Cumali ÇELİK

Synthesis and characterization of benzodioxinone mono-telechelics and their use in block copolymerization

Poly(methyl methacrylate) (PMMA) and poly(ethylene glycol) methyl ether (mPEG)-based monotelechelics were quantitatively prepared by copper (I)-catalyzed azide/alkyne cycloaddition (CuAAC) click reactions using azido-terminated polymers and alkyne functional benzodioxinones. The monotelechelic containing dimethyl moities (2,2-dimethyl-5-(prop-2-yn-1-yloxy)-4Hbenzo[d][1,3]dioxin-4-one) was heat-sensitive, whereas the monotelechelic containing diphenyl moieties (2,2-diphenyl-5-(prop-2-yn1-yloxy)-4H-benzo[d][1,3]dioxin-4-one) was UV light sensitive. Based on the FT-IR, $^{1} H-NMR$, and GPC investigations, the CuAAC click reactions enable the quantitative syntheses of monotelechelics under mild conditions. Moreover, the photosensitive mPEG-based monotelechelic was further utilized for the block copolymer synthesis upon UV-light irradiation. The photoinduced acylation of mPEG monotelechelic consist of (2,2-diphenyl-5-(prop-2-yn-1-yloxy)-4H-benzo[d][1,3]dioxin-4-one) in the presence of hydroxy-terminated poly(epsilon caprolactone) enabled the successful block copolymer formation.

PDF

___

1. Tasdelen MA, Kahveci MU, Yagci Y. Telechelic polymers by living and controlled/living polymerization methods. Progress in Polymer Science 2011; 36 (4): 455-567. doi: 10.1016/j.progpolymsci.2010.10.002
2. Liu P, Dong Z, Kilbinger AFM. Mono-telechelic polymers by catalytic living ring-opening metathesis polymerization with secondgeneration Hoveyda–Grubbs catalyst. Materials Chemistry Frontiers 2020; 4 (9): 2791-2796. doi: 10.1039/d0qm00417k
3. Yagci Y, Tasdelen MA. Mechanistic transformations involving living and controlled/living polymerization methods. Progress in Polymer Science 2006; 31 (12): 1133-1170. doi: 10.1016/j.progpolymsci.2006.07.003
4. Tasdelen MA, Yilmaz G, Iskin B, Yagci Y. Photoinduced free radical promoted copper (I)-catalyzed click chemistry for macromolecular syntheses. Macromolecules 2012; 45 (1): 56-61. doi: 10.1021/ma202438w
5. Arslan M, Tasdelen MA. Click chemistry in macromolecular design: complex architectures from functional polymers. Chemistry Africa 2019; 2 (2): 195-214. doi: 10.1007/s42250-018-0030-8
6. Altinkok C, Uyar T, Tasdelen MA, Yagci Y. In situ synthesis of polymer/clay nanocomposites by type II photoinitiated free radical polymerization. Journal of Polymer Science Part A: Polymer Chemistry 2011; 49 (16): 3658-3663. doi: 10.1002/pola.24788
7. Liu P, Yasir M, Ruggi A, Kilbinger, AFM. Heterotelechelic polymers by ring-opening metathesis and regioselective chain transfer. Angewandte Chemie International Edition 2018; 57 (4): 914-917. doi: 10.1002/anie.201708733
8. Arslan M, Aydin D, Degirmenci A, Sanyal A, Sanyal R. Embedding well-defined responsive hydrogels with nanocontainers: tunable materials from telechelic polymers and cyclodextrins. ACS Omega 2017; 2 (10): 6658-6667. doi: 10.1021/acsomega.7b00787
9. Vinciguerra D, Tran J, Nicolas J. Telechelic polymers from reversible-deactivation radical polymerization for biomedical applications. Chemical Communications 2018; 54 (3): 228-240. doi: 10.1039/c7cc08544c
10. Tasdelen MA, Yagci Y. Benzodioxinone Photochemistry in Macromolecular Science: Progress, Challenges, and Opportunities. ACS Macro Letters 2017; 6 (12): 1392-1397. doi: 10.1021/acsmacrolett.7b00788
11. Leibfarth FA, Hawker CJ. The emerging utility of ketenes in polymer chemistry. Journal of Polymer Science Part A: Polymer Chemistry 2013; 51 (18): 3769-3782. doi: 10.1002/pola.26797
12. Leibfarth FA, Kang M, Ham M, Kim J, Campos LM, Gupta N, Moon B, Hawker CJ. A facile route to ketene-functionalized polymers for general materials applications. Nature Chemistry 2010; 2 (3): 207-212. doi: 10.1038/nchem.538
13. Jung H, Leibfarth FA, Woo S, Lee S, Kang M, Moon B, Hawker CJ, Bang J. Efficient surface neutralization and enhanced substrate adhesion through ketene mediated crosslinking and functionalization. Advanced Functional Materials 2013; 23 (12): 1597-1602. doi: 10.1002/ adfm.201201352
14. Leibfarth FA, Wolffs M, Campos LM, Delany K, Treat N et al. Low-temperature ketene formation in materials chemistry through molecular engineering. Chemical Science 2012; 3 (3): 766-771. doi: 10.1039/C2SC00841F
15. Leibfarth FA, Schneider Y, Lynd NA, Schultz A, Moon B et al. Ketene functionalized polyethylene: control of cross-link density and material properties. Journal of the American Chemical Society 2010; 132 (42): 14706-14709. doi: 10.1021/ja1060643
16. Kumbaraci V, Talinli N, Yagci Y. Photoinduced crosslinking of polymers containing pendant hydroxyl groups by using bisbenzodioxinones. Macromolecular Rapid Communications 2007; 28 (1): 72-77. doi: 10.1002/marc.200600653
17. Arslan M, Motallebzadeh A, Kiskan B, Demirel AL, Kumbaraci IV, Yagci Y. Combining benzoxazine and ketene chemistries for selfhealing of high performance thermoset surfaces. Polymer Chemistry 2018; 9 (15): 2031-2039. doi: 10.1039/C8PY00293B
18. Aydogan C, Ciftci M, Kumbaraci V, Talinli N, Yagci Y. Hyperbranced polymers by photoinduced self-condensing vinyl polymerization using bisbenzodioxinone. Macromolecular Chemistry and Physics 2017; 218 (10): 1700045. doi: 10.1002/macp.201700045
19. Durmaz YY, Kumbaraci V, Demirel AL, Talinli N, Yagci Y. Graft copolymers by the combination of ATRP and photochemical acylation process by using benzodioxinones. Macromolecules 2009; 42 (11): 3743-3749. doi: 10.1002/macp.201700589
20. Tasdelen MA, Kumbaraci V, Jockusch S, Turro NJ, Talinli N, Yagci Y. Photoacid generation by stepwise two-photon absorption: photoinitiated cationic polymerization of cyclohexene oxide by using benzodioxinone in the presence of iodonium salt. Macromolecules 2008; 41 (2): 295-297. doi: 10.1021/ma7023649
21. Kumbaraci V, Aydogan B, Talinli N, Yagci Y. Naphthodioxinone-1, 3-benzodioxole as photochemically masked one-component type II photoinitiator for free radical polymerization. Journal of Polymer Science Part A: Polymer Chemistry 2012; 50 (13): 2612-2618. doi: 10.1002/pola.26034
22. Tasdelen MA, Kumbaraci V, Talinli N, Yagci Y. Photochemically masked benzophenone: photoinitiated free radical polymerization by using benzodioxinone. Polymer 2006; 47 (22): 7611-7614. doi: 10.1016/j.polymer.2006.09.020
23. Tasdelen MA, Taskin OS, Celik C. Orthogonal synthesis of block copolymer via photoinduced CuAAC and ketene chemistries. Macromolecular Rapid Communications 2016; 37 (6): 521-526. doi: 10.1002/marc.201500563
24. Alkan Goksu Y, Kumbaraci V, Yagci Y. Modular photoinduced grafting onto approach by ketene chemistry. Journal of Polymer Science Part A: Polymer Chemistry 2019; 57 (3): 274-280. doi: 10.1002/pola.29045
25. Doran S, Murtezi E, Barlas FB, Timur S, Yagci Y. One-Pot photo-induced sequential CuAAC and thiolene click strategy for bioactive macromolecular synthesis. Macromolecules 2014; 47 (11): 3608-3613. doi: 10.1021/ma5007039
26. Deshayes G, Mercier FAG, Degée P, Verbruggen I, Biesemans M, Willem R, Dubois P. Mechanistic study of Bu2SnCl2-mediated ringopening polymerization of ε-caprolactone by multinuclear NMR spectroscopy. Chemistry–A European Journal 2003; 9 (18): 4346-4352. doi: 10.1002/chem.200304769
27. Soltani O, De Brabander JK. Synthesis of Functionalized Synthesis of functionalized salicylate esters and amides by photochemical acylation. Angewandte Chemie International Edition 2005; 44 (11): 1696-1699. doi: 10.1002/anie.200462577
28. Kumbaraci V, Talinli N, Yagci Y. Photoinduced synthesis of oligoesters. Macromolecules 2006; 39 (18): 6031-6035. doi: 10.1021/ma0607721