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Small‐Angle X‐Ray Scattering Studies of Block Copolymer Nano‐Objects: Formation of Ordered Phases in Concentrated Solution During Polymerization‐Induced Self‐Assembly
Author(s) -
Rymaruk Matthew J.,
O'Brien Cate T.,
György Csilla,
Darmau Bastien,
Jennings James,
Mykhaylyk Oleksandr O.,
Armes Steven P.
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202101851
Subject(s) - copolymer , polymerization , materials science , small angle x ray scattering , dispersion polymerization , phase (matter) , polybutadiene , polymer chemistry , lyotropic , dodecane , scattering , cationic polymerization , chemical engineering , crystallography , chemical physics , liquid crystal , chemistry , optics , organic chemistry , composite material , polymer , liquid crystalline , physics , optoelectronics , engineering
We report that polymerization‐induced self‐assembly (PISA) can be used to prepare lyotropic phases comprising diblock copolymer nano‐objects in non‐polar media. RAFT dispersion polymerization of benzyl methacrylate (BzMA) at 90 °C using a trithiocarbonate‐capped hydrogenated polybutadiene (PhBD) steric stabilizer block in n‐dodecane produces either spheres or worms that exhibit long‐range order at 40 % w/w solids. NMR studies enable calculation of instantaneous copolymer compositions for each phase during the BzMA polymerization. As the PBzMA chains grow longer when targeting PhBD 80 –PBzMA 40 , time‐resolved small‐angle X‐ray scattering reveals intermediate body‐centered cubic (BCC) and hexagonally close‐packed (HCP) sphere phases prior to formation of a final hexagonal cylinder phase (HEX). The HEX phase is lost on serial dilution and the aligned cylinders eventually form disordered flexible worms. The HEX phase undergoes an order–disorder transition on heating to 150 °C and a pure HCP phase forms on cooling to 20 °C.