Redox-Responsive Polymer Brushes Grafted from Polystyrene Nanoparticles by Means of Surface Initiated Atom Transfer Radical Polymerization

Abstract

Well-defined poly(2-(methacryloyloxy)ethyl ferrocenecarboxylate) (PFcMA) brushes were synthesized by surface-initiated atom transfer radical polymerization (SI-ATRP) on cross-linked polystyrene particles. The ATRP of FcMA monomer was reinvestigated leading to molar masses up to 130 kg mol–1 with a good reaction control and high monomer conversion (91%). The SI-ATRP was done with different amounts of initiator in the PS particle shell leading to PFcMA surface conformations from “mushroom-like” to dense “brush-like” polymers, which could be confirmed by dynamic light scattering (DLS) experiments. Redox-responsive behavior of the PFcMA shell was investigated by DLS and cyclic voltammetry (CV) measurements indicating a tremendous increase in the hydrodynamic volume of the ferrocene-containing shell. The transformation of PFcMA-grafted PS particles to magnetic iron oxides after thermal treatment could be investigated by SQUID magnetization measurements showing the typical hysteresis for ferromagnetic material.

Polymer‐Modified Mesoporous Silica Thin Films for Redox‐Mediated Selective Membrane Gating

“…2-(methacryloyloxy)ethyl ferrocenecarboxylate (FcMA) monomer 1 was synthesized described elsewhere. [ 51 ] Triethoxy functionalized polyvinylferrocenes (PVFc-TEOS) were synthesized via anionic polymerization as recently reported. [ 49 ] Instrumentation : Standard SEC was performed with tetrahydrofuran (THF) as the mobile phase (fl ow rate 1 mL min −1 ) on a SDV column set from PSS (SDV 1000, SDV 100000, SDV 1000000) at 30 ° C. Calibration was carried out using PS standards (from Polymer Standard Service, Mainz).…”

“…It has been previously reported that molar masses for surface-attached PFcMA and PFcMA chains obtained by ATRP in solution were in a comparable range. [ 51 ] All SEC results for the samples used are compiled in Table 2 . The presence of polymer in the PFcMA-modifi ed mesoporous samples was monitored by infrared spectroscopy ( Figure 3 ) and corroborated by XRR.…”

Polymer Chain Conformation on Deuterated Polystyrene Nanoparticles Investigated by SANS

“…The shell of the particles was treated with divinylbenzene (DVB) as cross-linker and an atom transfer radical polymerization (ATRP) initiator, which additionally acts as a monomer (also referred to as ATRP-inimer) for the intended surface-initiated atom transfer radical polymerization (SI-ATRP) of protonated styrene monomer (see Fig. 2) (13). SI-ATRP of styrene was carried out to generate grafted PS chains with molar masses up to 50 kg mol −1 .…”

Immobilization of Poly(1,1-dimethysilacyclobutane) by Means of Anionic Ring-Opening Polymerization on Organic Nanoparticles and Reinvestigation of Crystallization

“…Those particles were used because of their simple synthesis via seeded emulsion polymerization, similar to a previously described procedure, leading to almost monodisperse particles [57]. For further purification, the particles were dried by three-fold azeotropic distillation with dry toluene under high vacuum conditions.…”