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.
Utilization of biomass for commodity polymers has gained tremendous interest. We report a method to prepare high molecular weight renewable homopolymers and block copolymers derived from natural rosin. Monomers with high renewable content (70 wt %) were prepared via a simple esterification reaction between dehydroabietic alcohol and 5exo-norbornenecarboxylic acid. Living and controlled polymerization of these monomers were achieved by ring-opening metathesis polymerization to obtain polymers with molecular weight up to ∼500 kg/mol. These homopolymers exhibit structure-dependent glass transition temperatures, excellent thermal stabilities, and thermoplastic properties. Chain entanglement molecular weight was determined via rheological assessments for such polymers with bulky side moieties. Using the living ROMP, dehydroabietic-based homopolymer was chainextended with a soybean oil-derived norbornene monomer to yield triblock copolymers, which showed behaviors of thermoplastic elastomers.
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