Block Copolymers Containing Rod Segments

Department of Organic and Polymeric Materials, Graduate School of Science and Engineering, Tokyo Institute of Technology, 2-12-1-H-120, Ookayama, Meguro-ku, Tokyo 152-8552, Japan 

Complex Macromolecular Architectures Synthesis, Characterization, and Self-Assembly, First Edition. 

Edited by Nikos Hadjichristidis, Akira Hirao, Yasuyuki Tezuka and Filip Du Prez. 

Herein, we review recent progress in the synthesis of well-defined BCPs containing rod segments, especially those based on living/controlled polymerization systems. It should be noted that BCPs with mesogenic rods have already been established and well reviewed by Myongsoo Lee and coworkers (Lee et al, 2001 Lim etal, 2008), therefore they are beyond the scope of this review. 

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Fig. 20 Cryo-TEM image of isolated micelles and segmented rods made from miktoarm ABC block copolymers containing PEO, PB and perfluorinated polyether blocks (scale bar is 50 nm). A schematic representation of the stacking of block copolymer chains in segmented worms is also shown. Reprinted with permission from [284], Copyright (2004) American Association for the Advancement of Science...

Finally the synthesis of block copolymers containing segments of the homopolymer types mentioned above together with other functionalities will be discussed. These polymers are accessible through the living character of ROMP. The main part of this paper is dealing with rod-coil block copolymers and their phase behaviour, especially phase separation in the nano range. 

Lee et al. reported the preparation of nanoporous crystalline sheets of penta-p-phenylene using a (oligomeric) block copolymer with a cleavable juncture approach in 2004 [63]. These so-called rod-coil block copolymers of penta-p-phenylene and PPO can self-assemble to give layered phases that contain sheets of perforated crystalline penta-p-phenylene in which the perforations are filled with PPO [64]. The PPO segment is covalently bound to the... 

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