In situ and real-time small-angle neutron scattering studies of living anionic polymerization process and polymerization-induced self-assembly of block copolymers

Tanaka, Hirokazu; Yamauchi, Kazuhiro*; Hasegawa, Hirokazu*; Miyamoto, Nobuyoshi; Koizumi, Satoshi; Hashimoto, Takeji

Polystyrene-block-polyisoprene were synthesized via living anionic polymerization. We have performed in-situ and real-time SANS, GPC, and UV-vis spectroscopy of the polymerization process in order to reveal the structure formation process of the block copolymers, especially the associated structures. From GPC and UV-vs spectroscopy. It is found that isoprene monomers are preferentially polymerized, and after that, styrene monomers are to be polymerized. It is also found from SANS measurements, that living polymers in the reaction solution formed the associated structures during the polymerization process. Moerover, it is also strongly suggested that in the earlier stage of polymerization, living polymers are mainly composed of polyisoprene with association number of 4, and once styrene monomers are polymerized, the association number drastically begins to decrease from 4 to 2.