title: Hierarchically porous polymers from hyper-cross-linked block polymer precursors.
abstract: We report synthesis of hierarchically porous polymers (HPPs) consisting of micropores and well-defined 3D continuous mesopores by combination of hyper-cross-linking and block polymer self-assembly. Copolymerization of 4-vinylbenzyl chloride (VBzCl) with divinylbenzene (DVB) in the presence of polylactide (PLA) macro-chain-transfer agent produced a cross-linked block polymer precursor PLA-b-P(VBzCl-co-DVB) via reversible addition-fragmentation chain transfer polymerization. A nanoscopic bicontinuous morphology containing PLA and P(VBzCl-co-DVB) microdomains was obtained as a result of polymerization-induced microphase separation. While a basic treatment of the precursor selectively removed PLA to yield a reticulated mesoporous polymer, hyper-cross-linking of the precursor by FeCl3 generated micropores in the P(VBzCl-co-DVB) microdomain via Friedel-Crafts alkylation and simultaneously degraded PLA to produce the HPP containing micropores in the mesoporous framework. The mesopore size of the HPP could be precisely controlled from 6 to 15 nm by controlling the molar mass of PLA. We demonstrate acceleration in adsorption rate in the HPP compared to a hyper-cross-linked microporous polymer.
authors.affiliation: Graduate School of Nanoscience and Technology, Korea Advanced Institute of Science and Technology (KAIST) , Daejeon 305-701, Korea.
authors.forename: Myungeun
authors.initials: M
authors.lastname: Seo
authors.forename: Soobin
authors.initials: S
authors.lastname: Kim
authors.forename: Jaehoon
authors.initials: J
authors.lastname: Oh
authors.forename: Sun-Jung
authors.initials: SJ
authors.lastname: Kim
authors.forename: Marc A
authors.initials: MA
authors.lastname: Hillmyer