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

ArticleinMacromolecular Rapid Communications 31(9-10):889-96 · May 2010with16 Reads
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.
    • "In earlier studies magnetic nano-lines, nanoscopic iron oxide patterns, separation tunable arrays and cobalt magnetic dot arrays were accessible by using PFS-based block copolymers as preceramic polymers279280281282. Besides PFS-based block copolymers, also some other ferrocene-containing polymers based on methacrylate derivatives and vinylferrocene were capable of forming fascinating micro morphologies283284285. As an example of iron oxide as the final ceramic material, Tang and coworkers investigated the self-assembly and template synthesis of triblock copolymers with a poly(2-(methacryloyloxy)ethyl ferrocenecarboxylate) (PFcMA) block for the preparation of ordered iron oxides [135]. "
    [Show abstract] [Hide abstract] ABSTRACT: The present Review addresses current developments related to polymer-derived ceramic nanocomposites (PDC-NCs). Different classes of preceramic polymers are briefly introduced and their conversion into ceramic materials with adjustable phase compositions and microstructures is presented. Emphasis is set on discussing the intimate relationship between the chemistry and structural architecture of the precursor and the structural features and properties of the resulting ceramic nanocomposites. Various structural and functional properties of silicon-containing ceramic nanocomposites as well as different preparative strategies to achieve nano-scaled PDC-NC-based ordered structures are highlighted, based on selected ceramic nanocomposite systems. Furthermore, prospective applications of the PDC-NCs such as high-temperature stable materials for thermal protection systems, membranes for hot gas separation purposes, materials for heterogeneous catalysis, nano-confinement materials for hydrogen storage applications as well as anode materials for secondary ion batteries are introduced and discussed in detail.
    Full-text · Article · Jun 2015
    • "In earlier studies magnetic nano-lines, nanoscopic iron oxide patterns, separation tunable arrays and cobalt magnetic dot arrays were accessible by using PFS-based block copolymers as preceramic polymers279280281282. Besides PFS-based block copolymers, also some other ferrocene-containing polymers based on methacrylate derivatives and vinylferrocene were capable of forming fascinating micro morphologies283284285. As an example of iron oxide as the final ceramic material, Tang and coworkers investigated the self-assembly and template synthesis of triblock copolymers with a poly(2-(methacryloyloxy)ethyl ferrocenecarboxylate) (PFcMA) block for the preparation of ordered iron oxides [135]. "
    [Show abstract] [Hide abstract] ABSTRACT: The present Review addresses current developments related to polymer-derived ceramic nanocomposites (PDC-NCs). Different classes of preceramic polymers are briefly introduced and their conversion into ceramic materials with adjustable phase compositions and microstructures is presented. Emphasis is set on discussing the intimate relationship between the chemistry and structural architecture of the precursor and the structural features and properties of the resulting ceramic nanocomposites. Various structural and functional properties of silicon-containing ceramic nanocomposites as well as different preparative strategies to achieve nano-scaled PDC-NC-based ordered structures are highlighted, based on selected ceramic nanocomposite systems. Furthermore, prospective applications of the PDC-NCs such as high-temperature stable materials for thermal protection systems, membranes for hot gas separation purposes, materials for heterogeneous catalysis, nano-confinement materials for hydrogen storage applications as well as anode materials for secondary ion batteries are introduced and discussed in detail.
    Article · Apr 2015 · Polymers
    • "Fascinating BC structures with PS have been obtained after BC self-assembly, and even after subsequent pyrolysis, highly-ordered ceramic structures could be maintained. The synthesis and microphase separation of BCs consisting of PDMSB and various ferrocene-containing polymers have also been reported [36]. In the present study, we firstly synthesize and investigate PDMSB homopolymers obtained by anionic ROP, and results are compared to previously reported studies. "
    [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.
    Full-text · Article · Mar 2013
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