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.
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