Issue 38, 2017

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

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 BlocBuilderĀ® (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

Supplementary files

Article information

Article type
Paper
Submitted
26 Jul 2017
Accepted
07 Sep 2017
First published
08 Sep 2017

Polym. Chem., 2017,8, 6000-6012

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, 8, 6000 DOI: 10.1039/C7PY01258F

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