearate as an activator . RSC Adv. , 2018 , 8 ( 20 ), 10727 – 10734 .
Wang, M. H. ; Yong, Z. F . Control of basic aggregate structure: application and mechanism analysis in nitrile rubber composite materials . Polym. Compos. , 2025 , 46 ( 1 ), 156 – 168 .
Hill, C. M. ; Koenig, J. L . Solid state carbon-13 NMR studies of silica-filled TBBS-accelerated, sulfur vulcanized, cis -1, 4 polyisoprene . Polym. Bull. , 1998 , 40 ( 2 ), 275 – 282 .
Gögelein, C. ; Van Duin, M . Sulfur vulcanization of low- versus high-unsaturated rubbers (IIR and EPDM versus NR and BR): Part II: network structure and tensile properties . Rubber Chem. Technol. , 2023 , 96 ( 3 ), 400 – 421 .
Hayichelaeh, C. ; Boonkerd, K . Enhancing the tire performances of truck tire tread based on rubber compounds containing biobased processing oil by adjusting sulfur contents . Ind. Crops Prod. , 2024 , 213 , 118451 .
Femina, G. ; de Ballesteros, O. R. ; Urciuoli, G. ; van Duin, M. ; Gögelein, C. ; Tammaro, D. ; Sotta, P. ; Auriemma, F . X-ray diffraction study of strain-induced crystallization of hydrogenated nitrile-butadiene rubbers: effect of crosslink density . Polymer , 2023 , 271 , 125782 .
Sęk, M. ; Kaewsakul, W. ; Anyszka, R. ; Schultz, S. ; Bandzierz, K. ; Blume, A . Interfacial coupling efficiency of functionalised rubbers on silica surfaces . Surf. Interfaces , 2024 , 44 , 103719 .
Bandzierz, K. ; Reuvekamp, L. ; Dryzek, J. ; Dierkes, W. ; Blume, A. ; Bielinski, D . Influence of network structure on glass transition temperature of elastomers . Materials , 2016 , 9 ( 7 ), 607 .
Jobando, V. O. ; Quarles, C. A . Effect of cross-linking on the free volume properties of natural rubber . Phys. Status Solidi C , 2007 , 4 ( 10 ), 3759 – 3762 .
Kong, Y. R. ; Chen, X. F. ; Li, Z. X. ; Li, G. X. ; Huang, Y. J . Evolution of crosslinking structure in vulcanized natural rubber during thermal aging in the presence of a constant compressive stress . Polym. Degrad. Stab. , 2023 , 217 , 110513 .
Fan, R. L. ; Zhang, Y. ; Li, F. ; Zhang, Y. X. ; Sun, K. ; Fan, Y. Z . Effect of high-temperature curing on the crosslink structures and dynamic mechanical properties of gum and N330-filled natural rubber vulcanizates . Polym. Test. , 2001 , 20 ( 8 ), 925 – 936 .
0
浏览量
0
下载量
0
CSCD
关联资源
相关文章
相关作者
相关机构
京公网安备11010802046898号