A Self-Healable High Glass Transition Temperature. Bio-Epoxy Material Based on Vitrimer Chemistry

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1 Supporting Information A Self-Healable High Glass Transition Temperature Bio-Epoxy Material Based on Vitrimer Chemistry Tuan Liu, Cheng Hao, Shuai Zhang, Xiaoning Yang, Liwei Wang, Jiarui Han, Yuzhan Li, Junna Xin, Jinwen Zhang* Table S1. The selected vitrimers and their T g values. Healing Refs Method of healing temperature ( C) Starting materials 1 Transesterfication >150 Epoxidised soybean oil, citric acid 2 Transalkylation >130 1,4-bis(2-(prop-2-yn-1-yloxy)ethoxy)benzene, 4,4-bis(azidomethyl)-1,1-biphenyl, 1,6-dibromohexane T g ( C) Transalkylation >130 4 Transesterfication >130 4 Transesterfication >130 5 Transcarbamoylation >150 6 Transesterfication >160 α-azide-ω-alkyne, 1,6-dibromohexane Dimer and trimer acids, BPA epoxy Glutaric anhydride, BPA epoxy Bis(cyclic carbonate), tris(2-aminoethyl)amine Diphenyl epoxy, sebacic acid Transamination >100 Amines and acetoamide monomers Disulfide exchange >130 Isosorbide epoxy and 4,4 disulfanediyldianiline

2 Figure S1. Chemical structure of (a) bisphenol A epoxy and (b) N,N,N,N -tetraglycidyl-4,4 -diaminodiphenylmethane (TGDDM). Figure S2. Chemical Structure of tri-(4-hydroxyphenyl) methane glycidyl ether. Figure S3. The setup for testing crack repairing of the cured epoxies. 2

3 Figure S4. (a) metal mold and (b) rubber mold for curing. Figure S5. DSC heating curves of triphenol and triepoxy (TEP). The liquid TEP was used in this test. 3

4 Figure S6. Derivative thermo-gravimetric (DTG) curve of crude triphenol before crystallization in chloroform. It shows a weak peak at ca. 200 C which belongs to the residue unreacted guaiacol. Figure S7. DSC curves of DER-1, DER-TEP, and TEP-1. The glass transition temperatures are labeled on the curves. 4

5 Figure S8. Storage modulus G and the tan δ curves of these cured epoxies as a function of temperature. 5

6 Figure S9. Stress relaxation of the cured TEP without loading of zinc catalyst. The strain was set at 1.5%. The black curve is the original data, and the red curve is result from polynomial fitting. Figure S10. Stress relaxation of TEP-1 from rheological test. The strain was set at 1.5%. The black curve is the original data, and the red curve is result from polynomial fitting. 6

7 Figure S11. Stress relaxation of TEP-2 from rheological test. The strain was set at 1.5%. The black curve is the original data, and the red curve is result from polynomial fitting. Figure S12. Stress relaxation of TEP-3 from rheological test. The strain was set at 1.5%. The black curve is the original data, and the red curve is result from polynomial fitting. 7

8 Figure S13. Stress relaxation of TEP-4 from rheological test. The strain was set at 1.5%. The black curve is the original data, and the red curve is result from polynomial fitting. Figure S14. Stress relaxation of TEP-1 from rheological test. The strain was set at 2.5%. The black curve is the original data, and the red curve is result from polynomial fitting. 8

9 Figure S15 The digital photos of the TEP-1 film before and after repairing References (1) Altuna, F. I.; Pettarin, V.; Williams, R. J. J. Self-healable polymer networks based on the cross-linking of epoxidised soybean oil by an aqueous citric acid solution. Green Chem. 2013, 15, (2) Tang, J.; Wan, L.; Zhou, Y.; Pan, H.; Huang, F. Strong and efficient self-healing adhesives based on dynamic quaternization cross-links. Journal of Materials Chemistry A 2017, 5, (3) Obadia, M. M.; Mudraboyina, B. P.; Serghei, A.; Montarnal, D.; Drockenmuller, E. Reprocessing and Recycling of Highly Cross-Linked Ion-Conducting Networks through Transalkylation Exchanges of C-N Bonds. J. Am. Chem. Soc. 2015, 137, (4) Montarnal, D.; Capelot, M.; Tournilhac, F.; Leibler, L. Silica-like malleable materials from permanent organic networks. Science 2011, 334, (5) Fortman, D. J.; Brutman, J. P.; Cramer, C. J.; Hillmyer, M. A.; Dichtel, W. R. Mechanically Activated, Catalyst-Free Polyhydroxyurethane Vitrimers. J. Am. Chem. Soc. 2015, 137, (6) Pei, Z.; Yang, Y.; Chen, Q.; Terentjev, E. M.; Wei, Y.; Ji, Y. Mouldable liquid-crystalline elastomer actuators with exchangeable covalent bonds. Nature materials 2014, 13,

10 (7) Denissen, W.; De Baere, I.; Van Paepegem, W.; Leibler, L.; Winne, J.; Du Prez, F. E. Vinylogous Urea Vitrimers and Their Application in Fiber Reinforced Composites. Macromolecules 2018, 51, (8) Ma, Z.; Wang, Y.; Zhu, J.; Yu, J.; Hu, Z. Bio based epoxy vitrimers: Reprocessibility, controllable shape memory, and degradability. Journal of Polymer Science Part A: Polymer Chemistry 2017, 55,