No abstract

A comprehensive investigation on the synthesis and properties of a series of ferrocene‐containing (meth)acrylate monomers and their polymers that differ in the linkers between the ferrocene unit and the backbone was carried out. The side‐chain ferrocene‐containing polymers were prepared via atom transfer radical polymerization. The kinetic studies indicated that polymerization of most monomers followed a “controlled”/living manner. The polymerization rates were affected by the vinyl monomer structures and decreased with an increase of the linker length. Methacrylate polymerization was much faster than acrylate polymerization. The optical absorption of monomers and polymers was affected by the linkers. Thermal properties of these polymers can be tuned by controlling the length of the linker between the ferrocene unit and the backbone. By increasing the length of the linker, the glass transition temperature ranged from over 100 to −20 °C. Electrochemical properties of both monomers and polymers were characterized. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

Cobaltocenium-containing methacrylate homopolymer, poly(2-(methacrylolyoxy)ethyl cobaltoceniumcarboxylate hexafluorophosphate) (PMAECoPF 6 ), was prepared by reversible addition−fragmentation chain transfer polymerization (RAFT). Using the homopolymer as a macroinitiator, three different diblock copolymers, including a novel heterobimetallic diblock copolymer with ferrocene units as the second block, were synthesized via chain extension. Kinetic studies showed that all chain extension followed a controlled/ living process under relatively lower conversion. The heterobimetallic diblock copolymer self-assembled into spherical micelles in selective solvents. The formation of aggregates depended on the location of the ferrocene block in the micelles. While the ferrocene units were susceptible to oxidation toward decomposition, the cobaltocenium moiety exhibited extraordinary stability to maintain its structure integrity.

The synthesis and radical polymerization of an 18-e cobaltocenium vinyl monomer, 2-acryloyloxyethyl cobaltoceniumcarboxylate hexafluorophosphate (AECoPF 6 ), are reported. The side-chain cobaltocenium-containing polymer, poly(acryloyloxyethyl cobaltoceniumcarboxylate hexafluorophosphate) (PAECoPF 6 ), is a water-soluble hydrophilic polyelectrolyte. Through an effective ion-exchange process, this polymer was transformed into a hydrophobic poly(acryloyloxyethyl cobaltoceniumcarboxylate tetraphenylborate) (PAECoBPh 4 ) polymer, soluble in strong polar solvents such as dimethylformamide and dimethyl sulfoxide. Electrochemical studies showed that both polymers have reversible redox processes in dimethylformamide. These polymers exhibited high thermal stability.

The synthesis of side-chain cobaltocenium-containing block copolymers and their self-assembly in solution was studied. Highly pure monocarboxycobaltocenium was prepared and subsequently attached to side chains of poly(tert-butyl acrylate)-block-poly(2-hydroxyethyl acrylate), yielding poly(tert-butyl acrylate)-block-poly(2-acryloyloxyethyl cobaltoceniumcarboxylate). The cobaltocenium block copolymers exhibited vesicle morphology in the mixture of acetone and water, while micelles of nanotubes were formed in the mixture of acetone and chloroform.