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Journal article
Miktoarm Stars via Grafting-Through Copolymerization: Self-Assembly and the Star-to-Bottlebrush Transition
Macromolecules, v 52(4), pp 1794-1802
26 Feb 2019
Featured in Collection : UN Sustainable Development Goals @ Drexel
Abstract
The grafting-through copolymerization of two distinct macromonomers via ring-opening metathesis polymerization is typically used to form statistical or diblock bottlebrush polymers with large total backbone degrees of polymerization (N-BB) relative to that of the side-chains (N-SC). Here, we demonstrate that Grubbs-type chemistry in the opposite limit, namely N-BB << N-SC, produces well-defined materials with excellent control over ensemble-averaged properties, including molar mass, dispersity, composition, and number of branch points. The dependence of self-assembly on these molecular design parameters was systematically probed using small-angle X-ray scattering and self-consistent field theoretic simulations. Our analysis supports the notion that two-component bottlebrush copolymers with small N-BB behave like miktoarm star polymers. The star-to-bottlebrush transition is quantifiable for both statistical and diblock sequences by unique signatures in the experimental scaling of domain spacing and simulated distribution of backbone/side-chain density within lamellar unit cells. These findings represent a conceptual framework that simplifies the synthesis of miktoarm star polymers when dispersity in the number of arms and composition can be tolerated. The analytical approach introduced to distinguish chain conformations in complex macromolecules also complements previous methods, for example, form factor scattering and rheology.
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Details
- Title
- Miktoarm Stars via Grafting-Through Copolymerization: Self-Assembly and the Star-to-Bottlebrush Transition
- Creators
- Adam E. Levi - University of California, Santa BarbaraJoshua Lequieu - University of California, Santa BarbaraJacob D. Horne - University of California, Santa BarbaraMorgan W. Bates - University of California, Santa BarbaraJing M. Ren - University of California, Santa BarbaraKris T. Delaney - University of California, Santa BarbaraGlenn H. Fredrickson - University of California, Santa BarbaraChristopher M. Bates - University of California, Santa BarbaraArgonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Publication Details
- Macromolecules, v 52(4), pp 1794-1802
- Publisher
- American Chemical Society; Washington, DC
- Number of pages
- 9
- Grant note
- NSF DMR 1720256 / UCSB MRSEC Center for Scientific Computing from the CNSI DMR-1720256 / MRL: an NSF MRSEC; National Science Foundation (NSF); NSF - Directorate for Mathematical & Physical Sciences (MPS) Mellichamp Academic Initiative in Sustainability W911NF-09-0001 / Institute for Collaborative Biotechnologies U.S. Army Research Office DE-SC0019001 / U.S. Department of Energy, Office of Basic Energy Sciences; United States Department of Energy (DOE) CNS-1725797 / NSF; National Science Foundation (NSF)
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- Chemical and Biological Engineering
- Web of Science ID
- WOS:000460199600041
- Scopus ID
- 2-s2.0-85061931330
- Other Identifier
- 991020950597204721
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- Web of Science research areas
- Polymer Science