Citation: Han Jia, Kun Chang, Shu-Ying Gu. Synthesis and Properties of Reversible Disulfide Bond-based Self-healing Polyurethane with Triple Shape Memory Properties[J]. Chinese Journal of Polymer Science, ;2019, 37(11): 1119-1129. doi: 10.1007/s10118-019-2268-2 shu

Synthesis and Properties of Reversible Disulfide Bond-based Self-healing Polyurethane with Triple Shape Memory Properties

Han Jia ^a ,
Kun Chang ^a ,
Shu-Ying Gu ^a,b,,

a.
Department of Polymeric Materials, School of Materials Science and Engineering, Tongji University, Shanghai 201804, China
b.
Key Laboratory of Advanced Civil Engineering Materials, Ministry of Education, Tongji University, Shanghai 201804, China

Corresponding author: Shu-Ying Gu, gushuying@tongji.edu.cn
Received Date: 28 February 2019
Revised Date: 30 March 2019
Available Online: 21 May 2019

A reversible disulfide bond-based self-healing polyurethane with triple shape memory properties was prepared by chain extending of random copolymer poly(lactide-co-caprolactone) (PCLA), hexamethylene diisocyanate (HDI), polytetrahydrofuran (PTMEG), and 4,4′-aminophenyl disulfide. The chemical structures were characterized using ¹H nuclear magnetic resonance (¹H-NMR) spectroscopy, Fourier transform infrared spectroscopy (FTIR), and gel permeation chromatography (GPC). The thermal properties, self-healing properties, triple-shape memory effect, and quantitative shape memory response were evaluated by differential scanning calorimetry (DSC), tensile tests, two-step programming process thermal mechanical experiments, and subsequent progressive thermal recovery. The self-healing mechanism and procedures were investigated using polarizing optical microscopy (POM) and an optical profiler. It was concluded that self-healing properties (up to 60%) and triple-shape memory properties around 35 and 50 °C (with shape fixation ratios of 94.3% and 98.3%, shape recovery ratios of 76.6% and 85.1%, respectively) were integrated to the shape memory polyurethane. As-prepared polyurethane is expected to have potential applications in multi-shape coatings, films, and step-by-step deploying structures.
- Self-healing,
- Reversible disulfide bond,
- Triple shape memory,
- Polyurethane
1. [1]
  Ye, L.; Zhang, S. F.; Lin, Y. C.; Min, J. K.; Ma, L.; Tang, I. Synthesis and characterization of butyl acrylate-based graft polymers with thermos-responsive branching sites via the Diels-Alder reaction of furan/maleimide chains. Chinese J. Polym. Sci. 2018, 36, 1011-1018. doi: 10.1007/s10118-018-2107-x
2. [2]
  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, 728-738. doi: 10.1007/s10118-017-1920-y
3. [3]
  Canadell, J.; Goossens, H.; Klumperman, B. Self-healing materials based on disulfide links. Macromolecules 2011, 44, 2536-2541. doi: 10.1021/ma2001492
4. [4]
  Ling, J.; Rong, M. Z.; Zhang, M. Q. Effect of molecular weight of PEG soft segments on photo-stimulated self-healing performance of coumarin functional polyurethane. Chinese J. Polym. Sci. 2014, 32, 1286-1297. doi: 10.1007/s10118-014-1522-x
5. [5]
  Li, W. T.; Dong, B. Q.; Yang, Z. X.; Xu, J.; Chen, Q.; Li, H. X.; Xing, F.; Jiang, Z. W. Recent advances in intrinsic self-healing cementitious materials. Adv. Mater. 2018, 30, 1705679. doi: 10.1002/adma.v30.17
6. [6]
  van Dijk, N.; van der Zwaag, S. Self-healing phenomena in metals. Adv. Mater. Interfaces 2018, 5, 1800226. doi: 10.1002/admi.v5.17
7. [7]
  Yang, H. J.; Shao, X. H.; Pei, Y. T.; Zhang, Z. F.; de Hosson, J. T. M. Enhanced efficiency of self-healing of Cr2AlC. Mater. Lett. 2018, 227, 51-54. doi: 10.1016/j.matlet.2018.05.038
8. [8]
  Cho, S. H.; White, S. R.; Braun, P. V. Self-healing polymer coatings. Adv. Mater. 2009, 21, 645-649. doi: 10.1002/adma.v21:6
9. [9]
  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, 1253-1267. doi: 10.1007/s10118-017-1971-0
10. [10]
  Raimondo, M.; de Nicola, F.; Volponi, R.; Binder, W.; Michael, P.; Russo, S.; Guadagno, L. Self-repairing CFRPs targeted towards structural aerospace applications. Int. J. Struct. Integ. 2016, 7, 656-670. doi: 10.1108/IJSI-11-2015-0053
11. [11]
  Michal, B. T.; Spencer, E. J.; Rowan, S. J. Stimuli-responsive reversible two-level adhesion from a structurally dynamic shape-memory polymer. ACS Appl. Mater. Interfaces 2016, 8, 11041-11049. doi: 10.1021/acsami.6b01251
12. [12]
  Zhang, B. L.; Zhang, P.; Zhang, H. Z.; Yan, C.; Zheng, Z. J.; Wu, B.; Yu, Y. A transparent, highly stretchable, autonomous self-healing poly(dimethyl siloxane) elastomer. Macromol. Rapid Comm. 2017, 28, 1700110.
13. [13]
  Ding, Z. J.; Yuan, L.; Guan, Q. B.; Gu, A. J.; Liang, G. Z. A reconfiguring and self-healing thermoset epoxy/chain-extended bismaleimide resin system with thermally dynamic covalent bonds. Polymer 2018, 147, 170-182. doi: 10.1016/j.polymer.2018.06.008
14. [14]
  Chang, K.; Jia, H.; Gu, S. Y. A transparent, highly stretchable, self-healing polyurethane based on disulfide bonds. Euro. Polym. J. 2019, 112, 822-831. doi: 10.1016/j.eurpolymj.2018.11.005
15. [15]
  Liu, C. C.; Zhang, A. Y.; Ye, L.; Feng, Z. G. Self-healing biodegradable poly(urea-urethane) elastomers based on hydrogen bonding interactions. Chinese J. Polym. Sci. 2013, 31, 251-262. doi: 10.1007/s10118-013-1211-1
16. [16]
  Luan, Y. G.; Zhang, X. A.; Jiang, S. L.; Chen, J. H.; Lyn, Y. F. Self-healing supramolecular polymer composites by hydrogen bonding interaction between hyperbranched polymer and graphene oxide. Chinese J. Polym. Sci. 2018, 36, 584-591. doi: 10.1007/s10118-018-2025-y
17. [17]
  Rekondo, A.; Martin, R.; de Luzuriaga, A. R.; Cabanero, G.; Grande, H. J.; Odriozola, I. Catalyst-free room-temperature self-healing elastomers based on aromatic disulfide metathesis. Mater. Horiz. 2014, 1, 237-240. doi: 10.1039/C3MH00061C
18. [18]
  Ling, L.; Li, J. H.; Zhang, G. P.; Sun, R.; Wong, C. P. Self-healing and shape memory linear polyurethane based on disulfide linkages with excellent mechanical property. Macromol. Res. 2018, 26, 365-373. doi: 10.1007/s13233-018-6037-9
19. [19]
  Lai, Y.; Kuang, X.; Zhu, P.; Huang, M. M.; Dong, X.; Wang, D. J. Colorless, transparent, robust, and fast scratch-self-healing elastomers via a phase-locked dynamic bonds design. Adv. Mater. 2018, 30, 1802556. doi: 10.1002/adma.v30.38
20. [20]
  Xu, Y.; Chen, D. Shape memory-assisted self-healing polyurethane inspired by a suture technique. J. Mater. Sci. 2018, 53, 10582-10592. doi: 10.1007/s10853-018-2346-9
21. [21]
  Zhang, L. H.; Chen, L. F.; Rowan, S. J. Trapping dynamic disulfide bonds in the hard segments of thermoplastic polyurethane elastomers. Macromol. Chem. Phys. 2017, 218, 1600320. doi: 10.1002/macp.201600320
22. [22]
  Gu, S. Y.; Gao, X. F.; Jin, S. P.; Liu, Y. L. Biodegradable shape memory polyurethanes with controllable trigger temperature. Chinese J. Polym. Sci. 2016, 34, 720-729. doi: 10.1007/s10118-016-1795-3
23. [23]
  Lutz, A.; van den Berg, O.; van Damme, J.; Verheyen, K.; Bauters, E.; de Graeve, I.; du Prez, F. E.; Terryn, H. A shape-recovery polymer coating for the corrosion protection of metallic surfaces. ACS Appl. Mater. Interfaces 2015, 7, 175-183. doi: 10.1021/am505621x
24. [24]
  Gu, S. Y.; Liu, L. L.; Gao, X. F. Triple-shape memory properties of polyurethane/polylactide- polytetramethylene ether blends. Polym. Int. 2015, 64, 1155-1162. doi: 10.1002/pi.2015.64.issue-9
25. [25]
  Zadeh, M. A.; van der Zwaag, S.; García, S. J. Assessment of healed scratches in intrinsic healing coatings by AC/DC/AC accelerated electrochemical procedure. Surf. Coat. Technol. 2016, 303, 396-405. doi: 10.1016/j.surfcoat.2015.11.001
26. [26]
  Zadeh, M. A.; Esteves, A. C. C.; van der Zwaag, S.; Garcia, S. J. Healable dual organic-inorganic crosslinked Sol-gel based polymers: Crosslinking density and tetrasulfide content effect. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1953-1961. doi: 10.1002/pola.v52.14
27. [27]
  Li, F. K.; Hou, J. N.; Zhu, W.; Zhang, X.; Xu, M.; Luo, X. L.; Ma, D. Z.; Kim, B. K. Crystallinity and morphology of segmented polyurethanes with different soft-segment length. J. Appl. Polym. Sci. 1996, 62, 631-638. doi: 10.1002/(ISSN)1097-4628
28. [28]
  Liaw, D. J. The relative physical and thermal properties of polyurethane elastomers: Effect of chain extenders of bisphenols diisocyanate and polyol structures. J. Appl. Polym. Sci. 1997, 66, 1251-1265. doi: 10.1002/(ISSN)1097-4628
29. [29]
  Jeon, O.; Lee, S. H.; Kim, S. H.; Lee, Y. M.; Kim, Y. H. Synthesis and characterization of poly(L-lactide)-poly(ε-caprolactone) multiblock copolymers. Macromolecules 2003, 36, 5585-5592. doi: 10.1021/ma034006v
30. [30]
  Sarma, R. J.; Otto, S.; Nitschke, J. R. Disulfides, imines, and metal coordination within a single system: Interplay between three dynamic equilibria. Chem. Eur. J. 2007, 13, 9542-9546. doi: 10.1002/(ISSN)1521-3765
31. [31]
  Belenguer, A. M.; Friscic, T.; Day, G. M.; Sanders, J. K. M. Solid-state dynamic combinatorial chemistry: Reversibility and thermodynamic product selection in covalent mechanosynthesis. Chem. Sci. 2011, 2, 696-700. doi: 10.1039/c0sc00533a
32. [32]
  Nevejans, S.; Ballard, N.; Miranda, J. I.; Reck, B.; Asua, J. M. The underlying mechanisms for self-healing of poly(disulfide)s. Phys. Chem. Chem. Phys. 2016, 18, 27577-27583. doi: 10.1039/C6CP04028D
33. [33]
  Wool, R. P.; O’Connor, K. M. A theory crack healing in polymers. J. Appl. Phys. 1981, 52, 5953-5963. doi: 10.1063/1.328526
34. [34]
  Du, W. N.; Jin, Y.; Pan, J. Z.; Fan, W. H.; Lai, S. Q.; Sun, X. P. Thermal induced shape-memory and self-healing of segmented polyurethane containing diselenide bonds. J. Appl. Polym. Sci. 2018, 135, 46326. doi: 10.1002/app.46326
35. [35]
  Rodriguez, E. D.; Luo, X. F.; Mather, P. T. Linear/network poly(ε-caprolactone blends exhibiting shape memory assisted self-healing (SMASH). ACS Appl. Mater. Interfaces 2011, 3, 152-161. doi: 10.1021/am101012c
36. [36]
  Zheng, N.; Hou, J. J.; Xu, Y.; Fang, Z. Z.; Zou, W. K.; Zhao, Q.; Xie, T. Catalyst-free thermoset polyurethane with permanent shape reconfigurability and highly tunable triple-shape memory performance. ACS Macro Lett. 2017, 6, 326-330. doi: 10.1021/acsmacrolett.7b00037
37. [37]
  Zhao, Q.; Qi, H. J.; Xie, T. Recent progress in shape memory polymer: New behavior, enabling materials, and mechanistic understanding. Prog. Polym. Sci. 2015, 49-50, 79-120.
38. [38]
  Zheng, N.; Xie, T. Thermadapt shape memory polymer. Acta Polymerica Sinica (in Chinese) 2017, 11, 1715-1724.
1. [1]
  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
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]
  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
4. [4]
  Fengyao Cui , Qiaona Zhang , Tangxin Xiao , Zhouyu Wang , Leyong Wang . Reversible phosphorescence in pseudopolyrotaxane elastomer. Chinese Chemical Letters, 2024, 35(10): 110061-. doi: 10.1016/j.cclet.2024.110061
5. [5]
  Lian Sun , Honglei Wang , Ming Ma , Tingting Cao , Leilei Zhang , Xingui Zhou . Shape and composition evolution of Pt and Pt₃M nanocrystals under HCl chemical etching. Chinese Chemical Letters, 2024, 35(9): 109188-. doi: 10.1016/j.cclet.2023.109188
6. [6]
  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
7. [7]
  Jingwen Zhao , Jianpu Tang , Zhen Cui , Limin Liu , Dayong Yang , Chi Yao . A DNA micro-complex containing polyaptamer for exosome separation and wound healing. Chinese Chemical Letters, 2024, 35(9): 109303-. doi: 10.1016/j.cclet.2023.109303
8. [8]
  Ping Wang , Ting Wang , Ming Xu , Ze Gao , Hongyu Li , Bowen Li , Yuqi Wang , Chaoqun Qu , Ming Feng . Keplerate polyoxomolybdate nanoball mediated controllable preparation of metal-doped molybdenum disulfide for electrocatalytic hydrogen evolution in acidic and alkaline media. Chinese Chemical Letters, 2024, 35(7): 108930-. doi: 10.1016/j.cclet.2023.108930
9. [9]
  Lin Li , Bingjun Sun , Jin Sun , Lin Chen , Zhonggui He . Binary prodrug nanoassemblies combining chemotherapy and ferroptosis activation for efficient triple-negative breast cancer therapy. Chinese Chemical Letters, 2024, 35(10): 109538-. doi: 10.1016/j.cclet.2024.109538
10. [10]
  Peizhe Li , Qiaoling Liu , Mengyu Pei , Yuci Gan , Yan Gong , Chuchen Gong , Pei Wang , Mingsong Wang , Xiansong Wang , Da-Peng Yang , Bo Liang , Guangyu Ji . Chlorogenic acid supported strontium polyphenol networks ensemble microneedle patch to promote diabetic wound healing. Chinese Chemical Letters, 2024, 35(8): 109457-. doi: 10.1016/j.cclet.2023.109457
11. [11]
  Simin Wei , Yaqing Yang , Junjie Li , Jialin Wang , Jinlu Tang , Ningning Wang , Zhaohui Li . The Mn/Yb/Er triple-doped CeO₂ nanozyme with enhanced oxidase-like activity for highly sensitive ratiometric detection of nitrite. Chinese Chemical Letters, 2024, 35(6): 109114-. doi: 10.1016/j.cclet.2023.109114
12. [12]
  Fanjun Kong , Yixin Ge , Shi Tao , Zhengqiu Yuan , Chen Lu , Zhida Han , Lianghao Yu , Bin Qian . Engineering and understanding SnS_0.5Se_0.5@N/S/Se triple-doped carbon nanofibers for enhanced sodium-ion batteries. Chinese Chemical Letters, 2024, 35(4): 108552-. doi: 10.1016/j.cclet.2023.108552
13. [13]
  Jianye Kang , Xinyu Yang , Xuhao Yang , Jiahui Sun , Yuhang Liu , Shutao Wang , Wenlong Song . Carbon dots-enhanced pH-responsive lubricating hydrogel based on reversible dynamic covalent bondings. Chinese Chemical Letters, 2024, 35(5): 109297-. doi: 10.1016/j.cclet.2023.109297
14. [14]
  Jie Zhou , Quanyu Li , Xiaomeng Hu , Weifeng Wei , Xiaobo Ji , Guichao Kuang , Liangjun Zhou , Libao Chen , Yuejiao Chen . Water molecules regulation for reversible Zn anode in aqueous zinc ion battery: Mini-review. Chinese Chemical Letters, 2024, 35(8): 109143-. doi: 10.1016/j.cclet.2023.109143
15. [15]
  Guoxing Liu , Yixin Li , Changming Tian , Yongmei Xiao , Lijie Liu , Zhanqi Cao , Song Jiang , Xin Zheng , Caoyuan Niu , Yun-Lai Ren , Liangru Yang , Xianfu Zheng , Yong Chen . Highly reversible photomodulated hydrosoluble stiff-stilbene supramolecular luminophor induced by cucurbituril. Chinese Chemical Letters, 2024, 35(8): 109403-. doi: 10.1016/j.cclet.2023.109403
16. [16]
  Qiongqiong Wan , Yanan Xiao , Guifang Feng , Xin Dong , Wenjing Nie , Ming Gao , Qingtao Meng , Suming Chen . Visible-light-activated aziridination reaction enables simultaneous resolving of C=C bond location and the sn-position isomers in lipids. Chinese Chemical Letters, 2024, 35(4): 108775-. doi: 10.1016/j.cclet.2023.108775
17. [17]
  Yi Luo , Lin Dong . Multicomponent remote C(sp²)-H bond addition by Ru catalysis: An efficient access to the alkylarylation of 2H-imidazoles. Chinese Chemical Letters, 2024, 35(10): 109648-. doi: 10.1016/j.cclet.2024.109648
18. [18]
  Changzhu Huang , Wei Dai , Shimao Deng , Yixin Tian , Xiaolin Liu , Jia Lin , Hong Chen . A self-cleaning window for high-efficiency photodegradation of indoor formaldehyde. Chinese Chemical Letters, 2024, 35(9): 109429-. doi: 10.1016/j.cclet.2023.109429
19. [19]
  Lishan Xiong , Xinyuan Li , Xiaojie Lu , Zhendong Zhang , Yan Zhang , Wen Wu , Chenhui Wang . Inhaled multilevel size-tunable, charge-reversible and mucus-traversing composite microspheres as trojan horse: Enhancing lung deposition and tumor penetration. Chinese Chemical Letters, 2024, 35(9): 109384-. doi: 10.1016/j.cclet.2023.109384
20. [20]
  Zhenzhu Wang , Chenglong Liu , Yunpeng Ge , Wencan Li , Chenyang Zhang , Bing Yang , Shizhong Mao , Zeyuan Dong . Differentiated self-assembly through orthogonal noncovalent interactions towards the synthesis of two-dimensional woven supramolecular polymers. Chinese Chemical Letters, 2024, 35(5): 109127-. doi: 10.1016/j.cclet.2023.109127

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(662)
HTML views(1)

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