Ruthenocene-Containing Homopolymers and Block Copolymers via ATRP and RAFT Polymerization

Abstract

Ruthenocene-containing methacrylate homopolymer, poly(2-(methacrylolyoxy)ethyl ruthenocenecarboxylate) (PMAERu), was prepared by controlled polymerization methods such as reversible addition−fragmentation chain transfer (RAFT) polymerization and atom transfer radical polymerization (ATRP). Kinetic studies showed that both the RAFT and ATRP process of monomer 2-(methacryloyloxy)ethyl ruthenocenecarboxylate (MAERu) followed a controlled/"living" polymerization behavior. The obtained polymer PMAERu was fully characterized by NMR, gel permeation chromatography, UV−vis spectroscopy, cyclic voltammetry, thermogravimetric analysis, and differential scanning calorimetry. By using the ruthenocene-containing homopolymer as a Macro-RAFT agent and 2-bromoisobutyryl end-capped poly(ethylene oxide) (PEO-Br) as a macroinitiator, different amphiphilic diblock copolymers were synthesized via successful chain extension. These amphiphilic diblock copolymers can self-assemble into micelles with different morphologies, including spherical and worm-like nanostructures.

Redox‐Switchable Supramolecular Graft Polymer Formation via Ferrocene–Cyclodextrin Assembly

“…The formation of undefined aggregates is most likely due to the drying process, which is rather uncontrolled. As noted in former studies, the hydrophobic Fc moieties form the core . In the current example, DMA provides the hydrophilic corona.…”

“…Amphiphilic block copolymers are well‐known systems to undergo self‐assembly in solvents to form spherical micelles and several other morphologies . Thus, metallocene‐containing amphiphilic block‐ or homopolymers exhibit interesting self‐assembly behavior . In comparison with the above‐mentioned examples, micellization behavior of statistical copolymers has only been investigated in selected studies .…”

“…The formation constants of diverse Fc‐β‐CD complexes have been investigated in organic solvents as well as in aqueous media . In contrast to analogous metallocenes such as ruthenocene, Fc can be reversibly oxidized and reduced via chemical and electrochemical stimuli . Oxidation of the Fc moiety to the corresponding ferrocenium cation changes the molecules electron density and leads to a decreasing complex formation constant.…”

Syntheses of Monosubstituted Rhodocenium Derivatives, Monomers, and Polymers

“…Two controlled/"living" polymerization techniques were then carried out on the η 4 /η 5 -Rh(I)-and rhodocenium-containing monomers: reversible addition−fragmentation chain transfer (RAFT) polymerization, 11 and ring-opening metathesis polymerization (ROMP) 22 (Figure 2a), the ROMP process followed a controlled/"living" characteristic. This η 4 /η 5 -Rh(I)-containing polymer is stable under N 2 and can be stored for at least 2 weeks, as indicated by 1 H NMR spectra ( Figure S17).…”

Ring‐Opening Metathesis Polymerization of 18‐e Cobalt(I)‐Containing Norbornene and Application as Heterogeneous Macromolecular Catalyst in Atom Transfer Radical Polymerization

“…Metallopolymers have received wide attention in the past decades due to their applications in the fields of materials and chemistry . One of facile strategies to synthesize metallopolymers starts from functional metallocenes . Both main‐chain and side‐chain ferrocene‐containing polymers have found numerous applications in a variety of areas .…”