RAFT “grafting-through” approach to surface-anchored polymers: Electrodeposition of an electroactive methacrylate monomer

Abstract

Abstract. The synthesis of homopolymer and diblock copolymers on surfaces was demonstrated using electrodeposition of a methacrylate-functionalized carbazole dendron and subsequent reversible additionfragmentation chain transfer (RAFT) "grafting-through" polymerization. First, the anodically electroactive carbazole dendron with methacrylate moiety (G1CzMA) was electrodeposited over a conducting surface (i.e. gold or indium tin oxide (ITO)) using cyclic voltammetry (CV). The electrodeposition process formed a crosslinked layer of carbazole units bearing exposed methacrylate moieties. This film was then used as the surface for RAFT polymerization process of methyl methacrylate (MMA), styrene (S), and tert-butyl acrylate (TBA) in the presence of a free RAFT agent and a free radical initiator, resulting in grafted polymer chains. The molecular weights and the polydispersity indices (PDI) of the sacrificial polymers were determined by gel permeation chromatography (GPC). The stages of surface modification were investigated using X-ray photoelectron spectroscopy (XPS), ellipsometry, and atomic force microscopy (AFM) to confirm the surface composition, thickness, and film morphology, respectively. UV-Vis spectroscopy also confirmed the formation of an electro-optically active crosslinked carbazole film with a π-π * absorption band from 450-650 nm. Static water contact angle measurements confirmed the changes in surface energy of the ultrathin films with each modification step. The controlled polymer growth from the conducting polymer-modified surface suggests the viability of combining electrodeposition and grafting-through approach to form functional polymer ultrathin films.

Emulsifier-free synthesis of crosslinkable ABA triblock copolymer nanoparticles via AGET ATRP

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Living Radical Polymerization by the RAFT Process – A Third Update

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Synthesis and characterization of silica–polyvinyl imidazole core–shell nanoparticles via combination of RAFT polymerization and grafting‐to method

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