The deposition of polyallylamine (PAA) adlayers by pulsed plasma polymerization on various types of polymeric substrates has been explored as a general route to amino functionalized polymeric surfaces. These amino groups are highly suitable for anchoring an atom transfer radical polymerization (ATRP) initiator via a robust amide linkage. Subsequent surface initiated ATRP (SI‐ATRP) of monomethoxy oligo(ethylene glycol) methacrylate (MeOEGMA) resulted in polyMeOEGMA brush grafted polymer surfaces. This combined strategy of pulsed plasma polymerization with SI‐ATRP was demonstrated for five different polymeric substrates namely polyether ether ketone (PEEK), polyethylene terephthalate (PET), polyimide (PI), polypropylene (PP), and polytetrafluoroethylene (PTFE). Analysis of brush layers by attenuated total reflection infrared (ATR‐IR) spectroscopy as well as X‐ray photoelectron spectroscopy (XPS) fully corroborated the success of the proposed strategy for all substrate types.
Self‐initiated photografting polymerization is used to couple the polymerizable initiator monomer 2‐(2‐chloropropanoyloxy)ethyl acrylate to a range of polymeric substrates. The technique requires only UV light to couple the initiator to surfaces. The initiator surface density can be varied by inclusion of a diluent monomer or via selection of initiator and irradiation parameters. The functionality of the initiator surface is demonstrated by subsequent surface‐initiated atom transfer radical polymerization. Surfaces are characterized by x‐ray photoelectron spectroscopy (XPS), ellipsometry, and atomic force microscopy (AFM), and UV‐induced changes to the initiator are assessed by 1H NMR and gel permeation chromatography (GPC). This is the first time this one‐reactant one‐step technique has been demonstrated for creating an initiator surface of variable density.
