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Transformation of gels via catalyst-free selective RAFT photoactivation

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Abstract

This work explores the concept of structurally tailored and engineered macromolecular (STEM) networks by proposing a novel metal-free approach to prepare the networks. STEM networks are composed of polymer networks with latent initiator sites affording post-synthesis modification. The proposed approach relies on selectively activating the fragmentation of trithiocarbonate RAFT agent by relying on visible light RAFT iniferter photolysis coupled with RAFT addition–fragmentation process. The two-step synthesis explored in this work generates networks that are compositionally and mechanically differentiated than their pristine network. In addition, by careful selection of crosslinkers, conventional poly(ethylene glycol) dimethacrylate (Mn = 750) or trithiocarbonate dimethacrylate crosslinker (bis[(2-propionate)ethyl methacrylate] trithiocarbonate (bisPEMAT)), and varying concentrations of RAFT inimer (2-(2-(n-butyltrithiocarbonate)-propionate)ethyl methacrylate (BTPEMA)), three different types of primary (STEM-0) poly(methyl methacrylate) (PMMA) networks were generated under green light irradiation. These networks were then modified with methyl acrylate (MA) or N,N-dimethylacrylamide (DMA), under blue light irradiation to yield STEM-1 gels that are either stiffer or softer with different responses to polarity (hydrophilicity/hydrophobicity).

Graphical abstract: Transformation of gels via catalyst-free selective RAFT photoactivation

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Publication details

The article was received on 11 Feb 2019, accepted on 08 Apr 2019 and first published on 15 Apr 2019


Article type: Paper
DOI: 10.1039/C9PY00213H
Citation: Polym. Chem., 2019, Advance Article

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    Transformation of gels via catalyst-free selective RAFT photoactivation

    S. Shanmugam, J. Cuthbert, J. Flum, M. Fantin, C. Boyer, T. Kowalewski and K. Matyjaszewski, Polym. Chem., 2019, Advance Article , DOI: 10.1039/C9PY00213H

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