Polystyrene-Based Diblock Copolymers

Living polymerization of azo monomers is one of the most effective ways to prepare well-defined azo BCs. Generally, a monodispersed macroinitiator should be prepared first. It is then used as an initiator for the subsequent polymerization of azo monomers. Finkelmann and Bohnert (1994) first reported the synthesis of LC-side chain AB azo BCs by direct anionic polymerization of an azo monomer. As shown in Scheme 12.1, the polymerization of polystyrene (PS)-based diblock copolymers was carried out from a PS-lithium capped with 1,1-diphenylethylene (DPE), whereas the poly(methyl methacrylate) (PMMA)-based diblock copolymers were prepared by addition of methyl methacrylate (MMA) monomers to the living azo polyanion, obtained by reaction of l,l-diphenyl-3-methylpentylithium (DPPL) with the azo monomer in tetrahydrofuran (THF) at lower temperature. By this method, a series of well-defined azo BCs were obtained with controlled molecular weights and narrow polydispersities (Lehmann et al., 2000). 

Wu et al. reported on a rod—coil diblock copolymers based on mesogen-jacketed liquid crystalline polymer as the rod block and polystyrene as the coil block (Scheme 6).82 Styrene was polymerized by TEMPO mediated radical polymerization, followed by sequential polymerization of 2,5-bis[4-methoxyphenyl]oxy-carbonylstyrene (MPCS) to produce the rod—coil diblock copolymer (20) containing 520 styrene and 119 MPCS repeating units. The rod—coil copolymer was observed to self-assemble into a core—shell nanostructure in a selective solvent for polystyrene... 

The second concept for the generation of monolithic polymers is based on diblock copolymers which were prepared by Hillmyer and coworkers [27]. These copolymers contain oriented nanoscopic cylinders of the degradable polymer polylactide (PLA) which were embedded in polystyrene. The latter served as an inert thermoplastic matrix, while PLA could be selectively removed under well-defined conditions using sodium hydroxide in aqueous methanol. The resulting mesoporous monolithic polystyrene contains nanochannels with defined pore size. The major drawback of this material free of any cross-linker is associated with reduced mechanical and chemical stability. 

Yu, X., Xiao, K., Chen, (., Lavrik, N.V., Hong, K Sumpter, B.G., and Geohegan, D.B. (2011) High-performance field-effect transistors based on polystyrene-b-poly(3-hexylthiophene) diblock copolymers. ACS Nano, 5,... 

Nghiem DQ, Kim P-D (2008) Direct preparation of high surface area mesoporous SiC-based ceramic by pyrolysis of a self-assembled polycarbosilane-block-polystyrene diblock copolymer. Chem Mater 20 3735-3739... 

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