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Updated: Jan 26, 2026

Anionic Polymerization of an Amphiphilic Copolymer for Preparation of Block Copolymer Micelles Stabilized by π-π Stacking Interactions
Published on: October 10, 2016
Downsizing feature of microphase-separated structures via intramolecular crosslinking of block copolymers
Kodai Watanabe1, Satoshi Katsuhara1, Hiroaki Mamiya2
1Faculty of Engineering and Graduate School of Chemical Sciences and Engineering , Hokkaido University , Sapporo 060-8628 , Japan . Email: isono.t@eng.hokudai.ac.jp ;
Abstract:
A novel strategy for downsizing the feature of microphase-separated structures was developed via the intramolecular crosslinking reaction of block copolymers (BCPs) without changing the molecular weight. A series of BCPs consisting of poly[styrene-st-(p-3-butenyl styrene)] and poly(rac-lactide) (SBS-LA) was subjected to Ru-catalyzed olefin metathesis under highly diluted conditions to produce intramolecularly crosslinked BCPs (SBS(cl)-LAs). Small-angle X-ray scattering measurement and transmission electron microscopy observation of the SBS(cl)-LAs revealed feature size reduction in lamellar (LAM) and hexagonally close-packed cylinder (HEX) structures in the bulk state, which was surely due to the restricted chain dimensions of the intramolecularly crosslinked SBS block. Notably, the degree of size reduction was controllable by varying the crosslink density, with a maximum decrease of 22% in the LAM spacing. In addition, we successfully observed the downsizing of the HEX structure in the thin film state using atomic force microscopy, indicating the applicability of the present methodology to next-generation lithography technology.
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