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Updated: Sep 22, 2025

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
Published on: April 22, 2016
Enhancing Initiation Efficiency in Metal-Free Surface-Initiated Atom Transfer Radical Polymerization (SI-ATRP)
Jiajun Yan1, Xiangcheng Pan2, Michael Schmitt2
1Department of Chemistry and ‡Department of Material Science and Engineering, Carnegie Mellon University, 5000 Forbes Avenue, Pittsburgh, Pennsylvania 15213, United States.
Abstract:
Well-defined polymer-inorganic hybrid materials were prepared via metal-free surface-initiated atom transfer radical polymerization (SI-ATRP) with 10-phenylphenothiazine (PhPTZ) as the photocatalyst and 2-bromo-2-phenylacetate initiator tethered to silica surfaces. Initiation efficiency and, hence, graft density were significantly enhanced by this very reactive initiator. The polymerization kinetics, effect of initiator structures, particle sizes, and catalyst concentrations were investigated. Well-defined hybrid particles were prepared at a low catalyst concentration (0.02 mol % or 0.1 mol % to monomer). Poly(methyl methacrylate) (PMMA) with number-average molecular weight of 3.65 × 104, dispersity of 1.43, and graft density of 0.60 chain/nm2 was grafted from the surface of silica nanoparticles. The hybrid materials were characterized with size exclusion chromatography (SEC), thermogravimetric analysis (TGA), dynamic light scattering (DLS), and transmission electron microscopy (TEM).
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