Abstract
Traditional silicone materials have poor mechanical properties, poor interfacial adhesion and lack the ability to be reprocessed or recycled. Herein, we developed a novel strategy of incorporating dynamic noncovalent bonds (2-amino-4-hydroxy-6-methylpyrimidine (UPy)) into side chain of silicone backbones to construct supramolecular silicone poly(urea-urethane) (SSPu) coatings with excellent mechanical performance, strong interfacial adhesion and multiple time recycling capability. Impressively, the prepared SSPu is endowed with simultaneously enhanced stiffness (272.0±23.2 MPa) and toughness (8.0±2.0 MJm−3). Besides, SSPu shows strong interfacial adhesion (up to 9.0±1.3 MPa) to diverse substrate (stainless steel, aluminum, copper, epoxy and glass) with long term stability. Moreover, SSPu exhibits excellent multi-recyclability and reusability without significantly decrease of its performance. In addition to the abovementioned features, the enrichment of siloxane backbones in the surface layer endows SSPu with robust repellency to water/oil. Our strategy provides a powerful route to fabricate a new multifunctional silicone elastomer. It is highly anticipated that our strategy can effectively extend the service life of silicone coating which can be applied in a wide variety of areas including self-cleaning, antifouling.
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References
Yilgör, E.; Yilgör, I. Silicone containing copolymers: synthesis, properties and applications. Prog. Polym. Sci. 2014, 39, 1165–1195.
Owen, M. J. Silicone surface fundamentals. Macromol. Rapid Commun. 2021, 42, e2000360.
Yi, B.; Wang, S.; Hou, C.; Huang, X.; Cui, J.; Yao, X. Dynamic siloxane materials: from molecular engineering to emerging applications. Chem. Eng. J. 2021, 405, 127023.
Hu, P.; Xie, Q.; Ma, C.; Zhang, G. Silicone-based fouling-release coatings for marine antifouling. Langmuir 2020, 36, 2170–2183.
Zhang, H.; Qi, Y.; Zhang, Z.; Yang, Q. Effect of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane on the adhesion of the modified silicone tie-coating to epoxy primer. Coatings 2021, 11, 71.
Selim, M. S.; El-Safty, S. A.; Shenashen, M. A.; Higazy, S. A.; Elmarakbi, A. Progress in biomimetic leverages for marine antifouling using nanocomposite coatings. J. Mater. Chem. B 2020, 8, 3701–3732.
Cheng, F.; Fan, Y.; Zhang, L.; Jiao, X.; Lai, G.; Hua, X.; Yang, X. An easy fabrication method to prepare inexpensive UV-cured transparent silicone modified polyacrylate coatings with good adhesion and UV resistance. Coatings 2020, 10, 675.
Liu, C.; Xie, Q.; Ma, C.; Zhang, G. Fouling release property of polydimethylsiloxane-based polyurea with improved adhesion to substrate. Ind. Eng. Chem. Res. 2016, 55, 6671–6676.
Pérez Das Dores, A.; Llorente, O.; Martin, L.; González, A.; Irusta, L. Polydimethylsiloxane containing waterborne hydrophobic polyurethane coatings with good adhesion to metals: synthesis and characterization. Prog. Org. Coat. 2022, 162, 106564.
Yan, Y.; Huang, J.; Qiu, X.; Zhuang, D.; Liu, H.; Huang, C.; Wu, X.; Cui, X. A strong underwater adhesive that totally cured in water. Chem. Eng. J. 2021, 431, 133460.
Sun, X.; Chen, R.; Gao, X.; Liu, Q.; Liu, J.; Zhang, H.; Yu, J.; Liu, P.; Takahashi, K.; Wang, J. Fabrication of epoxy modified polysiloxane with enhanced mechanical properties for marine antifouling application. Eur. Polym. J 2019, 117, 77–85.
Xiong, G.; Kang, P.; Zhang, J.; Li, B.; Yang, J.; Chen, G.; Zhou, Z.; Li, Q. Improved adhesion, heat resistance, anticorrosion properties of epoxy resins/POSS/methyl phenyl silicone coatings. Prog. Org. Coat. 2019, 135, 454–464.
Lin, Y.; Xie, Y.; Chen, F.; Gong, S.; Yang, W.; Liang, X.; Lian, Y.; Chen, J.; Wei, F.; Bai, W.; Xu, Y.; Jian, R. Bioinspired self-stratification fouling release silicone coating with strong adhesion to substrate. Chem. Eng. J. 2022, 446, 137043.
Yi, B.; Liu, P.; Hou, C.; Cao, C.; Zhang, J.; Sun, H.; Yao, X. Dual-cross-linked supramolecular polysiloxanes for mechanically tunable, damage-healable and oil-repellent polymeric coatings. ACS Appl. Mater. Interfaces 2019, 11, 47382–47389.
Zhao, P.; Wang, L.; Xie, L.; Wang, W.; Wang, L.; Zhang, C.; Li, L.; Feng, S. Mechanically strong, autonomous self-healing, and fully recyclable silicone coordination elastomers with unique photoluminescent properties. Macromol. Rapid Commun. 2021, 42, 2100519.
Lei, Y.; Huang, W.; Huang, Q.; Zhang, A. A novel polysiloxane elastomer based on reversible aluminum-carboxylate coordination. New J. Chem. 2019, 43, 261–268.
Wang, X.; Wang, L.; Fan, X.; Guo, J.; Li, L.; Feng, S. Multifunctional Polysiloxane with coordinative ligand for ion recognition, reprocessable elastomer, and reconfigurable shape memory. Polymer 2021, 229, 124021.
Kim, E. E.; Kononevich, Y. N.; Anisimov, A. A.; Buzin, M. I.; Vasil’ev, V. G.; Korlyukov, A. A.; Ionov, D. S.; Khanin, D. A.; Shtykova, E. V.; Volkov, V. V.; Muzafarov, A. M. Cross-linked polymer networks based on polysiloxane and nickel β-diketonate precursors. React. Funct. Polym. 2021, 164, 104896.
Liang, S.; Huang, Y.; Yuan, Y.; Wang, Y.; Yang, B.; Zhao, X.; Liu, L. Development of a strong, recyclable poly(dimethylsiloxane) elastomer with autonomic self-healing capabilities and fluorescence response properties at room temperature. Macromol. Mater. Eng. 2021, 306, 2100132.
Zhang, C.; Yang, Z.; Nghia Tuan, D.; Li, X.; Nishiyama, Y.; Wu, Q.; Zhang, R.; Sun, P. Using dynamic bonds to enhance the mechanical performance: from microscopic molecular interactions to macroscopic properties. Macromolecules 2019, 52, 5014–5025.
Ma, X.; Zhou, D.; Liu, L.; Wang, L.; Yu, H.; Li, L.; Feng, S. Reprocessable supramolecular elastomers of poly(siloxane-urethane) via self-complementary quadruple hydrogen bonding. Macromol. Chem. Phys. 2021, 222, 2100116.
Lamers, B. A. G.; Sleczkowski, M. L.; Wouters, F.; Engels, T. A. P.; Meijer, E. W.; Palmans, A. R. A. Tuning polymer properties of non-covalent crosslinked PDMS by varying supramolecular interaction strength. Polym. Chem. 2022, 11, 2847–2854.
Bui, R.; Brook, M. A. Dynamic covalent Schiff-base silicone polymers and elastomers. Polymer 2019, 160, 282–290.
Wang, N.; Feng, L.; Xu, X. D.; Feng, S. Dynamic covalent bond cross-linked luminescent silicone elastomer with self-healing and recyclable properties. Macromol. Rapid Commun. 2022, 43, 2100885.
Xu, X.; Hao, X.; Hu, J.; Gao, W.; Ning, N.; Yu, B.; Zhang, L.; Tian, M. Recyclable silicone elastic light-triggered actuator with a reconfigurable Janus structure and self-healable performance. Polym. Chem. 2022, 13, 829–837.
Feng, Z.; Yu, B.; Hu, J.; Zuo, H.; Li, J.; Sun, H.; Ning, N.; Tian, M.; Zhang, L. Multifunctional vitrimer-like polydimethylsiloxane (PDMS): recyclable, self-healable, and water-driven malleable covalent networks based on dynamic imine bond. Ind. Eng. Chem. Res. 2019, 58, 1212–1221.
Zhou, X.; Gong, Z.; Fan, J.; Chen, Y. Self-healable, recyclable, mechanically tough transparent polysiloxane elastomers based on dynamic microphase separation for flexible sensor. Polymer 2021, 237, 124357.
Xiang, H. P.; Rong, M. Z.; Zhang, M. Q. A facile method for imparting sunlight driven catalyst-free self-healability and recyclability to commercial silicone elastomer. Polymer 2017, 108, 339–347.
Gou, Z.; Zuo, Y.; Feng, S. Thermally self-healing silicone-based networks with potential application in recycling adhesives. RSC Adv. 2016, 6, 73140–73147.
Xu, Y.; Guo, M.; Lu, S.; Wei, Z.; Feng, S. Synthesis and characterization of novel poly(sulfone siloxane)s with good solubility and recyclability based on siloxane units. New J. Chem. 2022, 46, 10237–10245.
Liu, Z.; Hong, P.; Huang, Z.; Zhang, T.; Xu, R.; Chen, L.; Xiang, H.; Liu, X. Self-healing, reprocessing and 3D printing of transparent and hydrolysis-resistant silicone elastomers. Chem. Eng. J. 2020, 387, 124142.
Sun, W.; Luo, J.; Zhang, L.; Chen, Y.; Li, P.; Zheng, Y.; Cheng, Y. Insulating silicones based on dynamic hindered urea bonds with high dielectric healability and recyclability. ACS Appl. Polym. Mater. 2021, 3, 5622–5631.
Sun, W.; Zhang, L.; Wang, S.; Mao, J.; Luo, J.; Chen, Y.; Cheng, Y. Mechanically enhanced healable and recyclable silicone with dynamic hindered urea bond for flexible electronics. J. Mater. Chem. C 2021, 9, 8579–8588.
Guo, M.; Pitet, L. M.; Wyss, H. M.; Vos, M.; Dankers, P. Y. W.; Meijer, E. W. Tough stimuli-responsive supramolecular hydrogels with hydrogen-bonding network junctions. J. Am. Chem. Soc. 2014, 136, 6969–6977.
Liu, M.; Wang, Z.; Liu, P.; Wang, Z.; Yao, H.; Yao, X. Supramolecular silicone coating capable of strong substrate bonding, readily damage healing, and easy oil sliding. Sci. Adv. 2019, 5, eaaw5643.
Qin, B.; Zhang, S.; Sun, P.; Tang, B.; Yin, Z.; Cao, X.; Chen, Q.; Xu, J. F.; Zhang, X. Tough and multi-recyclable cross-linked supramolecular polyureas via incorporating noncovalent bonds into main-chains. Adv. Mater. 2020, 32, 2000096.
Sun, P.; Li, Y.; Qin, B.; Xu, J. F.; Zhang, X. Super strong and multi-reusable supramolecular epoxy hot melt adhesives. ACS Mater. Lett. 2021, 3, 1003–1009.
Shi, C. Y.; Zhang, Q.; Tian, H.; Qu, D. H. Supramolecular adhesive materials from small-molecule self-assembly. SmartMat 2020, 1, e1012.
Aida, T.; Meijer, E. W.; Stupp, S. I. Functional supramolecular polymers. Science 2012, 335, 813–817.
de Greef, T. F. A.; Meijer, E. W. Supramolecular polymers. Nature 2008, 453, 171–173.
Sijbesma, R. P.; Beijer, F. H.; Brunsveld, L.; Folmer, B. J. B.; Hirschberg, J. H. K. K.; Lange, R. F. M.; Lowe, J. K. L.; Meijer, E. W. Reversible polymers formed from self-complementary monomers using quadruple hydrogen bonding. Science 1997, 278, 1601–1604.
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.
Acknowledgments
This work was financially supported by the National Natural Science Foundation of China (Nos. 22005053 and 21978050), the Fujian Provincial Department of Science and Technology (No. 2021J05032) and Department of Education (Fujian province) (No. JAT190076).
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Mechanical Strong, Highly Adhesive, Recyclable and Transparent Supramolecular Silicone Coatings with Easy Water/Oil Sliding
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Lin, YC., Chen, F., Yang, SB. et al. Mechanical Strong, Highly Adhesive, Recyclable and Transparent Supramolecular Silicone Coatings with Easy Water/Oil Sliding. Chin J Polym Sci 41, 1796–1804 (2023). https://doi.org/10.1007/s10118-023-2966-7
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DOI: https://doi.org/10.1007/s10118-023-2966-7