Issue 31, 2024

Main chain selective polymer degradation: controlled by the wavelength and assembly

Abstract

The advent of reversible deactivation radical polymerization (RDRP) revolutionized polymer chemistry and paved the way for accessing synthetic polymers with controlled sequences based on vinylic monomers. An inherent limitation of vinylic polymers stems from their all-carbon backbone, which limits both function and degradability. Herein, we report a synthetic strategy utilizing radical ring-opening polymerization (rROP) of complementary photoreactive cyclic monomers in combination with RDRP to embed photoresponsive functionality into desired blocks of polyvinyl polymers. Exploiting different absorbances of photoreactive cyclic monomers, it becomes possible to degrade blocks selectively by irradiation with either UVB or UVA light. Translating such primary structures of polymer sequences into higher order assemblies, the hydrophobicity of the photodegradable monomers allowed for the formation of micelles in water. Upon exposure to light, the nondegradable blocks detached yielding a significant reduction in the micelle hydrodynamic diameter. As a result of the self-assembled micellar environment, telechelic oligomers with photoreactive termini (e.g., coumarin or styrylpyrene) resulting from the photodegradation of polymers in water underwent intermolecular photocycloaddition to photopolymerize, which usually only occurs efficiently at longer wavelengths and a much higher concentration of photoresponsive groups. The reported main chain polymer degradation is thus controlled by the irradiation wavelength and the assembly of the polymers.

Graphical abstract: Main chain selective polymer degradation: controlled by the wavelength and assembly

Supplementary files

Article information

Article type
Edge Article
Submitted
02 Apr 2024
Accepted
23 Jun 2024
First published
02 Jul 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2024,15, 12410-12419

Main chain selective polymer degradation: controlled by the wavelength and assembly

P. T. Do, F. Sbordone, H. Kalmer, A. Sokolova, C. Zhang, L. D. Thai, D. V. Golberg, R. Chapman, B. L. J. Poad and H. Frisch, Chem. Sci., 2024, 15, 12410 DOI: 10.1039/D4SC02172J

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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