Citation: Yan Song, Kai-Feng Chen, Jing-Jing Wang, Yuan Liu, Tao Qi, Guo Liang Li. Synthesis of Polyurethane/Poly(urea-formaldehyde) Double-shelled Microcapsules for Self-healing Anticorrosion Coatings[J]. Chinese Journal of Polymer Science, ;2020, 38(1): 45-52. doi: 10.1007/s10118-019-2317-x shu

Synthesis of Polyurethane/Poly(urea-formaldehyde) Double-shelled Microcapsules for Self-healing Anticorrosion Coatings

Yan Song ^a ,
Kai-Feng Chen ^b,c ,
Jing-Jing Wang ^b,c ,
Yuan Liu ^a ,
Tao Qi ^a ,
Guo Liang Li ^a,,

a.
National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
b.
Xiamen Advanced Materials Academy of Luoyang Ship Material Research Institute, Xiamen 361101, China
c.
Science and Technology on Marine Corrosion and Protection Laboratory, Qingdao 266101, China

Corresponding author: Guo Liang Li, glli@ipe.ac.cn
Received Date: 18 February 2019
Revised Date: 28 May 2019
Available Online: 3 September 2019

One-component, catalyst-free self-healing coatings with double-shelled polymer microcapsules have drawn considerable attention due to wide applications. In this work, the synthesis parameters of double-shelled polymer microcapsules and the mechanism of the self-healing process were systematically investigated. Apart from the chemical structure of the microcapsule shell, the shell thickness, the microcapsule size, and the core fraction could affect the self-healing anticorrosion properties. The synthesis parameters were further optimized in terms of the agitation rate, pH, weight ratio of core to shell, and temperature. Under these conditions, the microcapsule shell consisting of a rough surface formed by poly(urea-formaldehyde) and a smooth inner wall by polyurethane was prepared. The size of the microcapsules and core fraction were calculated to be approximately 30 μm and 75%, respectively. The self-healing anticorrosion coating incorporating as-synthesized microcapsules exhibited corrosion resistance in artificially scratched areas, which was further characterized by electrochemical impedance spectroscopy.
- Double-shelled,
- Microcapsules,
- Anticorrosion,
- Self-healing
1. [1]
  Patrick, J. F.; Robb, M. J.; Sottos, N. R.; Moore, J. S.; White, S. R. Polymers with autonomous life-cycle control. Nature 2016, 540, 363−370. doi: 10.1038/nature21002
2. [2]
  Zhang, P.; Li, G. Advances in healing-on-demand polymers and polymer composites. Prog. Polym. Sci. 2016, 57, 32−63. doi: 10.1016/j.progpolymsci.2015.11.005
3. [3]
  Diesendruck, C. E.; Sottos, N. R.; Moore, J. S.; White, S. R. Biomimetic self-healing. Angew. Chem. Int. Ed. 2015, 54, 10428−10447. doi: 10.1002/anie.201500484
4. [4]
  Hughes, A. E.; Cole, I. S.; Muster, T. H.; Varley, R. J. Designing green, self-healing coatings for metal protection. NPG Asia Mater. 2010, 2, 143−151. doi: 10.1038/asiamat.2010.136
5. [5]
  Zhang, F.; Ju, P.; Pan, M.; Zhang, D.; Huang, Y.; Li, G.; Li, X. Self-healing mechanisms in smart protective coatings: a review. Corros. Sci. 2018, 144, 74−88. doi: 10.1016/j.corsci.2018.08.005
6. [6]
  Shchukin, D.; Mohwald, H. A coat of many functions. Science 2013, 341, 1458−1459. doi: 10.1126/science.1242895
7. [7]
  Wang, L. T.; Deng, L. P.; Zhang, D. W.; Qian, H. C.; Du, C. W.; Li, X. G.; Mol, J. M. C.; Terryn, H. A. Shape memory composite (SMC) self-healing coatings for corrosion protection. Prog. Org. Coat. 2016, 97, 261−268. doi: 10.1016/j.porgcoat.2016.04.041
8. [8]
  Qian, H. C.; Xu, D. K.; Du, C. W.; Zhang, D. W.; Li, X. G.; Huang, L. Y.; Deng, L. P.; Tu, Y. C.; Mol, J. M. C.; Terryn, H. A. Dual-action smart coatings with a self-healing superhydrophobic surface and anti-corrosion properties. J. Mater. Chem. A 2017, 5, 2355−2364. doi: 10.1039/C6TA10903A
9. [9]
  Song, Y.; Liu, Y.; Qi, T.; Li, G. L. Towards dynamic but supertough healable polymers through biomimetic hierarchical hydrogen-bonding interactions. Angew. Chem. Int. Ed. 2018, 57, 13838−13842. doi: 10.1002/anie.201807622
10. [10]
  Lai, Y.; Kuang, X.; Zhu, P.; Huang, M.; Dong, X.; Wang, D. 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
11. [11]
  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
12. [12]
  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
13. [13]
  Shchukin, D. G.; Möhwald, H. Surface-engineered nanocontainers for entrapment of corrosion inhibitors. Adv. Funct. Mater. 2007, 17, 1451−1458. doi: 10.1002/adfm.v17:9
14. [14]
  Zheludkevich, M. L.; Shchukin, D. G.; Yasakau, K. A.; Möhwald, H.; Ferreira, M. G. S. Anticorrosion coatings with self-healing effect based on nanocontainers impregnated with corrosion inhibitor. Chem. Mater. 2007, 19, 402−411. doi: 10.1021/cm062066k
15. [15]
  Liu, X.; Zhang, H.; Wang, J.; Wang, Z.; Wang, S. Preparation of epoxy microcapsule based self-healing coatings and their behavior. Surf. Coat. Techol. 2012, 206, 4976−4980. doi: 10.1016/j.surfcoat.2012.05.133
16. [16]
  Song, Y. K.; Jo, Y. H.; Lim, Y. J.; Cho, S. Y.; Yu, H. C.; Ryu, B. C.; Lee, S. I.; Chung, C. M. Sunlight-induced self-healing of a microcapsule-type protective coating. ACS Appl. Mater. Interfaces 2013, 5, 1378−1384. doi: 10.1021/am302728m
17. [17]
  Chen, K.; Zhou, S.; Yang, S.; Wu, L. Fabrication of all-water-based self-repairing superhydrophobic coatings based on UV-responsive microcapsules. Adv. Funct. Mater. 2015, 25, 1035−1041. doi: 10.1002/adfm.v25.7
18. [18]
  Suryanarayana, C.; Rao, K. C.; Kumar, D. Preparation and characterization of microcapsules containing linseed oil and its use in self-healing coatings. Prog. Org. Coat. 2008, 63, 72−78. doi: 10.1016/j.porgcoat.2008.04.008
19. [19]
  Samadzadeh, M.; Boura, S. H.; Peikari, M.; Ashrafi, A.; Kasiriha, M. Tung oil: an autonomous repairing agent for self-healing epoxy coatings. Prog. Org. Coat. 2011, 70, 383−387. doi: 10.1016/j.porgcoat.2010.08.017
20. [20]
  Yang, J.; Keller, M. W.; Moore, J. S.; White, S. R.; Sottos, N. R. Microencapsulation of isocyanates for self-healing polymers. Macromolecules 2008, 41, 9650−9655. doi: 10.1021/ma801718v
21. [21]
  Huang, M.; Yang, J. Salt spray and EIS studies on HDI microcapsule-based self-healing anticorrosive coatings. Prog. Org. Coat. 2014, 77, 168−175. doi: 10.1016/j.porgcoat.2013.09.002
22. [22]
  Sun, D. W.; Zhang, H.; Tang, X. Z.; Yang, J. L. Water resistant reactive microcapsules for self-healing coatings in harsh environments. Polymer 2016, 91, 33−40. doi: 10.1016/j.polymer.2016.03.044
23. [23]
  Khun, N. W.; Sun, D. W.; Huang, M. X.; Yang, J. L.; Yue, C. Y. Wear resistant epoxy composites with diisocyanate-based self-healing functionality. Wear 2014, 313, 19−28. doi: 10.1016/j.wear.2014.02.011
24. [24]
  Wu, G.; An, J. L.; Sun, D. W.; Tang, X. Z.; Xiang, Y.; Yang, J. L. Robust microcapsules with polyurea/silica hybrid shell for one-part self-healing anticorrosion coatings. J. Mater. Chem. A 2014, 2, 11614−11620. doi: 10.1039/C4TA01312C
25. [25]
  Gite, V. V.; Tatiya, P. D.; Marathe, R. J.; Mahulikar, P. P.; Hundiwale, D. G. Microencapsulation of quinoline as a corrosion inhibitor in polyurea microcapsules for application in anticorrosive PU coatings. Prog. Org. Coat. 2015, 83, 11−18. doi: 10.1016/j.porgcoat.2015.01.021
26. [26]
  Lang, S.; Zhou, Q. Synthesis and characterization of poly(urea-formaldehyde) microcapsules containing linseed oil for self-healing coating development. Prog. Org. Coat. 2017, 105, 99−110. doi: 10.1016/j.porgcoat.2016.11.015
27. [27]
  Sun, D.; An, J.; Wu, G.; Yang, J. Double-layered reactive microcapsules with excellent thermal and non-polar solvent resistance for self-healing coatings. J. Mater. Chem. A 2015, 3, 4435−4444. doi: 10.1039/C4TA05339G
28. [28]
  Caruso, M. M.; Blaiszik, B. J.; Jin, H.; Schelkopf, S. R.; Stradley, D. S.; Sottos, N. R.; White, S. R.; Moore, J. S. Robust, double-walled microcapsules for self-healing polymeric materials. ACS Appl. Mater. Interfaces 2010, 2, 1195−1199. doi: 10.1021/am100084k
29. [29]
  Ming, Y.; Hu, J.; Xing, J.; Wu, M.; Qu, J. Preparation of polyurea/melamine formaldehyde double-layered self-healing microcapsules and investigation on core fraction. J. Microencapsulation 2016, 33, 307−314. doi: 10.1080/02652048.2016.1178352
30. [30]
  Jobdeedamrong, A.; Jenjob, R.; Crespy, D. Encapsulation and release of essential oils in functional silica nanocontainers. Langmuir 2018, 34, 13235−13243. doi: 10.1021/acs.langmuir.8b01652
31. [31]
  Liu, G.; Xie, B.; Fu, D.; Wang, Y.; Fu, Q.; Wang, D. Preparation of nearly monodisperse microcapsules with controlled morphology by in situ polymerization of a shell layer. J. Mater. Chem. 2009, 19, 6605−6609. doi: 10.1039/b901102a
32. [32]
  Alizadegan, F.; Pazokifard, S.; Mirabedini, S. M.; Danaei, M.; Farnood, R. Polyurethane-based microcapsules containing reactive isocyanate compounds: study on preparation procedure and solvent replacement. Colloid. Surface. A 2017, 529, 750−759. doi: 10.1016/j.colsurfa.2017.06.058
33. [33]
  Rule, J. D.; Sottos, N. R.; White, S. R. Effect of microcapsule size on the performance of self-healing polymers. Polymer 2007, 48, 3520−3529. doi: 10.1016/j.polymer.2007.04.008
34. [34]
  Deng, W.; Guo, H. C.; Yu, W. L.; Kan, C. Y. Effects of shell composition, dosage and alkali type on the morphology of polymer hollow microspheres. Chinese J. Polym. Sci. 2018, 36, 43−48. doi: 10.1007/s10118-018-2012-3
35. [35]
  Shi, X. D.; Sun, P. J.; Gan, Z. H. Preparation of porous polylactide microspheres and their application in tissue engineering. Chinese J. Polym. Sci. 2018, 36, 712−719. doi: 10.1007/s10118-018-2079-x
36. [36]
  Yuan, Y.; Sun, P. J.; Shi, X. D.; Gan, Z. H.; Wang, F. S. Biodegradable microspheres with poly(N-isopropylacrylamide) Enriched surface: thermo-responsibility, biodegradation and drug release. Chinese J. Polym. Sci. 2015, 33, 1598−1605. doi: 10.1007/s10118-015-1702-3
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