Issue 19, 2014

Functionalization of aliphatic polyesters by nitroxide radical coupling

Abstract

Functionalized poly(butylene succinate) (PBS) samples were prepared by a post-polymerization method based on the coupling reaction between TEMPO derivatives bearing different functionalities and PBS macroradicals generated by H-abstraction using a peroxide. 4-Benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl (BzO-TEMPO) and 4-(1-naphthoate)-2,2,6,6-tetramethylpiperidine-1-oxyl (NfO-TEMPO), a pro-fluorescent nitroxide, were successfully grafted on PBS, as revealed by MALDI TOF MS and UV-Vis spectroscopy. The functionalization degrees were accurately determined by UV-Vis analysis and confirmed by 1H-NMR spectroscopy. The grafting site was identified by combining theoretical calculations with experimental evidence. This evidence was collected by both EPR analysis of a functionalized sample subjected to controlled heating in the EPR cavity, and by 1H-NMR spectroscopy. Our functionalization method, which was also tested for poly(lactic acid) (PLA), preserves the original polymer structure. This avoids the crosslinking-branching side reaction, which generally affects the free radical treatment of biodegradable aliphatic polyesters. In addition, using a pro-fluorescent nitroxide to form functionalized samples is a significant step towards unambiguously demonstrating the radical grafting on these types of polymer. It also proves that well-defined fluorescently labeled biodegradable polyesters can be tailored.

Graphical abstract: Functionalization of aliphatic polyesters by nitroxide radical coupling

Supplementary files

Article information

Article type
Paper
Submitted
07 May 2014
Accepted
22 May 2014
First published
29 May 2014

Polym. Chem., 2014,5, 5656-5667

Functionalization of aliphatic polyesters by nitroxide radical coupling

F. Cicogna, S. Coiai, P. Rizzarelli, S. Carroccio, C. Gambarotti, I. Domenichelli, C. Yang, N. Tz. Dintcheva, G. Filippone, C. Pinzino and E. Passaglia, Polym. Chem., 2014, 5, 5656 DOI: 10.1039/C4PY00641K

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