Synthesis and characterization of polymers and copolymers of vinylruthenocene

Abstract

Homopolymers of vinylruthenocene and its copolymers with methyl acrylate, styrene, and n‐vinylpyrrolidinone have been prepared by free‐radical polymerization. No evidence for the electron transfer termination mechanism postulated for polymerization of vinylferrocene was observed. Yields of soluble polymers were 40–90% with Mw (4–25) × 103 and Mw/Mn = 3.0–13.2. TGA analysis showed little weight loss up to 300°C but rapid decomposition above 300°C. Polyvinylruthenocene is a highly brittle material with Tg above 250°C. Torsional braid analysis of the copolymer samples showed Tg in the range 90–130°C which in some samples increased upon cooling and reheating. Several samples showed weak thermal transitions occurring prior to or following Tg. The rise in Tg upon cooling and reheating is indicative of possible decomposition, crosslinking, or realignment of the polymer chains.

Side‐Chain Metallocene‐Containing Polymers by Living and Controlled Polymerizations

“…Ruthenocene is an 18‐electron metallocene, isoelectronic to ferrocene and cobaltocenium. In principle, it is possible to carry out electrophilic substitution on ruthenocene to prepare derivatives or monomers 167. Similar to cobaltocene, 19‐electron rhodocene is not stable.…”

Ruthenocenes and Osmocenes

“…199 Various x-ray studies 200 and applications of hollow spheres made from these homo-and copolymers to inertial fusion were reported. " …”

Side‐Chain Metal‐Containing Polymers

“…For example, ruthenium and osmium analogues of poly(vinylferrocene) have been described, but their characterization has been fairly limited [16,42,43]. For example, ruthenium and osmium analogues of poly(vinylferrocene) have been described, but their characterization has been fairly limited [16,42,43].…”

“…For example, ruthenium and osmium analogues of poly(vinylferrocene) have been described, but their characterization has been fairly limited [16,42,43]. Copolymers with other organic vinyl monomers have also been prepared [43]. The polymers were proposed to possess a branched structure as a result of chain-transfer steps.…”