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Grafting well-defined CO2-responsive polymers to cellulose nanocrystals via nitroxide-mediated polymerisation: effect of graft density and molecular weight on dispersion behaviour

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Abstract

A grafting to approach on a cellulose derivative using reversible deactivation radical polymerisation (RDRP) is reported for the first time. SG1-capped poly(N,N-(diethylamino)ethyl methacrylate) (PDEAEMA) and poly(N-3-(dimethylamino) propyl methacrylamide) (PDMAPMAm) macroalkoxyamines of different molecular weights, showing low dispersity, high livingness and end group fidelity were grown in bulk through Nitroxide-Mediated Polymerisation (NMP) using the alkoxyamine N-hydroxysuccinimidyl BlocBuilder® (NHS-BlocBuilder). In the second step, these CO2-responsive macroalkoxyamines were grafted to glycidyl methacrylate (GMA) modified cellulose nanocrystals (CNC) to obtain CO2-responsive CNC. Two different tertiary amine polymers were selected to investigate how differences in their pKaH and Tg affected the final properties of the graft-modified CNC. The effect of the macroalkoxyamines molecular weight on the graft density was investigated in detail and was shown to have a direct influence on the dispersion behaviour and CO2-responsiveness of the grafted CNC particles, as demonstrated by zeta potential measurements in water and phase shuttling experiments between oil and water. The results suggested that a particular pKaH, minimum graft density and graft length are required to effectively switch the CNC from a hydrophilic to a fully hydrophobic state.

Graphical abstract: Grafting well-defined CO2-responsive polymers to cellulose nanocrystals via nitroxide-mediated polymerisation: effect of graft density and molecular weight on dispersion behaviour

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Publication details

The article was received on 26 Jul 2017, accepted on 07 Sep 2017 and first published on 08 Sep 2017


Article type: Paper
DOI: 10.1039/C7PY01258F
Citation: Polym. Chem., 2017, Advance Article
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    Grafting well-defined CO2-responsive polymers to cellulose nanocrystals via nitroxide-mediated polymerisation: effect of graft density and molecular weight on dispersion behaviour

    J. Glasing, J. Bouchard, P. G. Jessop, P. Champagne and M. F. Cunningham, Polym. Chem., 2017, Advance Article , DOI: 10.1039/C7PY01258F

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