Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 53, Issue 34, Pages 9000-9003Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201404089
Keywords
block copolymers; hierarchical self-assembly; lamellae; polymer crystallinity; rod micelles
Categories
Funding
- Fonds Quebecois de la Recherche sur la Nature et les Technologies (FQRNT)
- Centre for Self-Assembled Chemical Structures (CSACS)
- National Sciences and Engineering Research Council of Canada (NSERC)
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Block copolymers can form a broad range of self-assembled aggregates. In solution, planar assemblies usually form closed structures such as vesicles; thus, free-standing sheet formation can be challenging. While most polymer single crystals are planar, their growth usually occurs by uptake of individual chains. Here we report a novel lamella formation mechanism: core-crystalline spherical micelles link up to form rods in solution, which then associate to yield planar arrays. For the system of poly(ethylene oxide)-block-polycaprolactone in water, co-assembly with homopolycaprolactone can induce a series of morphological changes that yield either rods or lamellae. The underlying lamella formation mechanism was elucidated by electron microscopy, while light scattering was used to probe the kinetics. The hierarchical growth of lamellae from one-dimensional rod subunits, which had been formed from spherical assemblies, is novel and controllable in terms of product size and aspect ratio.
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