1. 1 Contents 1 Atom transfer radical polymerization (ATRP) Yadollah Shariati Supervisor: Prof. Foad Kazemi June 2021

2. 2 2 2 60 Review Polymer characterization Outline Overview of ATRP

3. 3 Part B Part A Living Free radical polymerization Stable free radical polymerization (SFRP) Reversible addition fragmentation transfer (RAFT) Atom transfer radical polymerization (ATRP) Overview of ATRP Ribelli, T. G., Lorandi, F., Fantin, M., & Matyjaszewski, K. (2019) Macromolecular rapid communications, 40(1), 1800616.‏

4. 4 60 Overview of ATRP ATRP is a means of forming a carbon-carbon bond with a transition metal catalyst. The polymerization from this method is called atom transfer radical addition polymerization (ATRAP). As the name implies, the atom transfer step is crucial in the reaction responsible for uniform polymer chain growth. ATRP (or transition metal-mediated living radical polymerization) was independently discovered by Mitsuo Sawamoto, and by Krzysztof Matyjaszewski and Jin-Shan Wang in 1995. Mitsuo SawamotoKrzysztof MatyjaszewskiJin-Shan Wang Ribelli, T. G., Lorandi, F., Fantin, M., & Matyjaszewski, K. (2019) Macromolecular rapid communications, 40(1), 1800616.‏

5. 5 Overview of ATRP Transition metal :Cu, Fe, Ru, Ni, and Os Ribelli, T. G., Lorandi, F., Fantin, M., & Matyjaszewski, K. (2019) Macromolecular rapid communications, 40(1), 1800616.‏

6. 6 Overview of ATRP Part B Part A Monomer Initiator Ligand Catalyst Solvents Ribelli, T. G., Lorandi, F., Fantin, M., & Matyjaszewski, K. (2019) Macromolecular rapid communications, 40(1), 1800616.‏

7. 7 Overview of ATRP  Polymerization of a wide variety of monomers  Control of molecular weight  Use of multi-functional initiators Advantages Disadvantages  High concentrations of catalyst  Removal of the copper from the polymer  Air-sensitive  The difficulty of conducting ATRP in aqueous media Ribelli, T. G., Lorandi, F., Fantin, M., & Matyjaszewski, K. (2019) Macromolecular rapid communications, 40(1), 1800616.‏

8. 8 Overview of ATRP Ribelli, T. G., Lorandi, F., Fantin, M., & Matyjaszewski, K. (2019) Macromolecular rapid communications, 40(1), 1800616.‏

9. 9 Overview of ATRP  aryl amine < aryl imine < alkyl imine < alkyl amine ≈ pyridine.  bidentate < tridentate < tetradentate. Hexadentate Ribelli, T. G., Lorandi, F., Fantin, M., & Matyjaszewski, K. (2019) Macromolecular rapid communications, 40(1), 1800616.‏

10. 10 Polymer characterization  Nuclear magnetic resonance (NMR)  Infrared spectroscopy (IR)  Thermogravimetric analysis (TGA)  Transmission Electron Microscopy (TEM)  Scanning electron microscope (SEM)  Gel permeation chromatography (GPC) (M n, M w, PDI), P D I = M w / M n Ribelli, T. G., Lorandi, F., Fantin, M., & Matyjaszewski, K. (2019) Macromolecular rapid communications, 40(1), 1800616.‏

11. 11 Treat, Nicolas J., Hazel Sprafke, John W. Kramer, Paul G. Clark, Bryan E. Barton, Javier Read de Alaniz, Brett P. Fors, and Craig J. Hawker." Journal of the American Chemical Society 136, no. 45 (2014): 16096-16101.

12. 12 Proposed mechanism of metal-free photomediated ATRP with 10-phenylphenothiazine as the catalyst (Pn = polymer chain). Treat, Nicolas J., Hazel Sprafke, John W. Kramer, Paul G. Clark, Bryan E. Barton, Javier Read de Alaniz, Brett P. Fors, and Craig J. Hawker." Journal of the American Chemical Society 136, no. 45 (2014): 16096-16101.

13. 13 Optimization of a light-mediated polymerization of methyl methacrylate using organic photoredox catalysts.[a] [a] Reaction conditions: MMA (1 equiv.), photocatalyst (0.001 equiv.), 1 (0.008-0.01 equiv), DMA (2.7 M of MMA) at room temperature with irradiation from 380 nm LEDs for 4 h (Mn = number average molecular weight; Mw = weight average molecular weight). Mn and Mw / Mn determined using size exclusion chromatography (SEC) [b] reaction run with benzyl methacrylate (1 equiv.) for 7 h [c] reaction run in the dark [d] reaction run in the absence of 1 [e] reaction run in the absence of catalyst [f] irradiated with visible light (50 W fluorescent bulbs). Methylene Blue Eosin Y

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15. 15 [a] Reaction conditions: DMAEMA (1 equiv.), photocatalyst (0.001 equiv.), 1 (0.01 equiv), DMA (2.7 M of DMAEMA) at room temperature with irradiation from 380 nm LEDs for 0.5-2 h (Mn = number average molecular weight; Mw = weight average molecular weight). Mn and Mw / Mn determined using size exclusion chromatography (SEC) [b] used 0.00005 equiv. Ir(ppy)3 (0.005 mol % relative to monomer) Treat, Nicolas J., Hazel Sprafke, John W. Kramer, Paul G. Clark, Bryan E. Barton, Javier Read de Alaniz, Brett P. Fors, and Craig J. Hawker." Journal of the American Chemical Society 136, no. 45 (2014): 16096-16101.

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17. 17 Wang, Z., Pan, X., Yan, J., Dadashi-Silab, S., Xie, G., Zhang, J.,... & Matyjaszewski, K. (2017). ACS Macro Letters, 6(5), 546-549.

18. 18 Table 1. Results of MechanoATRP of MA under Various Conditions Wang, Z., Pan, X., Yan, J., Dadashi-Silab, S., Xie, G., Zhang, J.,... & Matyjaszewski, K. (2017). ACS Macro Letters, 6(5), 546-549.

19. 19 Wang, Z., Pan, X., Yan, J., Dadashi-Silab, S., Xie, G., Zhang, J.,... & Matyjaszewski, K. (2017). ACS Macro Letters, 6(5), 546-549.

20. 20 Wang, Z., Pan, X., Yan, J., Dadashi-Silab, S., Xie, G., Zhang, J.,... & Matyjaszewski, K. (2017). ACS Macro Letters, 6(5), 546-549.

21. 21 Rolland, M., Truong, N. P., Whitfield, R., & Anastasaki, A. (2020). ACS Macro Letters, 9(4), 459-463.

22. 22 Rolland, M., Truong, N. P., Whitfield, R., & Anastasaki, A. (2020). ACS Macro Letters, 9(4), 459-463.

23. 23 a.All polymerizations were performed in anisole with MMA as the monomer, MPBA as the initiator, and FeBr3/TBABr as the catalyst. The targeted DP was 150, and the volume ratio of anisole to MMA was maintained at 1:1 in all entries. b.Conversion was calculated by NMR Rolland, M., Truong, N. P., Whitfield, R., & Anastasaki, A. (2020). ACS Macro Letters, 9(4), 459-463.

24. 24 Rolland, M., Truong, N. P., Whitfield, R., & Anastasaki, A. (2020). ACS Macro Letters, 9(4), 459-463.

25. 25 Rolland, M., Truong, N. P., Whitfield, R., & Anastasaki, A. (2020). ACS Macro Letters, 9(4), 459-463.

26. 26 Conclusion