Intrinsically Hierarchical Nanoporous Polymers via Polymerization-Induced Microphase Separation

Larsen, Michael B.; Van Horn, J. David; Wu, Fei; Hillmyer, Marc A.

doi:10.1021/acs.macromol.7b00808

Intrinsically Hierarchical Nanoporous Polymers via Polymerization-Induced Microphase Separation

Journal Article · Wed May 24 00:00:00 EDT 2017 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.7b00808· OSTI ID:1373793

^[1]; Van Horn, J. David ^[2]; Wu, Fei ^[2]; ^[1]

Univ. of Minnesota, Minneapolis, MN (United States)
Univ. of Missouri, Kansas City, MO (United States)

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 (T_g) 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.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: National Science Foundation (NSF); Northwestern University; E.I. DuPont de Nemours & Co.; The Dow Chemical Company; USDOE Office of Science (SC)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1373793

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 11 Vol. 50; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

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