Effect of Surface Charge on Surface-Initiated Atom Transfer Radical Polymerization from Cellulose Nanocrystals in Aqueous Media

Cellulose nanocrystals (CNCs) with different charge densities were utilized to examine the role of electrostatic interactions on surface-initiated atom transfer radical polymerization (SI-ATRP) in aqueous media. To this end, growth of hydrophilic uncharged poly­(N,N-dimethylacrylamide) (PDMAM) brush...

Full description

Saved in:
Bibliographic Details
Published inBiomacromolecules Vol. 17; no. 4; pp. 1404 - 1413
Main Authors Zoppe, Justin O, Xu, Xingyu, Känel, Cindy, Orsolini, Paola, Siqueira, Gilberto, Tingaut, Philippe, Zimmermann, Tanja, Klok, Harm-Anton
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 11.04.2016
Subjects
Acrylamides - chemistry
Cellulose - chemistry
Nanoparticles - chemistry
Polymerization
Polymers - chemistry
Static Electricity
Surface Properties
Water - chemistry
Online AccessGet full text

Cover

More Information
Summary:Cellulose nanocrystals (CNCs) with different charge densities were utilized to examine the role of electrostatic interactions on surface-initiated atom transfer radical polymerization (SI-ATRP) in aqueous media. To this end, growth of hydrophilic uncharged poly­(N,N-dimethylacrylamide) (PDMAM) brushes was monitored by electrophoresis, 1H NMR spectroscopy, and dynamic light scattering (DLS). Molecular weight and polydispersity of PDMAM brushes was determined by GPC analysis of hydrolytically cleaved polymers. Initiator and polymer brush grafting densities, and thus, initiator efficiencies were derived from elemental analysis. Higher initiator efficiency of polymer brush growth was observed for CNCs with higher anionic surface sulfate half-ester group density, but at the expense of high polydispersity caused by inefficient deactivation. PDMAM grafts with number-average molecular weights up to 530 kDa and polydispersity indices <1.5 were obtained under highly diluted monomer concentrations. The role of surface chemistry on the growth of neutral polymer brushes from CNCs in water is emphasized and a model of the interfacial region at the onset of polymerization is proposed. The results presented here could have implications for other substrates that present surface charges and for the assumption that the kinetics of Cu-mediated SI-CRP are analogous to those conducted in solution.
Bibliography:ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:1525-7797
1526-4602
DOI:10.1021/acs.biomac.6b00011