Intrinsically Hierarchical Nanoporous Polymers via Polymerization-Induced Microphase Separation
Abstract
The synthesis of microporous polymers generally requires postpolymerization modification via hyper-cross-linking to trap the polymeric network in a state with high void volume. An alternative approach utilizes rigid, sterically demanding monomers to inhibit efficient packing, thus leading to a high degree of free volume between polymer side groups and main chains. In this work we combine polymers of intrinsic microporosity with polymerization-induced microphase separation (PIMS), a versatile methodology for the synthesis of nanostructured materials that can be rendered mesoporous. Copolymerization of various styrenic monomers with divinylbenzene in the presence of a poly(lactide) terminated with a chain-transfer agent (PLA-CTA) results in kinetic trapping of a microphase-separated state. Subsequent etching of PLA provides a bicontinuous mesoporous network. Using equilibrium and kinetic nitrogen sorption experiments as well as positron annihilation lifetime spectroscopy (PALS), we demonstrate that variations in the steric characteristics of the styrenic monomer impart the network with microporosity, resulting in hierarchically (meso and micro) porous materials. Additionally, structure–property relationships of the styrenic monomer with total surface area and pore volume indicate that the glass transition temperature (Tg) of the corresponding styrenic homopolymers provides a reasonable measure of the steric interactions and resultant microporosity in these systems. Finally, PALS provides insight intomore »
- Authors:
-
[1];
[1]
- Univ. of Minnesota, Minneapolis, MN (United States)
- Univ. of Missouri, Kansas City, MO (United States)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Org.:
- National Science Foundation (NSF); Northwestern University; E.I. DuPont de Nemours & Co.; The Dow Chemical Company; USDOE Office of Science (SC)
- OSTI Identifier:
- 1373793
- Grant/Contract Number:
- AC02-06CH11357; 0960140
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Macromolecules
- Additional Journal Information:
- Journal Volume: 50; Journal Issue: 11; Journal ID: ISSN 0024-9297
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- ENGLISH
- Subject:
- 36 MATERIALS SCIENCE; Porosity; Monomers; Materials; Catalyst supports; Polymers
Citation Formats
Larsen, Michael B., Van Horn, J. David, Wu, Fei, and Hillmyer, Marc A. Intrinsically Hierarchical Nanoporous Polymers via Polymerization-Induced Microphase Separation. United States: N. p., 2017.
Web. doi:10.1021/acs.macromol.7b00808.
Larsen, Michael B., Van Horn, J. David, Wu, Fei, & Hillmyer, Marc A. Intrinsically Hierarchical Nanoporous Polymers via Polymerization-Induced Microphase Separation. United States. https://doi.org/10.1021/acs.macromol.7b00808
Larsen, Michael B., Van Horn, J. David, Wu, Fei, and Hillmyer, Marc A. Wed .
"Intrinsically Hierarchical Nanoporous Polymers via Polymerization-Induced Microphase Separation". United States. https://doi.org/10.1021/acs.macromol.7b00808. https://www.osti.gov/servlets/purl/1373793.
@article{osti_1373793,
title = {Intrinsically Hierarchical Nanoporous Polymers via Polymerization-Induced Microphase Separation},
author = {Larsen, Michael B. and Van Horn, J. David and Wu, Fei and Hillmyer, Marc A.},
abstractNote = {The synthesis of microporous polymers generally requires postpolymerization modification via hyper-cross-linking to trap the polymeric network in a state with high void volume. An alternative approach utilizes rigid, sterically demanding monomers to inhibit efficient packing, thus leading to a high degree of free volume between polymer side groups and main chains. In this work we combine polymers of intrinsic microporosity with polymerization-induced microphase separation (PIMS), a versatile methodology for the synthesis of nanostructured materials that can be rendered mesoporous. Copolymerization of various styrenic monomers with divinylbenzene in the presence of a poly(lactide) terminated with a chain-transfer agent (PLA-CTA) results in kinetic trapping of a microphase-separated state. Subsequent etching of PLA provides a bicontinuous mesoporous network. Using equilibrium and kinetic nitrogen sorption experiments as well as positron annihilation lifetime spectroscopy (PALS), we demonstrate that variations in the steric characteristics of the styrenic monomer impart the network with microporosity, resulting in hierarchically (meso and micro) porous materials. Additionally, structure–property relationships of the styrenic monomer with total surface area and pore volume indicate that the glass transition temperature (Tg) of the corresponding styrenic homopolymers provides a reasonable measure of the steric interactions and resultant microporosity in these systems. Finally, PALS provides insight into micro- and mesoscopic void volume differences between porous monoliths containing either tert-butyl or TMS-modified styrenic monomers compared to the parent, unmodified styrene.},
doi = {10.1021/acs.macromol.7b00808},
journal = {Macromolecules},
number = 11,
volume = 50,
place = {United States},
year = {Wed May 24 00:00:00 EDT 2017},
month = {Wed May 24 00:00:00 EDT 2017}
}
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