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Metal-free, visible light-mediated atom transfer radical polymerization of hydroxypropyl cellulose-graft-poly(methyl methacrylate)s: effect of polymer side chains on thermo-responsive behavior of hydroxypropyl cellulose

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Abstract

We exploited organic photo-redox-catalyzed atom transfer radical polymerization (O-ATRP) to synthesize a thermo-responsive polymer with a narrow molecular weight distribution. Poly(methyl methacrylate) (PMMA) chains were polymerized from a hydroxypropyl cellulose (HPC)-based macroinitiator using metal-free O-ATRP under visible-light irradiation. This O-ATRP is mediated by 1,2,3,5-tetrakis (carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN), a photoredox catalyst with a substantial excited-state reduction potential, low cost, and ease of preparation. The synthesis of a series of PMMA-grafted HPC (PMMA-g-HPC) was characterized by various analytical methods, including FTIR spectroscopy, NMR spectroscopy, TGA, and GPC analysis. The lower critical solution temperature (LCST) of the polymers was determined by measuring the transmittance of the polymer solution as a function of the temperature at various pH values. Consequently, we expanded the LCST window of the HPC-based polymers and generated the opposite pH dependency of the LCST by forming PMMA-g-HPCs. Our “grafting-from” synthetic approach and thermo-responsive polymers, which are controllable in full range of physiological conditions, are promising in a variety of biological, electronics, and biosensor applications, particularly in drug delivery systems.

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Acknowledgments

The authors would like to acknowledge the Researcher’s Supporting Project Number (RSP2023R43), King Saud University, Riyadh, Saudi Arabia. This work was also supported by the Gachon University research fund of 2022 (GCU-202205700001).

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Authors and Affiliations

  1. Department of Chemistry, School of Science, University of Management and Technology, C-II, Johar Town, Lahore, 54770, Pakistan

    Muhammad Asif Iqbal, Toheed Akhter, Muhammad Faheem & Sohail Nadeem

  2. Department of Chemical Engineering, College of Engineering, King Saud University, Riyadh, 11421, Saudi Arabia

    Asif Mahmood & Waheed Al-Masry

  3. Department of Chemistry, COMSATS University Islamabad, Lahore Campus, Lahore, Pakistan

    Sadaf Ul Hassan

  4. Department of Chemical and Biological Engineering, Gachon University, 1342 Seongnam-daero, Seongnam, 13120, Republic of Korea

    Chan Ho Park

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  1. Muhammad Asif Iqbal
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  2. Toheed Akhter
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  3. Muhammad Faheem
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  4. Asif Mahmood
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Contributions

Conceptualization, TA, AM.; methodology, MAI.; validation, TA and CHP.; formal analysis, MAI and WA.; investigation, MAI.; resources, SN, MF and WA.; writing—original draft preparation, MAI, TA, SUH, CHP.; writing—review and editing, TA and CHP; supervision, TA and AM, SUH.; All authors have read and agreed to the published version of the manuscript.

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Correspondence to Toheed Akhter or Chan Ho Park.

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Iqbal, M.A., Akhter, T., Faheem, M. et al. Metal-free, visible light-mediated atom transfer radical polymerization of hydroxypropyl cellulose-graft-poly(methyl methacrylate)s: effect of polymer side chains on thermo-responsive behavior of hydroxypropyl cellulose. Cellulose 30, 7519–7533 (2023). https://doi.org/10.1007/s10570-023-05345-y

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