Silacyclobutane-based diblock copolymers with vinylferrocene, ferrocenylmethyl methacrylate, and dimethylsilaferrocenophane.
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.
- [show abstract] [hide abstract]
ABSTRACT: A convenient two-step protocol is presented for synthesis of linear-hyperbranched diblock copolymers consisting of a linear, organometallic poly(ferrocenylsilane) (PFS) block and hyperbranched poly(carbosilane) (hbPCS) segments. Linear PFS diblock copolymers were synthesized through photolytic ring-opening polymerization of dimethylsilaferrocenophane as the first block and methylvinylsilaferrocenophane as the second. These block copolymers served as polyfunctional cores in a subsequent hydrosilylation polyaddition of different silane-based AB(2) monomers. Three AB(2) monomers (methyldiallylsilane; methyldiundecenylsilane, and ferrocenyldiallylsilane) were investigated; they introduced structural diversity to the hyperbranched block and showed variable reactivity for the hydrosilylation reaction. In the case with the additional ferrocene moiety in the ferrocenyldiallylsilane monomer, an electroactive hyperbranched block was generated. No slow monomer addition was necessary for molecular-weight control of the hyperbranching polyaddition, as the core had much higher functionality and reactivity than the carbosilane monomers. Different block ratios were targeted and hybrid block copolymers with narrow polydispersity (<1.2) were obtained. All the resulting polymers were investigated and characterized by size exclusion chromatography, NMR spectroscopy, cyclic voltammetry, and TEM, and exhibited strongly anisotropic aggregation.Chemistry 07/2009; 15(36):9068-77. · 5.93 Impact Factor
- [show abstract] [hide abstract]
ABSTRACT: The study of metallopolymers has blossomed into a mature field over the last few decades. Especially, polyferrocenylsilane (PFS) chemistry has taken a tremendous leap and continues to raise intense interest. Since the discovery of thermal ring-opening polymerization (ROP) of silaferrocenophanes, PFSs have been also accessed by anionic, cationic, transition-metal-catalyzed, and photolytic anionic ROP methodologies. A plethora of synthetic strategies have been devised, enabling access to a wide variety of copolymers, polyelectrolytes, and nanostructured materials. The distinctive physical properties and functions of many PFS-based polymers have been explored, leading to their apt exploitation in technical applications. Therefore, it is conceivable that PFS-related platforms might be indispensable nano-objects in the near future, as they stand on the verge of a new generation of sophisticated materials.Angewandte Chemie International Edition 02/2007; 46(27):5082-104. · 13.73 Impact Factor
Chapter: Organic/Inorganic Hybrid Polymers[show abstract] [hide abstract]
ABSTRACT: Poly(N-acetylethylenimine) (polyoxazoline) (POZO) with a terminal triethoxysilyl group was successfully synthesized by the ring-opening polymerization of 2-methyl-2-oxazoline followed by termination with 3-aminopropyltriethoxysilane. Triethoxysilyl-terminated telechelic POZO was prepared by using a bifunctional initiator. These silane coupling POZOs were subjected to acid-catalyzed cohydrolysis polymerization with tetraethoxysilane by the so-called “sol-gel” method to produce a novel organic/inorganic hybrid polymer (block copolymer), which was a homogeneous transparent/glassy composite material. The obtained hybrid showed higher hydrophilic properties compared with silica gel without POZO segments. On the other hand, a hybrid polymer consisting of poly(2-ethyl-2-oxazoline) and silica gel, which absorbed both water and organic solvents, showed amphiphilic properties. POZO segments were eliminated by pyrolysis of the present hybrid polymer to produce a silica with micropores.Synthesis of Polymers, 04/2008: pages 319 - 374; , ISBN: 9783527619313