SYNTHESIS OF PMMA THROUGH PHOTO-INDUCED ATOM TRANSFER RADICAL POLYMERIZATION USING NOVEL PERYLENE-PHENOXAZINE-BASED ORGANO-CATALYST

Đức Châu Trần 1, , Trần Hà Nguyễn 2, Quốc Việt Nguyễn 2, Hoàng Tâm Lưu 1, Lê Hải Trần 3
1 Khoa Công Nghệ Vật Liệu - Trường Đại Học Bách Khoa TP. HCM
2 Phòng Thí Nghiệm Trọng Điểm Quốc Gia Polymer và Composite - Trường Đại Học Bách Khoa - Đại Học Quốc Gia TP. HCM
3 Khoa Kỹ Thuật Hóa Học - Trường Đại Học Bách Khoa - Đại Học Quốc Gia TP. HCM

Main Article Content

Abstract

Poly(methyl methacrylate) (PMMA) is synthesized using a novel organo-catalyst derived from 10-(perylen-yl)-10H-phenoxazine (PHP) under UV irradiation at an ambient temperature. The study aims to demonstrate the capability of PHP in synthesizing PMMA via photo-induced ATRP and suggests a proper molar ratio of reactants engaged in the synthesis process to obtain outcome PMMA in terms of molecular weight and low polydispersity. In the O-ATRP process, the influence of the reaction conditions, including the molar ratios of catalyst and monomer, the initiator content, solvents, and the reaction time on the polymerization of PMMA were studied. The obtained PMMA was characterized using gel permeation chromatography (GPC) measurements to reveal the effect of the individual reaction condition on the outcome polymer. The experiment result shows a high monomer conversion of MMA with the novel PHP organo-photocatalyst (~75%). Among the investigated parameters, the concentration of PHP photocatalyst and polymerization time strongly affect the conversion and polydispersity of the obtained PMMA. Meanwhile, the concentration of the initiator is found to not significantly impact the outcomes of the O-ATRP. Furthermore, the characteristics of PMMA considerably depend on the polarity of the solvent. The higher conversion resulting in a higher molecular weight could be achieved with the solvent having lower polarity. With the increase in conversion, the PHP photocatalyst-based O-ATRP was demonstrated to produce well-controlled PMMA, which has polydispersity lower than 1.5. The optimized reacting system with a molar ratio of [Monomer]:[Initiator]:[PHP] = [100]:[1]:[0.05] under the UV irradiating period of 8 hours produced PMMA with Mn = 28,360 and polydispersity  Đ = 1.25, respectively.

 

Article Details

Author Biography

Đức Châu Trần, Khoa Công Nghệ Vật Liệu - Trường Đại Học Bách Khoa TP. HCM

Phòng Thí Nghiệm Trọng Điểm Quốc Gia Vật Liệu Polymer và Composite

References

Bhattacherjee, A., Sneha, M., Borrell, L., Amoruso, L., Oliver, G., Tyler, J., & Clark, I. P. (2021). Orr-Ewing A J. Singlet and triplet contributions to the excited-state activities of dihydrophenazine, Phenoxazine, and phenothiazine organocatalysts used in atom transfer radical polymerization. Journal of the American Chemical Society, 143, 3613-3627. Retrieved from https://doi.org/10.1021/jacs.1c00279
Borrell, L. Sneha, L., Bhattacherjee, A., Clark, I. P., & Orr-Ewing A. J. (2020). Mapping the multi-step mechanism of a photoredox catalyzed atom-transfer radical polymerization reaction by direct observation of the reactive intermediates. Chemistry Science, 11, 4475-4481. Retrieved from https://doi.org/10.1039/D0SC01194K.
Corbin, D. A., & Miyake, G. M. (2022). Photoinduced Organocatalyzed Atom Transfer Radical Polymerization (O-ATRP): Precision Polymer Synthesis Using Organic Photoredox Catalysis. Chemical Reviews. 122(2), 1830-1874. Retrieved from https://doi.org/10.1021/acs.chemrev.1c00603
Liu, X., Zhang, L., Cheng, Z., & Zhua, X. (2016). Metal-free photoinduced electron transfer–atom transfer radical polymerization (PET–ATRP) via a visible light organic photocatalyst. Polymer Chemistry, 3, 1-12; Retrieved from https://doi.org/10.1039/C5PY01765C
Matyjaszewski, K., Jakubowski, W., Min, K., Tang, W., Huang, J., Braunecker, A. W., & Tsarevsky, V. N. (2006). Diminishing catalyst concentration in atom transfer radical polymerization with reducing agents. PNAS, 103(42), 15309-15314. Retrieved from https://doi.org/10.1073/pnas.0602675103
Matyjaszewski, K. (2012). Atom Transfer Radical Polymerization: From Mechanisms to Applications. Israel Journal of Chemistry, 52, 206-220. Retrieved from https://doi.org/10.1002/ijch.201100101
McCarthy, B., Sartor, S., Cole, J., Damrauer, N., & Miyake, M. G. (2020). Solvent Effects and Side Reactions in Organocatalyzed Atom Transfer Radical Polymerization for Enabling the Controlled Polymerization of Acrylates Catalyzed by Diaryl Dihydrophenazines. Macromolecules, 53(21), 9208-9219. Retrieved from https://doi.org/10.1021/acs.macromol.0c02245
Miyake, G. M., & Theriot, J. C. (2014). Perylene as an Organic Photocatalyst for the Radical Polymerization of Functionalized Vinyl Monomers through Oxidative Quenching with Alkyl Bromides and Visible Light. Macromolecules, 47, 8255-8261. Retrieved from https://doi.org/10.1021/ma502044f
Pan, X., Fang, C., Fantin, M., Malhotra, N., So, W. Y., … Matyjaszewski K. (2016). Mechanism of Photoinduced Metal-Free Atom Transfer Radical Polymerization: Experimental and Computational Studies. Journal of the American Chemical Society, 138(7), 2411-2425. Retrieved from: https://doi.org/10.1021/jacs.5b13455
Pearson, R. M, Lim, C. H., McCarthy, B. G., Musgrave, C. B., & Miyake, G. M. (2016). Organocatalyzed atom transfer radical polymerization using N-aryl phenoxazines as photoredox catalysts. Journal of the American Chemical Society, 138(35), 11399-11407. Retrieved from https://doi.org/10.1021/jacs.6b08068
Quasdorf, K., Murray, I. J., Nguyen, H., Elip, S. V., Ericson. A., … Caille S. (2022). Development of a Continuous Photochemical Bromination/Alkylation Sequence En Route to AMG 423. Organic Process Research & Development, 26(2), 458-466. Retrieved from https://doi.org/10.1021/acs.oprd.1c00469
Swisher, N. A., Corbin, D. A., & Miyake, M. G. (2021). Synthesis, Characterization, and Reactivity of N-Alkyl Phenoxazines in Organocatalyzed Atom Transfer Radical Polymerization. ACS Macro Letters, 10(4), 453-459. Retrieved from https://doi.org/10.1021/acsmacrolett.1c00055
Theriot, J. C., Lim, C. H., Yang, H., Ryan, M. D., Musgrave, C. B., & Miyake, G. M. (2016). Organocatalyzed atom transfer radical polymerization driven by visible light. Science, 352, 1082-1086. Retrieved from https:// doi.org/ 10.1126/science.aaf3935
Theriot, J. C., McCarthy, B. G., Lim, C. H., & Miyake, G. M. (2017). Organocatalyzed Atom Transfer Radical Polymerization: Perspectives on Catalyst Design and Performance. Macromolecular Rapid Communication, 38, 1-12. Retrieved from https://doi.org/10.1002/marc.201700040
Tran, M. H., Phan, T. N. L., Le, V. T., Truong, T. T., Nguyen, H. T., … Nguyen T H. (2019). Phenothiazine Derivative as Organic Photocatalyst for Metal Free Atom Transfer Radical Polymerization. Polymer (Korea), 43(4), 496-502. Retrieved from https://doi.org/10.7317/pk.2019.43.4.496
Truong, P. N., Jones, R. G., Bradford, G. K., Konkolewicz, D., & Anastasaki, A. (2021). A comparison of RAFT and ATRP methods for controlled radical polymerization. Nature Reviews Chemistry, 5, 859-869. Retrieved from https://doi.org/10.1038/s41570-021-00328-8
Vieira, P. R., & Lona, F. M. (2016). Optimization of reaction conditions in functionalized polystyrene synthesis via ATRP by simulations and factorial design. Polymer Bulletin, 73, 1795-1810. Retrieved from https://doi.org/10.1007/s00289-015-1577-z
Vo, H. T., Le, T. H., Nguyen, T. A., Ho, Q. N., Le, V. T.,… Nguyen, T. H. (2020). Synthesis of novel organocatalyzed phenoxazine for free metal atom transfer radical polymerization. Polímeros, 30(2), e2020018. Retrieved from https://doi.org/10.1590/0104-1428.10119