Mesoporous Polymer Frameworks from End-Reactive Bottlebrush Copolymers
Reticulated nanoporous materials generated by versatile molecular framework approaches are limited to pore dimensions on the scale of the utilized rigid molecular building blocks (<5 nm). The inherent flexibility of linear polymers precludes their utilization as long framework connectors for the extension of this strategy to larger length scales. We report a method for the fabrication of mesoporous frameworks by using bottlebrush copolymers with reactive end blocks serving as rigid macromolecular interconnectors with directional reactivity. End-reactive bottlebrush copolymers with pendant alkene functionalities were synthesized by a combination of controlled radical polymerization and polymer modification protocols. Ru-catalyzed cross-metathesis cross-linking of bottlebrush copolymers with two reactive end blocks resulted in the formation of polymer frameworks where isolated cross-linked domains were interconnected with bottlebrush copolymer bridges. The resulting materials were characterized by a continuous network pore structure with average pore sizes of 9–50 nm, conveniently tunable by the length of the utilized bottlebrush copolymer building blocks. As a result, the materials fabrication strategy described in this work expands the length scale of molecular framework materials and provides access to mesoporous polymers with a molecularly tunable reticulated pore structure without the need for templating, sacrificial component etching, or supercritical fluid drying.
- Authors:
-
[1]
; [2]
;
[1]
- Univ. at Buffalo, The State Univ. of New York, Buffalo, NY (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Report Number(s):
- BNL-114443-2017-JA
Journal ID: ISSN 1936-0851
- Grant/Contract Number:
- SC0012704
- Type:
- Accepted Manuscript
- Journal Name:
- ACS Nano
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 8; Journal ID: ISSN 1936-0851
- Publisher:
- American Chemical Society (ACS)
- Research Org:
- Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
- Sponsoring Org:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 77 NANOSCIENCE AND NANOTECHNOLOGY; nanoporous materials; organic frameworks; bottlebrush copolymers; polymer networks; Center for Functional Nanomaterials; cross-linking
- OSTI Identifier:
- 1405935