Preparation of ZnO hybrid nanoparticles by ATRP

• Published in: Polymer (Guilford) Vol. 107; no. C; pp. 492 - 502
• Main Authors: Ding, Hangjun, Yan, Jiajun, Wang, Zongyu, Xie, Guojun, Mahoney, Clare, Ferebee, Rachel, Zhong, Mingjiang, Daniel, William F.M., Pietrasik, Joanna, Sheiko, Sergei S., Bettinger, Christopher J., Bockstaller, Michael R., Matyjaszewski, Krzysztof
• Format: Journal Article
• Language: English
• Published: Kidlington Elsevier Ltd 19.12.2016; Elsevier BV; Elsevier
• Subjects: Acetic acid; Acrylic acid; Acrylonitrile; Block copolymers; Brushes; Chemical synthesis; Crosslinking; Divinylbenzene; Graft copolymers; Grafting; Initiators; Nanocomposites; Nanoparticles; Polymer matrix composites; Polymer templates; Polymerization; Polymers; Polymethyl methacrylate; Polymethyl methacrylates; Polymethylmethacrylate; Polystyrene resins; Precursors; Semiconductors; SI-ATRP; Sonication; Star templates; Stars; Studies; Styrene; Synthesis (chemistry); Zinc; Zinc acetate; Zinc oxide; Zinc oxides; ZnO nanoparticle; Star templates; Polymer templates; ZnO nanoparticle; SI-ATRP
• ISSN: 0032-3861; 1873-2291
• DOI: 10.1016/j.polymer.2016.09.022

Zinc oxide (ZnO) is a wide bandgap semiconductor material that has attracted widespread interest as particle filler in polymer nanocomposite materials. However, its applications have been hindered by the limited dispersibility and surface-modification techniques. Herein, three distinct approaches for the synthesis of polymer-tethered ZnO hybrid materials are compared in terms of uniformity and yield of the particle-brush product: “grafting-from”, “grafting-onto”, and “grafted-copolymer template” methods. In the “grafting-from” method, pristine ZnO nanoparticles (NP) were first functionalized with atom transfer radical polymerization (ATRP) initiators followed by grafting-from process to form poly(methyl methacrylate) (PMMA) or poly(styrene-co-acrylonitrile) (PSAN) tethered polymer chains. In the “grafting-onto” method, PMMA-b-PAA (poly[acrylic acid]) and PSAN-b-PAA diblock copolymers were prepared and attached onto the surface of ZnO NPs using sonication bath. For the “grafted-copolymer template” method, PSAN-b-PtBA-Br (poly[tert-butyl acrylate]-Br) macroinitiators were crosslinked with divinylbenzene (DVB) to form PSAN-b-PtBA-PDVB core-shell star polymers. After hydrolysis to form PSAN-b-PAA-PDVB star polymers, the functional stars were used as polymer templates for the synthesis of ZnO NPs within the PAA-core of the stars. Core-shell molecular bottlebrushes with PAA-b-PS block-copolymer side chains were also used as anisotropic analogues of star template to prepared worm-like ZnO particles. Several ZnO precursors, zinc nitrite, zinc 2-ethylhexanoate, and zinc acetate were evaluated as precursors of ZnO. Conditions were identified that enable the synthesis of polymer-tethered ZnO with excellent size uniformity and dispersion characteristics using the star-template method. [Display omitted] •ZnO hybrids were prepared via “grafting-from”, “grafting-onto”, & “templating”.•ZnO hybrids with relatively high size uniformity and dispersibility were obtained.•ZnO hybrid nanoparticles were prepared using molecular bottlebrush templates.