烷基化木质素/炭黑复配体系对天然橡胶复合材料性能的影响

曾舒芬; 陈淑婷; 曾奇斌; 叶晓霞; 刘以凡; 刘明华

doi:10.11777/j.issn1000-3304.2025.25285

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烷基化木质素/炭黑复配体系对天然橡胶复合材料性能的影响

研究论文 | 更新时间：2026-01-30

- 烷基化木质素/炭黑复配体系对天然橡胶复合材料性能的影响
- Influence of Dodecylated Lignin/Carbon Black Hybrid Filler System on the Performance of Natural Rubber
- 高分子学报 2026年页码：1-12
- 作者机构：
  
  1.福州大学环境与安全工程学院福州 350108
  2.莆田学院环境与生物工程学院莆田 351100
- 作者简介：
  
  E-mail: mhliu2000@fzu.edu.cn
- 基金信息：
  
  福厦泉国家自主创新示范区城乡生态环境质量提升关键技术协同创新平台项目(2022-P-024)
- DOI：10.11777/j.issn1000-3304.2025.25285
  中图分类号：
- CSTR：32057.14.GFZXB.2025.7543
- 收稿：2025-10-27，
  
  录用：2025-12-18，
  
  网络出版：2026-01-30，
- 稿件说明：
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曾舒芬, 陈淑婷, 曾奇斌, 叶晓霞, 刘以凡, 刘明华. 烷基化木质素/炭黑复配体系对天然橡胶复合材料性能的影响. 高分子学报, doi: 10.11777/j.issn1000-3304.2025.25285.

Zeng, S. F.; Chen, S. T.; Zeng, Q. B.; Ye, X. X.; Liu, Y. F.; Liu, M. H. Influence of dodecylated lignin/carbon black hybrid filler system on the performance of natural rubber. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2025.25285.
曾舒芬, 陈淑婷, 曾奇斌, 叶晓霞, 刘以凡, 刘明华. 烷基化木质素/炭黑复配体系对天然橡胶复合材料性能的影响. 高分子学报, doi: 10.11777/j.issn1000-3304.2025.25285. DOI： CSTR： 32057.14.GFZXB.2025.7543.

Zeng, S. F.; Chen, S. T.; Zeng, Q. B.; Ye, X. X.; Liu, Y. F.; Liu, M. H. Influence of dodecylated lignin/carbon black hybrid filler system on the performance of natural rubber. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2025.25285. DOI： CSTR： 32057.14.GFZXB.2025.7543.

摘要

通过烷基化改性工艺制备了十二烷基化木质素(DL)，并将其与炭黑(CB)复配构建双相填料体系，系统探究了不同DL/CB复配比例对天然橡胶复合材料性能的影响. 结果表明，DL的引入使复合材料的正硫化时间缩短，门尼黏度降低，并且有效改善了填料在橡胶基体中的分散状态，进而减弱复合材料的Payne效应，显著提升力学性能、耐热氧老化性能与耐屈挠性能. 其中NR-10DL/40CB复合材料表现出最佳的综合性能，其在维持与NR-50CB相当的热稳定性、拉伸强度及抗湿滑性能的基础上，断裂伸长率提高了21.1%. 此外，热氧老化系数与屈挠龟裂周数分别提升了31.1%与41.4%，滚动阻力及耐切割性也得到同步优化，在轮胎、传送带等橡胶制品领域具有良好的应用前景.

Abstract

To enhance the interfacial compatibility and dispersion of lignin within the natural rubber (NR) matrix

thereby enhancing the mechanical properties of the rubber composite

dodecylated lignin (DL) was synthesized through alkylation modification

and a hybrid filler system was constructed by incorporating it with carbon black (CB). The influence of the DL/CB ratio on the properties of NR composites was systematically investigated. The results indicated that the incorporation of DL reduced the optimum curing time and Mooney viscosity of the composites

effectively improved the dispersion of the fillers in the rubber matrix

and significantly enhanced the mechanical properties

thermo-oxidative aging resistance

and flex resistance of the composites. Among the tested formulations

the NR-10DL/40CB composite exhibited the best performance. While maintaining thermal stability

tensile strength

and wet skid resistance comparable to those of the NR-50CB benchmark

the NR-10DL/40CB composite achieved a remarkable 21.1% increase in elongation at break. Furthermore

the thermal oxidative aging coefficient and the number of flex cracking cycles were improved by 31.1% and 41.4%

respectively

while the rolling resistance and cut resistance were optimized. These findings demonstrate the promising potential of the composite for application in rubber products such as tires and conveyor belts.

关键词

Keywords

references

Tang S. F. ; Li Z. X. ; Sun W. C. ; Liu Y. L. ; Wang J. ; Wang X. ; Lin J. Natural rubber/styrene-butadiene rubber blend composites potentially applied in damping bearings . Polymers , 2024 , 16 ( 13 ), 1945 . doi: 10.3390/polym16131945 http://dx.doi.org/10.3390/polym16131945

Le H. H. ; Abhijeet S. ; Ilisch S. ; Klehm J. ; Henning S. ; Beiner M. ; Sarkawi S. S. ; Dierkes W. ; Das A. ; Fischer D. ; Stöckelhuber K. W. ; Wiessner S. ; Khatiwada S. P. ; Adhikari R. ; Pham T. ; Heinrich G. ; Radusch H. J. The role of linked phospholipids in the rubber-filler interaction in carbon nanotube (CNT) filled natural rubber (NR) composites . Polymer , 2014 , 55 ( 18 ), 4738 - 4747 . doi: 10.1016/j.polymer.2014.07.043 http://dx.doi.org/10.1016/j.polymer.2014.07.043

Zhao S. ; Jie X. ; Ma Z. ; Wang Z. ; Zhang J. C. ; Li Y. S. ; Nie Q. H. ; Ma Y. Preparation of taraxacum kok-saghyz rubber and biofuel ethanol simultaneously by the yeast fermentation process . ACS Omega , 2023 , 8 ( 27 ), 24185 - 24197 . doi: 10.1021/acsomega.2c07870 http://dx.doi.org/10.1021/acsomega.2c07870

Tang Z. H. ; Huang J. ; Wu X. H. ; Guo B. C. ; Zhang L. Q. ; Liu F. Interface engineering toward promoting silanization by ionic liquid for high-performance rubber/silica composites . Ind. Eng. Chem. Res. , 2015 , 54 ( 43 ), 10747 - 10756 . doi: 10.1021/acs.iecr.5b03146 http://dx.doi.org/10.1021/acs.iecr.5b03146

汪传生 , 张鲁琦 , 边慧光 , 李海涛 . 碳纤维/天然橡胶复合材料的性能研究 . 橡胶工业 , 2018 , 65 ( 11 ), 1243 - 1247 .

Atif M. ; Bongiovanni R. ; Giorcelli M. ; Celasco E. ; Tagliaferro A. Modification and characterization of carbon black with mercaptopropyltrimethoxysilane . Appl. Surf. Sci. , 2013 , 286 , 142 - 148 . doi: 10.1016/j.apsusc.2013.09.037 http://dx.doi.org/10.1016/j.apsusc.2013.09.037

Fan Y. R. ; Fowler G. D. ; Zhao M. The past, present and future of carbon black as a rubber reinforcing filler-a review . J. Clean. Prod. , 2020 , 247 , 119115 . doi: 10.1016/j.jclepro.2019.119115 http://dx.doi.org/10.1016/j.jclepro.2019.119115

Wang Z. P. ; Wang S. J. ; Yu X. Y. ; Zhang H. ; Yan S. K. Study on the use of CTAB-treated illite as an alternative filler for natural rubber . ACS Omega , 2021 , 6 ( 29 ), 19017 - 19025 . doi: 10.1021/acsomega.1c02304 http://dx.doi.org/10.1021/acsomega.1c02304

Wang Y. Y. ; Meng X. Z. ; Pu Y. Q. ; Ragauskas A. J. Recent advances in the application of functionalized lignin in value-added polymeric materials . Polymers , 2020 , 12 ( 10 ), 2277 . doi: 10.3390/polym12102277 http://dx.doi.org/10.3390/polym12102277

Collins M. N. ; Nechifor M. ; Tanasă F. ; Zănoagă M. ; McLoughlin A. ; Stróżyk M. A. ; Culebras M. ; Teacă C. A. Valorization of lignin in polymer and composite systems for advanced engineering applications-a review . Int. J. Biol. Macromol. , 2019 , 131 , 828 - 849 . doi: 10.1016/j.ijbiomac.2019.03.069 http://dx.doi.org/10.1016/j.ijbiomac.2019.03.069

Zheng Y. ; Moreno A. ; Zhang Y. Q. ; Sipponen M. H. ; Dai L. Harnessing chemical functionality of lignin towards stimuli-responsive materials . Trends Chem. , 2024 , 6 ( 2 ), 62 - 78 . doi: 10.1016/j.trechm.2023.12.001 http://dx.doi.org/10.1016/j.trechm.2023.12.001

Gordobil O. ; Moriana R. ; Zhang L. M. ; Labidi J. ; Sevastyanova O. Assesment of technical lignins for uses in biofuels and biomaterials: structure-related properties, proximate analysis and chemical modification . Ind. Crops Prod. , 2016 , 83 , 155 - 165 . doi: 10.1016/j.indcrop.2015.12.048 http://dx.doi.org/10.1016/j.indcrop.2015.12.048

Spiridon I. ; Leluk K. ; Resmerita A. M. ; Darie R. N. Evaluation of PLA-lignin bioplastics properties before and after accelerated weathering . Compos. Part B Eng. , 2015 , 69 , 342 - 349 . doi: 10.1016/j.compositesb.2014.10.006 http://dx.doi.org/10.1016/j.compositesb.2014.10.006

Setua D. K. ; Shukla M. K. ; Nigam V. ; Singh H. ; Mathur G. N. Lignin reinforced rubber composites . Polym. Compos. , 2000 , 21 ( 6 ), 988 - 995 . doi: 10.1002/pc.10252 http://dx.doi.org/10.1002/pc.10252

Frigerio P. ; Zoia L. ; Orlandi M. ; Hanel T. ; Castellani L. Application of sulphur-free lignins as a filler for elastomers: effect of hexamethylenetetramine treatment . BioResources , 2014 , 9 ( 1 ), 1387 - 1400 . doi: 10.15376/biores.9.1.1387-1400 http://dx.doi.org/10.15376/biores.9.1.1387-1400

侯世航 , 任顺强 , 王司晨 , 张继川 , 樊永明 . 异戊二烯共聚改性木质素补强橡胶复合材料 . 北京林业大学学报 , 2025 , 47 ( 3 ), 162 - 170 .

Mark J. E. Experimental determinations of crosslink densities . Rubber Chem. Technol. , 1982 , 55 ( 3 ), 762 - 768 . doi: 10.5254/1.3535902 http://dx.doi.org/10.5254/1.3535902

Xie L. L. ; Zhang T. ; Karrar E. ; Xie D. ; Zheng L. Y. ; Jin J. ; Wang X. G. ; Jin Q. Z. Highly efficient synthesis of 4,4-dimethylsterol oleates using acyl chloride method through esterification . Food Chem. , 2021 , 364 , 130140 . doi: 10.1016/j.foodchem.2021.130140 http://dx.doi.org/10.1016/j.foodchem.2021.130140

宋俊 , 王梦蝶 , 王林锋 , 李传盟 . 烷基化木质素/PVA基碳纤维前驱体的制备及其性能 . 天津工业大学学报 , 2025 , 44 ( 1 ), 8 - 13 .

Singh G. ; Kumar P. Extraction, gas chromatography-mass spectrometry analysis and screening of fruits of Terminalia chebula Retz. for its antimicrobial potential . Pharmacognosy Res. , 2013 , 5 ( 3 ), 162 - 168 . doi: 10.4103/0974-8490.112421 http://dx.doi.org/10.4103/0974-8490.112421

Lv X. Y. ; Li Q. X. ; Jiang Z. C. ; Wang Y. ; Li J. D. ; Hu C. W. Structure characterization and pyrolysis behavior of organosolv lignin isolated from corncob residue . J. Anal. Appl. Pyrolysis , 2018 , 136 , 115 - 124 . doi: 10.1016/j.jaap.2018.10.016 http://dx.doi.org/10.1016/j.jaap.2018.10.016

Poyraz B. ; Güner Y. ; Tozluoğlu A. ; Aslan R. Cellulose and lignin in place of EPDM and carbon black for automotive sealing profiles . Int. J. Biol. Macromol. , 2023 , 236 , 123964 . doi: 10.1016/j.ijbiomac.2023.123964 http://dx.doi.org/10.1016/j.ijbiomac.2023.123964

Han J. ; Li W. ; Liu D. Y. ; Qin L. B. ; Chen W. S. ; Xing F. T. Pyrolysis characteristic and mechanism of waste tyre: a thermogravimetry-mass spectrometry analysis . J. Anal. Appl. Pyrolysis , 2018 , 129 , 1 - 5 . doi: 10.1016/j.jaap.2017.12.016 http://dx.doi.org/10.1016/j.jaap.2017.12.016

Mohamad Aini N. A. ; Othman N. ; Hussin M. H. ; Sahakaro K. ; Hayeemasae N. Lignin as alternative reinforcing filler in the rubber industry: a review . Front. Mater. , 2020 , 6 , 329 . doi: 10.3389/fmats.2019.00329 http://dx.doi.org/10.3389/fmats.2019.00329

孙佳峰 , 朱彦铭 , 吴明生 . 桉树木质素对天然橡胶的补强性能研究 . 橡胶工业 , 2025 , 72 ( 8 ), 563 - 571 .

Xu H. S. ; Fan T. ; Ye N. ; Wu W. D. ; Huang D. Y. ; Wang D. L. ; Wang Z. ; Zhang L. Q. Plasticization effect of bio-based plasticizers from soybean oil for tire tread rubber . Polymers , 2020 , 12 ( 3 ), 623 . doi: 10.3390/polym12030623 http://dx.doi.org/10.3390/polym12030623

Banda-Villanueva A. ; González-Zapata J. L. ; Martínez-Cartagena M. E. ; Magaña I. ; Córdova T. ; López R. ; Valencia L. ; Medina S. G. ; Rodríguez A. M. ; Soriano F. ; Díaz de León R. Synthesis and vulcanization of polymyrcene and polyfarnesene bio-based rubbers: influence of the chemical structure over the vulcanization process and mechanical properties . Polymers , 2022 , 14 ( 7 ), 1406 . doi: 10.3390/polym14071406 http://dx.doi.org/10.3390/polym14071406

Pérez-Aguilar H. ; Serrano-Martínez V. M. ; Carbonell-Blasco M. P. ; García-García A. ; Orgilés-Calpena E. Sustainable extraction of lignin from rice straw: utilizing fractionated lignin for antimicrobial functionalization of polymeric materials . Biofuels Bioprod. Biorefin. , 2025 , 19 ( 5 ), 1378 - 1399 . doi: 10.1002/bbb.70030 http://dx.doi.org/10.1002/bbb.70030

Liu R. Y. ; Li J. X. ; Lu T. Y. ; Han X. K. ; Yan Z. P. ; Zhao S. G. ; Wang H. Comparative study on the synergistic reinforcement of lignin between carbon black/lignin and silica/lignin hybrid filled natural rubber composites . Ind. Crops Prod. , 2022 , 187 , 115378 . doi: 10.1016/j.indcrop.2022.115378 http://dx.doi.org/10.1016/j.indcrop.2022.115378

Payne A. R. The dynamic properties of carbon black-loaded natural rubber vulcanizates. Part I . J. Appl. Polym. Sci. , 1962 , 6 ( 19 ), 57 - 63 . doi: 10.1002/app.1962.070061906 http://dx.doi.org/10.1002/app.1962.070061906

陈楚楚 , 金永灿 , 姜波 . 木质素基强韧复合材料的界面分子设计策略 . 高分子材料科学与工程 , 2025 , 41 ( 7 ), 181 - 190 .

Zhong B. C. ; Jia Z. X. ; Luo Y. F. ; Jia D. M. ; Liu F. Understanding the effect of filler shape induced immobilized rubber on the interfacial and mechanical strength of rubber composites . Polym. Test. , 2017 , 58 , 31 - 39 . doi: 10.1016/j.polymertesting.2016.12.010 http://dx.doi.org/10.1016/j.polymertesting.2016.12.010

蔡长庚 , 朱立新 , 贾德民 . 动态力学分析在复合材料界面中的应用 . 纤维复合材料 , 2004 , 21 ( 1 ), 46 - 49 .

魏绪玲 , 黄庆东 , 龚光碧 , 张华强 , 徐典宏 , 朱晶 , 梁滔 , 李晶 . 丁基橡胶及卤化丁基橡胶阻尼材料的研究进展 . 合成橡胶工业 , 2021 , 44 ( 2 ), 145 - 149 .

Naebpetch W. ; Thumrat S. ; Indriasari , Nakaramontri Y. ; Sattayanurak S. Effect of glycerol as processing oil in natural rubber/carbon black composites: processing, mechanical, and thermal aging properties . Polymers , 2023 , 15 ( 17 ), 3599 . doi: 10.3390/polym15173599 http://dx.doi.org/10.3390/polym15173599

Wang X. L. ; Yang K. ; Zhang P. Evaluation of the aging coefficient and the aging lifetime of carbon black-filled styrene-isoprene-butadiene rubber after thermal-oxidative aging . Compos. Sci. Technol. , 2022 , 220 , 109258 . doi: 10.1016/j.compscitech.2021.109258 http://dx.doi.org/10.1016/j.compscitech.2021.109258

Hu Q. C. ; Chen Q. ; Song P. R. ; Gong X. Y. ; Chen J. Y. ; Zhao Y. X. Performance of thermal-oxidative aging on the structure and properties of ethylene propylene diene monomer (EPDM) vulcanizates . Polymers , 2023 , 15 ( 10 ), 2329 . doi: 10.3390/polym15102329 http://dx.doi.org/10.3390/polym15102329

Maciejewska M. ; Sowińska A. ; Kucharska J. Organic zinc salts as pro-ecological activators for sulfur vulcanization of styrene-butadiene rubber . Polymers , 2019 , 11 ( 10 ), 1723 . doi: 10.3390/polym11101723 http://dx.doi.org/10.3390/polym11101723

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