Silacyclobutane-Based Diblock Copolymers with Vinylferrocene, Ferrocenylmethyl Methacrylate, and [1]Dimethylsilaferrocenophane

Ernst-Berl-Institut für Technische und Makromolekulare Chemie, Technische Universität Darmstadt, Petersenstrasse 22, D-64287 Darmstadt, Germany
Macromolecular Rapid Communications (Impact Factor: 4.61). 05/2010; 31(9-10):889-96. DOI: 10.1002/marc.200900897
Source: PubMed

ABSTRACT Well-defined diblock copolymers have been prepared in which three different ferrocene-based monomers are combined with 1,1-dimethylsilacyclobutane (DMSB) and 1-methylsilacyclobutane, respectively, as their carbosilane counterparts. Optimized procedures are reported for the living anionic chain growth following sequential monomer addition protocols, ensuring narrow polydispersities and high blocking efficiencies. The DMSB-containing copolymers show phase segregation in the bulk state, leading to micromorphologies composed of crystalline DMSB phases and amorphous polymetallocene phases.

1 Follower
  • [Show abstract] [Hide abstract]
    ABSTRACT: A novel strategy for the preparation of poly(ferrocenylsilane) (PFS) immobilized on the surface of crosslinked polystyrene (PS) nanoparticles is reported. The ferrocene-containing core/shell architectures are shown to be excellent candidates as preceramic polymers yielding spherical ceramic materials consisting of iron silicide (Fe3Si) and metallic iron after thermal treatment. For this purpose, dimethyl- and hydromethyl[1]silaferrocenophane monomers are polymerized by surface initiated ring-opening polymerization upon taking advantage of residual vinylic moieties at the PS particle surface. A strategy for selective chain growth from the particle surface is developed without the formation of free PFS homopolymer in solution. The grafted particles were characterized using transmission electron microscopy (TEM) and dynamic light scattering (DLS). These particles are excellent precursors for ceramics as studied by thermogravimetric analysis (TGA). The composition of the ceramics is studied using x-ray diffraction (XRD) measurements, while the morphology is probed by scanning electron microscopy (SEM) revealing the original spherical shape of the precursor particles. Obtained ceramic materials – predominantly based on iron silicides – show ferromagnetic behavior as investigated by superconducting quantum interference device (SQUID) magnetization measurements at different temperatures.
    Macromolecular Rapid Communications 12/2014; 36(7). DOI:10.1002/marc.201400581 · 4.61 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: In the present study, the synthesis of poly(1,1-dimethylsilacyclobutane) (PDMSB) by anionic ring opening polymerization (ROP) is reinvestigated, leading to narrowly distributed molar masses (polydispersities 1.04-1.15) in the range of 2.3 to 60 kg mol(-1). Investigations of thermal behavior for low molar mass PDMSB revealed an untypical multiple peaks melting phenomenon, which at first glance, seems to be of the same origin as low molar mass poly(ethylene oxide)s. Small angle X-ray scattering (SAXS) and X-ray diffraction (XRD) measurements are done, proving the fast crystallization and subsequent recrystallization for investigated low molar mass samples. Synthetic attempts are expanded to the surface-initiated anionic ROP of 1,1-dimethylsilacyclobutane (DMSB) monomer from the surface of cross-linked polystyrene (PS) nanoparticles. Novel polycarbosilanes (PCS)/organic core/shell particles are obtained, which are investigated by using transmission electron microscopy (TEM) and dynamic light scattering (DLS) experiments. First insights into the crystallization behavior of surface-attached PDMSB chains reveal that crystallization seems to be hindered.
    Polymers 03/2013; 5(1):284-302. DOI:10.3390/polym5010284 · 2.51 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: The synthesis of metal-containing polymers and block copolymers has led to a rapidly expanding field of research interest for manifold potential applications. Within this contribution, some recent advances in the field of side chain ferrocene-containing polymers focusing on poly(vinylferrocene) and poly(ferrocenyl methacrylates) are presented. Synthetic developments shown focus on living and controlled polymerizations as well as surface-initiated polymerization strategies. First attempts and recent developments for these novel redox-responsive materials towards feasible applications are addressed.
    Macromolecular Chemistry and Physics 04/2014; 215(8). DOI:10.1002/macp.201300762 · 2.45 Impact Factor