纤维素纳米晶交联与补强氯丁橡胶的双重功能机制

宋鑫龙; 朱本康; 胡洁; 蒋敏; 段咏欣

doi:10.14028/j.cnki.1003-3726.2026.26.093

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纤维素纳米晶交联与补强氯丁橡胶的双重功能机制

研究论文 | 更新时间：2026-07-27

- 纤维素纳米晶交联与补强氯丁橡胶的双重功能机制
- Improved Vulcanization and Mechanical Properties of Chloroprene Rubber Using Cellulose Nanocrystal Powder as Both Reinforcing and Cross-linking Agents
- 高分子通报 2026年39卷第8期页码：1413-1424
- 作者机构：
  
  青岛科技大学高分子科学与工程学院橡塑材料与工程教育部重点实验室　青岛 266042
- 作者简介：
  
  *段咏欣，E-mail: dyx@qust.edu.cn
- 基金信息：
  
  国家重点研发计划(2022YFC2603502)
- DOI：10.14028/j.cnki.1003-3726.2026.26.093
  中图分类号：
- 收稿：2026-04-13，
  
  录用：2026-05-11，
  
  网络首发：2026-07-10，
  
  纸质出版：2026-08-20
- 稿件说明：
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宋鑫龙, 朱本康, 胡洁, 蒋敏, 段咏欣. 纤维素纳米晶交联与补强氯丁橡胶的双重功能机制. 高分子通报, 2026, 39(8), 1413–1424.

Song, X. L.; Zhu, B. K.; Hu, J.; Jiang, M.; Duan, Y. X. Improved vulcanization and mechanical properties of chloroprene rubber using cellulose nanocrystal powder as both reinforcing and cross-linking Agents. Polym. Bull. (in Chinese), 2026, 39(8), 1413–1424.
宋鑫龙, 朱本康, 胡洁, 蒋敏, 段咏欣. 纤维素纳米晶交联与补强氯丁橡胶的双重功能机制. 高分子通报, 2026, 39(8), 1413–1424. DOI： 10.14028/j.cnki.1003-3726.2026.26.093.

Song, X. L.; Zhu, B. K.; Hu, J.; Jiang, M.; Duan, Y. X. Improved vulcanization and mechanical properties of chloroprene rubber using cellulose nanocrystal powder as both reinforcing and cross-linking Agents. Polym. Bull. (in Chinese), 2026, 39(8), 1413–1424. DOI： 10.14028/j.cnki.1003-3726.2026.26.093.

摘要

氧化锌(ZnO)与乙烯硫脲(ETU)是广泛应用于氯丁橡胶(CR)硫化的关键组分，其中ZnO作为硫化剂与活化剂，ETU作为促进剂，二者协同实现CR的高效硫化；然而，鉴于ETU的潜在致癌性及ZnO的水生毒性，开发环境友好型CR硫化剂已成为关注的焦点。本研究通过喷雾干燥法制备了富含碱性氨基基团的纤维素纳米晶粉末(CCP)，并将其作为一种多功能绿色助剂，凭借 CCP表面氨基实现CR的交联硫化，用于替代ZnO和ETU，同时依托CCP 自身结构特性发挥高效补强作用。对CR/CCP硫化体系的深入研究表明：在150 ℃条件下，CCP的氨基与CR分子链中的叔烯丙基1

2-结构单元几乎不发生反应；而在180 ℃时，二者则发生交联反应。氧化镁(MgO)能显著促进CCP氨基与CR叔烯丙基1

2-结构单元的交联反应，使CR在150 ℃即可发生一定程度的硫化交联，而180 ℃的硫化效果更为显著，为该CR复合材料的最佳硫化温度。除CCP与CR的主交联反应外，CR的自交联及MgO与CR的交联反应共同参与硫化过程。得益于CCP对CR的多重效应，CR复合材料的物理机械性能随CCP用量的增加而逐步提升；当CCP用量为7.5 phr时，复合材料C/M/7.5P展现出最优的物理机械性能，其拉伸强度、300%定伸应力、断裂伸长率、硬度及撕裂强度分别是对照组C/M的1.60、1.33、1.34、1.11及1.61倍。此外，具有疏油特性的CCP显著改善了CR复合材料的耐油性。本研究系统阐释了CCP粉末硫化CR的机理，并且为新型CR硫化体系的开发提供理论指导。

Abstract

Zinc oxide (ZnO) and ethylene thiourea (ETU) are the key components of the vulcanization system of chloroprene rubber (CR)

which endows CR with excellent properties. ZnO acts as both a vulcanizing agent and an activator

whereas ETU serves as an accelerator; they work synergistically to achieve efficient vulcanization of CR. However

the carcinogenicity of ETU and the aquatic toxicity of ZnO have made the development of environment-friendly vulcanizing agents for CR a highly concerning topic. Herein

cellulose nanocrystal powder with alkaline amino groups (CCP) was prepared by spray drying the aqueous suspension of CCP. CCP powder was then employed as a multifunctional green auxiliary to replace ZnO and ETU for CR vulcanization and to reinforce CR. A detailed study of CR/CCP vulcanization indicated that the amino groups of CCP hardly reacted with the tertiary allyl 1

2 units of CR at 150 ℃

while they had a certain cross-linking effect on CR at 180 ℃. Under the activation of magnesium oxide (MgO)

CCP powder showed significant cross-linking effects on CR at 150 and 180 ℃

suggesting that the presence of MgO promotes the reaction between the amino groups of CCP and the tertiary allyl 1

2 units of CR. The optimal vulcanization temperature for the CR composites was 180 ℃. In addition to the main reaction of CCP cross-linking CR

the self-crosslinking of CR and the cross-linking of MgO on CR were also involved during the vulcanization of CR composites. Owing to the multiple effects of CCP on CR

the physical and mechanical properties of CR composites gradually increased with increasing CCP content. The mechanical properties of the CR composite with 7.5 phr CCP (C/M/7.5P) exhibited significant improvements compared to the C/M control

with increases in tensile strength

300% modulus

elongation at break

hardness

and tear strength by factors of 1.60

1.33

1.34

1.11

and 1.61

respectively. The oleophobic CCP significantly improved the oil resistance of the CR composites. This study thoroughly explored the vulcanization of CR with CCP powder and may provide a theoretical reference for the development of new CR vulcanization systems.

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Keywords

references

De Sarkar, M. ; Fujii, N. ; Abe, Y. ; Kamba, Y. ; Sunada, T . Quest for sustainable curatives for chloroprene rubber: a comprehensive review . Rubber Chem. Technol. , 2022 , 95 ( 4 ), 550 – 574 .

李卉 , 李云峰 , 赵红霞 , 王才朋 . 环保促进剂MTT在氯丁橡胶中的应用试验 . 橡胶科技 , 2018 , 16 ( 8 ), 40 – 41 .

王宁 , 刘丹 , 谢敏伟 , 李启彬 , 刘庆梅 . 水环境中纳米氧化锌的环境行为及生物毒性研究进展 . 环境化学 , 2016 , 35 ( 12 ), 2528 – 2534 .

徐治松 . 橡胶硫化促进剂选配技术 . 橡胶科技 , 2023 , 21 ( 5 ), 226 – 231 .

Das, A. ; Naskar, N. ; Datta, R. N. ; Bose, P. P. ; Debnath, S. C . Naturally occurring amino acid: novel curatives for chloroprene rubber . J. Appl. Polym. Sci. , 2006 , 100 ( 5 ), 3981 – 3986 .

Ji, Z. W. ; Yin, Z. Y. ; Jia, Z. Q. ; Wei, J. J . Carbon nanodots derived from urea and citric acid in living cells: cellular uptake and antioxidation effect . Langmuir , 2020 , 36 ( 29 ), 8632 – 8640 .

Song, Y. K. ; Jiang, M. ; Zhou, L. J. ; Yang, H. S. ; Zhang, J. M . Rapidly regenerated CNC/TiO 2 /MnO 2 p orous microspheres for high-efficient dye removal . Carbohydr. Polym. , 2022 , 292 , 119644 .

Liu, Y. X. ; Liu, L. H. ; Wang, K. T. ; Zhang, H. ; Yuan, Y. ; Wei, H. X. ; Wang, X. ; Duan, Y. X. ; Zhou, L. J. ; Zhang, J. M . Modified ammonium persulfate oxidations for efficient preparation of carboxylated cellulose nanocrystals . Carbohydr. Polym. , 2020 , 229 , 115572 .

Zhang, L. Y. ; Sun, Y. H. ; Huang, S. S. ; Xu, H. Z. ; Zhang, Z. J. ; Jiang, M. ; Li, B. X. ; Zong, L. ; Wang, S. X. ; Zhang, J. M . Poly(acrylic acid)-grafted cellulose nanocrystal reinforced supramolecular adhesives: ultrahigh strength, humidity resistance, and pH-controlled recyclability . Carbohydr. Polym. , 2025 , 363 , 123705 .

Hu, J. ; Yang, F. ; Liu, K. ; Kong, Z. Q. ; Qin, J. L. ; Duan, Y. X. ; Zhang, J. M . Effects of cellulose nanocrystals on the vulcanization of natural rubber/cellulose nanocrystals nanocomposite and corresponding regulating strategies . J. Polym. Sci. , 2021 , 59 ( 23 ), 2990 – 3000 .

甘旗星 , 刘浩 , 魏锡均 , 宋英泽 , 宋丽贤 . CNC/GENR自修复复合材料的制备 . 西南科技大学学报 , 2024 , 39 ( 1 ), 18 – 24 .

Jantachum, P. ; Phinyocheep, P . Compatibilization of cellulose nanocrystal-reinforced natural rubber nanocomposite by modified natural rubber . Polymers , 2024 , 16 ( 3 ), 363 .

Vanderfleet, O. M. ; Cranston, E. D . Production routes to tailor the performance of cellulose nanocrystals . Nat. Rev. Mater. , 2021 , 6 ( 2 ), 124 – 144 .

Song, X. Y. ; Zhou, L. J. ; Ding, B. B. ; Cui, X. ; Duan, Y. X. ; Zhang, J. M . Simultaneous improvement of thermal stability and redispersibility of cellulose nanocrystals by using ionic liquids . Carbohydr. Polym. , 2018 , 186 , 252 – 259 .

Hu, J. ; Wu, H. P. ; Liang, S. ; Tian, X. ; Liu, K. ; Jiang, M. ; Midhun Dominic, C. D. ; Zhao, H. Y. ; Duan, Y. X. ; Zhang, J. M . Effects of the surface chemical groups of cellulose nanocrystals on the vulcanization and mechanical properties of natural rubber/cellulose nanocrystals nanocomposites . Int. J. Biol. Macromol. , 2023 , 230 , 123168 .

Liu, C. ; Jin, R. N. ; Ouyang, X. K. ; Wang, Y. G . Adsorption behavior of carboxylated cellulose nanocrystal: polyethyleneimine composite for removal of Cr(VI) ions . Appl. Surf. Sci. , 2017 , 408 , 77 – 87 .

庞松 , 徐新建 , 陈家辉 , 吴友平 . 硫化体系加料方式对天然橡胶/顺丁橡胶并用胶性能的影响 . 橡胶工业 , 2020 , 67 ( 2 ), 135 – 141 .

Wu, H. ; Nagarajan, S. ; Shu, J. ; Zhang, T. P. ; Zhou, L. J. ; Duan, Y. X. ; Zhang, J. M . Green and facile surface modification of cellulose nanocrystal as the route to produce poly(lactic acid) nanocomposites with improved properties . Carbohydr. Polym. , 2018 , 197 , 204 – 214 .

Desai, H. ; Hendrikse, K. G. ; Woolard, C. D . Vulcanization of polychloroprene rubber. I. A revised cationic mechanism for ZnO crosslinking . J. Appl. Polym. Sci. , 2007 , 105 ( 2 ), 865 – 876 .

Kovacic, P . Bisalkylation theory of neoprene vulcanization . Rubber Chem. Technol. , 1955 , 28 ( 4 ), 1021 – 1031 .

Jiang, M. Y. ; Qin, L. K. ; Han, J. J. ; Li, Q. Y . Changes in crosslinking structure of thermo-oxidative aging chloroprene rubber and its effect on strain-induced crystallization . J. Appl. Polym. Sci. , 2024 , 141 ( 4 ), e54858 .

Glenn, F. E . Chloroprene polymers. In: Encyclopedia of Polymer Science and Technology , 3 rd ed . New York : John Wiley & Sons, Inc. , 2004 , 9 , 191 – 225 .

Kong, L. M. ; Zhu, Y. ; Huang, G. S. ; Wu, J. R . Carbon nanodots as dual role of crosslinking and reinforcing chloroprene rubber . Compos. Commun. , 2020 , 22 , 100441 .

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