Citation: Zhi-Fei Zhang, Kun Yang, Shu-Gao Zhao, Lai-Na Guo. Self-healing Behavior of Ethylene Propylene Diene Rubbers Based on Ionic Association[J]. Chinese Journal of Polymer Science, ;2019, 37(7): 700-707. doi: 10.1007/s10118-019-2241-0 shu

Self-healing Behavior of Ethylene Propylene Diene Rubbers Based on Ionic Association

Zhi-Fei Zhang ^a ,
Kun Yang ^a,b,, ,
Shu-Gao Zhao ^a,, ,
Lai-Na Guo ^c

a.
Key Laboratory of Rubber-plastics, Ministry of Education/Shandong Provincial Key Laboratory of Rubber-Plastics, Qingdao University of Science & Technology, Qingdao 266042, China
b.
College of Chemical Engineering and Materials Science, Tianjin University of Science & Technology, Tianjin 300457, China
c.
Hutchinson, research center, Rue Gustave Nourry, Chalette sur Loing, 45120, France

Corresponding author: Kun Yang, yangkun1463@126.com Shu-Gao Zhao, zhaosgqd@hotmail.com
Received Date: 25 December 2018
Revised Date: 19 February 2019
Accepted Date: 1 January 2018
Available Online: 4 April 2019

To meet the increasing demand for safe, environmentally friendly and high-performance smart materials, self-healing rubbers are highly desired. Here, the self-healing performance of ethylene propylene diene monomer rubber (EPDM) is reported, which was designed by graft-polymerization of zinc dimethacrylate (ZDMA) onto rubber chains to form a reversible ionic cross-linked network. Single ionic cross-linked network and dual network, combining covalent and ionic cross-links, could be tuned by controlling vulcanization process to achieve tailorable mechanical and self-healing properties. It was found that ionic cross-linked EPDM showed a recovery of more than 95% of the original mechanical strength through a healing process of 1 h at 100 °C. The covalent cross-links could improve mechanical properties but block self-healing. Adding 50 wt% liquid rubber to “dry” EPDM could effectively enhance self-healing capability of the dual cross-linked network and the healed tensile strength could reach 0.9 MPa. A compromise between mechanical performance and healing capability could be potentially tailored by controlling vulcanization process and liquid rubber content.
- Ionic bond,
- Self-healing,
- Ethylene propylene diene rubber,
- Dual-network
1. [1]
  Vélez, J. S.; Velásquez, S.; Giraldo, D. Mechanical and rheometric properties of gilsonite/carbon black/natural rubber compounds cured using conventional and efficient vulcanization systems. Polym. Test. 2016, 56, 1-9. doi: 10.1016/j.polymertesting.2016.09.005
2. [2]
  Hosseini, S. M.; Razzaghi-Kashani, M. On the role of nano-silica in the kinetics of peroxide vulcanization of ethylene propylene diene rubber. Polymer 2017, 133, 8-19. doi: 10.1016/j.polymer.2017.10.061
3. [3]
  Movahed, S. O.; Ansarifar, A.; Zohuri, G.; Ghaneie, N.; Kermany, Y. Devulcanization of ethylene-propylene-diene waste rubber by microwaves and chemical agents. J. Elastomer Plast. 2014, 48(2), 122-144.
4. [4]
  Yu, B. C.; Jung, J. W.; Park, K.; Goodenough, J. B. A new approach for recycling waste rubber products in Li-S batteries. Energ. Environ. Sci. 2017, 10(1), 86-90. doi: 10.1039/C6EE02770A
5. [5]
  Molanorouzi, M.; Mohaved, S. O. Reclaiming waste tire rubber by an irradiation technique. Polym. Degrad. Stabil. 2016, 128(C), 115-125.
6. [6]
  Keller, M. W.; White, S. R.; Sottos, N. R. A self-healing poly(dimethyl siloxane) elastomer. Adv. Funct. Mater. 2007, 17(14), 2399-2404. doi: 10.1002/(ISSN)1616-3028
7. [7]
  Chowdhury, R. A.; Hosur, M. V.; Nuruddin, M.; Tcherbi-Narteh, A.; Kumar, A.; Boddu, V.; Jeelani, S. Self-healing epoxy composites: preparation, characterization and healing performance. J. Mater. Res. Technol. 2015, 4(1), 33-43. doi: 10.1016/j.jmrt.2014.10.016
8. [8]
  Pepels, M.; Filot, I.; Klumperman, B.; Goossens, H. Self-healing systems based on disulfide-thiol exchange reactions. Polym. Chem. 2013, 4(18), 4955-11. doi: 10.1039/c3py00087g
9. [9]
  Guo, Y. K.; Li, H.; Zhao, P. X.; Wang, X. F.; Astruc, D.; Shuai, M. B. Thermo-reversible MWCNTs/epoxy polymer for use in self-healing and recyclable epoxy adhesive. Chinese J. Polym. Sci 2017, 35(6), 728-738. doi: 10.1007/s10118-017-1920-y
10. [10]
  Kang, J.; Son, D.; Wang, G. J. N.; Liu, Y.; Lopez, J.; Kim, Y.; Oh, J. Y.; Katsumata, T.; Mun, J.; Lee, Y.; Jin, L.; Tok, J. B. H.; Bao, Z. Tough and water-insensitive self-healing elastomer for robust electronic skin. Adv. Mater. 2018, 15, 1706846.
11. [11]
  Liu, X.; Lu, C.; Wu, X.; Zhang, X. Self-healing strain sensors based on nanostructured supramolecular conductive elastomers. J. Mater. Chem. A 2017, 5(20), 9824-9832. doi: 10.1039/C7TA02416A
12. [12]
  Luan, Y. G.; Zhang, X. A.; Jiang, S. L.; Chen, J. H.; Lyu, Y. F. Self-healing supramolecular polymer composites by hydrogen bonding interactions between hyperbranched polymer and graphene oxide. Chinese J. Polym. Sci. 2018, 36(5), 584-591. doi: 10.1007/s10118-018-2025-y
13. [13]
  Liu, J.; Liu, J.; Wang, S.; Huang, J.; Wu, S.; Tang, Z.; Guo, B.; Zhang, L. An advanced elastomer with an unprecedented combination of excellent mechanical properties and high self-healing capability. J. Mater. Chem. A 2017, 5(48), 25660-25671. doi: 10.1039/C7TA08255J
14. [14]
  Jia, X. Y.; Mei, J. F.; Lai, J. C.; Li, C. H.; You, X. Z. A highly stretchable polymer that can be thermally healed at mild temperature. Macromol. Rapid Commun. 2016, 37(12), 952-956. doi: 10.1002/marc.v37.12
15. [15]
  Rahman, M. A.; Penco, M.; Peroni, I.; Ramorino, G.; Grande, A. M.; Di Landro, L. Self-repairing systems based on ionomers and epoxidized natural rubber blends. ACS Appl. Mater. Interfaces 2011, 3(12), 4865-4874. doi: 10.1021/am201417h
16. [16]
  García-Huete, N.; Post, W.; Laza, J. M.; Vilas, J. L.; León, L. M.; García, S. J. Effect of the blend ratio on the shape memory and self-healing behaviour of ionomer-polycyclooctene cross-linked polymer blends. Eur. Polym. J. 2018, 98, 154-161. doi: 10.1016/j.eurpolymj.2017.11.006
17. [17]
  Das, A.; Sallat, A.; Böhme, F.; Suckow, M.; Basu, D.; Wießner, S.; Stöckelhuber, K. W.; Voit, B.; Heinrich, G. Ionic modification turns commercial rubber into a self-healing material. ACS Appl. Mater. Interfaces 2015, 7(37), 20623-20630. doi: 10.1021/acsami.5b05041
18. [18]
  Li, C.-H.; Wang, C.; Keplinger, C.; Zuo, J.-L.; Jin, L.; Sun, Y.; Zheng, P.; Cao, Y.; Lissel, F.; Linder, C.; You, X. Z.; Bao, Z. A highly stretchable autonomous self-healing elastomer. Nat. Chem. 2016, 8(6), 618-624. doi: 10.1038/nchem.2492
19. [19]
  Chen, Y.; Kushner, A. M.; Williams, G. A.; Guan, Z. Multiphase design of autonomic self-Healing thermoplastic elastomers. Nat. Chem. 2012, 4(6), 467-472. doi: 10.1038/nchem.1314
20. [20]
  Kalista, S. J., Jr.; Ward, T. C.; Oyetunji, Z. Self-healing of poly(ethylene-co-methacrylic acid) copolymers following projectile puncture. Mech. Adv. Mater. Struc. 2007, 14(5), 391-397. doi: 10.1080/15376490701298819
21. [21]
  Zhong, M.; Liu, Y. T.; Xie, X. M. Self-healable, super tough graphene oxide-poly(acrylic acid) nanocomposite hydrogels facilitated by dual cross-linking effects through dynamic ionic interactions. J. Mater. Chem. B 2015, 3(19), 4001-4008. doi: 10.1039/C5TB00075K
22. [22]
  Xu, C.; Cao, L.; Lin, B.; Liang, X.; Chen, Y. Design of self-healing supramolecular rubbers by introducing ionic cross-links into natural rubber via a controlled vulcanization. ACS Appl. Mater. Interfaces 2016, 8(27), 17728-17737. doi: 10.1021/acsami.6b05941
23. [23]
  Zhang, J.; Huo, M.; Li, M.; Li, T.; Li, N.; Zhou, J.; Jiang, J. Shape memory and self-healing materials from supramolecular block polymers. Polymer 2018, 134, 35-43. doi: 10.1016/j.polymer.2017.11.043
24. [24]
  Miwa, Y.; Kurachi, J.; Kohbara, Y.; Kutsumizu, S. Dynamic ionic cross-links enable high strength and ultrastretchability in a single elastomer. Commun. Chem. 2018.
25. [25]
  Peng, Z.; Liang, X.; Zhang, Y.; Zhang, Y. Reinforcement of EPDM by in situ prepared zinc dimethacrylate. J. Appl. Polym. Sci. 2002, 84(7), 1339-1345. doi: 10.1002/(ISSN)1097-4628
26. [26]
  Nie, Y.; Huang, G.; Qu, L.; Zhang, P.; Weng, G.; Wu, J. Cure kinetics and morphology of natural rubber reinforced by the in situpolymerization of zinc dimethacrylate. J. Appl. Polym. Sci. 2010, 115(1), 99-106. doi: 10.1002/app.v115:1
27. [27]
  Chen, Y.; Xu, C. Cross-link network evolution of nature rubber/zinc dimethacrylate composite during peroxide vulcanization. Polym. Composite. 2011, 32(10), 1505-1514. doi: 10.1002/pc.v32.10
28. [28]
  Xu, C.; Huang, X.; Li, C.; Chen, Y.; Lin, B.; Liang, X. Design of “Zn²⁺ salt-bondings” cross-linked carboxylated styrene butadiene rubber with reprocessing and recycling ability via rearrangements of ionic cross-linkings. ACS Sustain. Chem. Eng. 2016, 4(12), 6981-6990. doi: 10.1021/acssuschemeng.6b01897
29. [29]
  Xu, C.; Cao, L.; Huang, X.; Chen, Y.; Lin, B.; Fu, L. Self-healing natural rubber with tailorable mechanical properties based on ionic supramolecular hybrid network. ACS Appl. Mater. Interfaces 2017, 9(34), 29363-29373. doi: 10.1021/acsami.7b09997
30. [30]
  Wang, D.; Guo, J.; Zhang, H.; Cheng, B.; Shen, H.; Zhao, N.; Xu, J. Intelligent rubber with tailored properties for self-healing and shape memory. J. Mater. Chem. A 2015, 3, 12864-12872. doi: 10.1039/C5TA01915J
31. [31]
  Cao, L.; Huang, J.; Chen, Y. Dual cross-linked epoxidized natural rubber reinforced by tunicate cellulose nanocrystals with improved strength and extensibility. ACS Sustain. Chem. Eng. 2018, 6(11), 14802-14811. doi: 10.1021/acssuschemeng.8b03331
32. [32]
  Xu, C.; Cui, R.; Fu, L.; Lin, B. Recyclable and heat-healable epoxidized natural rubber/bentonite composites. Compos. Sci. Technol. 2018, 167, 421-430. doi: 10.1016/j.compscitech.2018.08.027
33. [33]
  Flory, P. J. Statistical mechanics of swelling of network structures. J. Chem. Phys. 1950, 18(1), 108-111. doi: 10.1063/1.1747424
34. [34]
  Bala, P.; Samantaray, B. K.; Srivastava, S. K.; Nando, G. B. Organomodified montmorillonite as filler in natural and synthetic rubber. J. Appl. Polym. Sci. 2004, 92(6), 3583-3592. doi: 10.1002/(ISSN)1097-4628
35. [35]
  Liu, X. Y.; Zhong, M.; Shi, F. K.; Xu, H.; Xie, X. M. Multi-bond network hydrogels with robust mechanical and self-healable properties. Chinese J. Polym. Sci. 2017, 35(10), 1253-1267. doi: 10.1007/s10118-017-1971-0
36. [36]
  Yarmohammadi, M.; Shahidzadeh, M.; Ramezanzadeh, B. Designing an elastomeric polyurethane coating with enhanced mechanical and self-healing properties- the influence of disulfide chain extender. Prog. Org. Coat. 2018, 121, 45-52. doi: 10.1016/j.porgcoat.2018.04.009
37. [37]
  Wool, R. P.; O’Connor, K. M. A Theory crack healing in polymers. J. Appl. Phys. 1981, 52(10), 5953-5963. doi: 10.1063/1.328526
1. [1]
  Salim Ullah , Jianliang Shen , Hong-Tao Xu . Innovative self-healing conductive organogel: Pioneering the future of electronics. Chinese Chemical Letters, 2025, 36(3): 110553-. doi: 10.1016/j.cclet.2024.110553
2. [2]
  Supphachok Chanmungkalakul , Syed Ali Abbas Abedi , Federico J. Hernández , Jianwei Xu , Xiaogang Liu . The dark side of cyclooctatetraene (COT): Photophysics in the singlet states of “self-healing” dyes. Chinese Chemical Letters, 2024, 35(8): 109227-. doi: 10.1016/j.cclet.2023.109227
3. [3]
  Yixia Zhang , Caili Xue , Yunpeng Zhang , Qi Zhang , Kai Zhang , Yulin Liu , Zhaohui Shan , Wu Qiu , Gang Chen , Na Li , Hulin Zhang , Jiang Zhao , Da-Peng Yang . Cocktail effect of ionic patch driven by triboelectric nanogenerator for diabetic wound healing. Chinese Chemical Letters, 2024, 35(8): 109196-. doi: 10.1016/j.cclet.2023.109196
4. [4]
  Jiajia Wang , XinXin Ge , Yajing Xiang , Xiaoliang Qi , Ying Li , Hangbin Xu , Erya Cai , Chaofan Zhang , Yulong Lan , Xiaojing Chen , Yizuo Shi , Zhangping Li , Jianliang Shen . An ionic liquid functionalized sericin hydrogel for drug-resistant bacteria-infected diabetic wound healing. Chinese Chemical Letters, 2025, 36(2): 109819-. doi: 10.1016/j.cclet.2024.109819
5. [5]
  Luyu Zhang , Zirong Dong , Shuai Yu , Guangyue Li , Weiwen Kong , Wenjuan Liu , Haisheng He , Yi Lu , Wei Wu , Jianping Qi . Ionic liquid-based in situ dynamically self-assembled cationic lipid nanocomplexes (CLNs) for enhanced intranasal siRNA delivery. Chinese Chemical Letters, 2024, 35(7): 109101-. doi: 10.1016/j.cclet.2023.109101
6. [6]
  Saadullah Khattak , Hong-Tao Xu , Jianliang Shen . Bio-electronic bandage: Self-powered performances to accelerate intestinal wound healing. Chinese Chemical Letters, 2024, 35(12): 110210-. doi: 10.1016/j.cclet.2024.110210
7. [7]
  Zhong-Hui Sun , Yu-Qi Zhang , Zhen-Yi Gu , Dong-Yang Qu , Hong-Yu Guan , Xing-Long Wu . CoPSe nanoparticles confined in nitrogen-doped dual carbon network towards high-performance lithium/potassium ion batteries. Chinese Chemical Letters, 2025, 36(1): 109590-. doi: 10.1016/j.cclet.2024.109590
8. [8]
  Xu Qu , Pengzhao Wu , Kaixuan Duan , Guangwei Wang , Liang-Liang Gao , Yuan Guo , Jianjian Zhang , Donglei Shi . Self-calibrating probes constructed on a unique dual-emissive fluorescence platform for the precise tracking of cellular senescence. Chinese Chemical Letters, 2024, 35(12): 109681-. doi: 10.1016/j.cclet.2024.109681
9. [9]
  Yan Wang , Huixin Chen , Fuda Yu , Shanyue Wei , Jinhui Song , Qianfeng He , Yiming Xie , Miaoliang Huang , Canzhong Lu . Oxygen self-doping pyrolyzed polyacrylic acid as sulfur host with physical/chemical adsorption dual function for lithium-sulfur batteries. Chinese Chemical Letters, 2024, 35(7): 109001-. doi: 10.1016/j.cclet.2023.109001
10. [10]
  Pei Cao , Yilan Wang , Lejian Yu , Miao Wang , Liming Zhao , Xu Hou . Dynamic asymmetric mechanical responsive carbon nanotube fiber for ionic logic gate. Chinese Chemical Letters, 2024, 35(6): 109421-. doi: 10.1016/j.cclet.2023.109421
11. [11]
  Qiangwei Wang , Huijiao Liu , Mengjie Wang , Haojie Zhang , Jianda Xie , Xuanwei Hu , Shiming Zhou , Weitai Wu . Observation of high ionic conductivity of polyelectrolyte microgels in salt-free solutions. Chinese Chemical Letters, 2024, 35(4): 108743-. doi: 10.1016/j.cclet.2023.108743
12. [12]
  Hao-Cong Li , Ming Zhang , Qiyan Lv , Kai Sun , Xiao-Lan Chen , Lingbo Qu , Bing Yu . Homogeneous catalysis and heterogeneous separation: Ionic liquids as recyclable photocatalysts for hydroacylation of olefins. Chinese Chemical Letters, 2025, 36(2): 110579-. doi: 10.1016/j.cclet.2024.110579
13. [13]
  Yang Qin , Jiangtian Li , Xuehao Zhang , Kaixuan Wan , Heao Zhang , Feiyang Huang , Limei Wang , Hongxun Wang , Longjie Li , Xianjin Xiao . Toeless and reversible DNA strand displacement based on Hoogsteen-bond triplex. Chinese Chemical Letters, 2024, 35(5): 108826-. doi: 10.1016/j.cclet.2023.108826
14. [14]
  Tong Zhang , Xiaojing Liang , Licheng Wang , Shuai Wang , Xiaoxiao Liu , Yong Guo . An ionic liquid assisted hydrogel functionalized silica stationary phase for mixed-mode liquid chromatography. Chinese Chemical Letters, 2025, 36(1): 109889-. doi: 10.1016/j.cclet.2024.109889
15. [15]
  Congyan Liu , Xueyao Zhou , Fei Ye , Bin Jiang , Bo Liu . Confined electric field in nano-sized channels of ionic porous framework towards unique adsorption selectivity. Chinese Chemical Letters, 2025, 36(2): 109969-. doi: 10.1016/j.cclet.2024.109969
16. [16]
  Jingyu Shi , Xiaofeng Wu , Yutong Chen , Yi Zhang , Xiangyan Hou , Ruike Lv , Junwei Liu , Mengpei Jiang , Keke Huang , Shouhua Feng . Structure factors dictate the ionic conductivity and chemical stability for cubic garnet-based solid-state electrolyte. Chinese Chemical Letters, 2025, 36(5): 109938-. doi: 10.1016/j.cclet.2024.109938
17. [17]
  Fangzhou Wang , Wentong Gao , Chenghui Li . A weak but inert hindered urethane bond for high-performance dynamic polyurethane polymers. Chinese Chemical Letters, 2024, 35(5): 109305-. doi: 10.1016/j.cclet.2023.109305
18. [18]
  Yunkang Tong , Haiqiao Huang , Haolan Li , Mingle Li , Wen Sun , Jianjun Du , Jiangli Fan , Lei Wang , Bin Liu , Xiaoqiang Chen , Xiaojun Peng . Cooperative bond scission by HRP/H₂O₂ for targeted prodrug activation. Chinese Chemical Letters, 2024, 35(12): 109663-. doi: 10.1016/j.cclet.2024.109663
19. [19]
  Junmeng Luo , Qiongqiong Wan , Suming Chen . Chemistry-driven mass spectrometry for structural lipidomics at the C=C bond isomer level. Chinese Chemical Letters, 2025, 36(1): 109836-. doi: 10.1016/j.cclet.2024.109836
20. [20]
  Yang Yang , Jing-Li Luo , Xian-Zhu Fu . Water-oxidation intermediates enabling electrochemical propylene epoxidation. Chinese Journal of Structural Chemistry, 2024, 43(5): 100269-100269. doi: 10.1016/j.cjsc.2024.100269

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(790)
HTML views(6)

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