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Issue 8, 2017
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Photocatalytic decarboxylation of diacids for the initiation of free radical polymerization

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Abstract

Photopolymerization, which is one of the most attractive polymerization methods, has been recently studied for the development of new photoinitiators. Herein, we use a binary mixture of titanium dioxide (TiO2) nanoparticles and carboxylic diacid as a novel photoinitiator to initiate the free radical polymerization of vinyl acetate (VAc). The polymerization of VAc is achieved both in aqueous medium and bulk. The initiation mechanism of TiO2/diacids is studied via nuclear magnetic resonance (NMR) spectroscopy using 13C labeled diacids as probing molecules. Further, a universal reaction mechanism is established, where the polymerization of VAc is initiated by the HOOC-R˙ radical, which is generated from the photocatalytic decarboxylation of the diacid. The polymerization kinetics results indicate that the polymerization rate is strongly dependant on the diacid structure. Compared to the use of diacids with an odd number of carbons, it is found that using diacids with an even number of carbons results in the polymerization rate reaching the maximum value faster.

Graphical abstract: Photocatalytic decarboxylation of diacids for the initiation of free radical polymerization

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Publication details

The article was received on 17 Jan 2017, accepted on 19 Jun 2017 and first published on 20 Jun 2017


Article type: Paper
DOI: 10.1039/C7PP00013H
Citation: Photochem. Photobiol. Sci., 2017,16, 1211-1219
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    Photocatalytic decarboxylation of diacids for the initiation of free radical polymerization

    W. Liao and X. Ni, Photochem. Photobiol. Sci., 2017, 16, 1211
    DOI: 10.1039/C7PP00013H

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