Fluorous Microgel Star Polymers: Selective Recognition and Separation of Polyfluorinated Surfactants and Compounds in Water

Abstract

Immiscible with either hydrophobic or hydrophilic solvents, polyfluorinated compounds (PFCs) are generally "fluorous", some of which have widely been employed as surfactants and water/oil repellents. Given the prevailing concern about the environmental pollution and the biocontamination by PFCs, their efficient removal and recycle from industrial wastewater and products are critically required. This paper demonstrates that fluorous-core star polymers consisting of a polyfluorinated microgel core and hydrophilic PEG-functionalized arms efficiently and selectively capture PFCs in water into the cores by fluorous interaction. For example, with over 10 000 fluorine atoms in the core and approximately 100 hydrophilic arms, the fluorous stars remove perfluorooctanoic acid (PFOA) and related PFCs in water from 10 ppm to as low as a parts per billion (ppb) level, or an over 98% removal. Dually functionalized microgel-core star polymers with perfluorinated alkanes and additional amino (or ammonium) groups cooperatively recognize PFOA or its ammonium salt and, in addition, release the guests upon external stimuli. The "smart" performance shows that the fluorous-core star polymers are promising PFC separation, recovery, and recycle materials for water purification toward sustainable society.

Mesoporous Fluorinated Metal–Organic Frameworks with Exceptional Adsorption of Fluorocarbons and CFCs

“…[1,4] Thus,t heir capture and sequestration are of significant interest. Fluorocarbon capture and storage have been performed on fluorous microgel star polymers, [5] self-assembled coordination cages, [6] fluorinated porous molecular crystals, [7] and MOFs. [8] Fluorinated MOFs, [9] such as FMOF-1 pioneered by Omary and coworkers, [9e] are ap articularly appealing platform for the adsorption of fluorocarbons and CFCs on account of their large pore sizes,f luorophilic character,a nd low affinity for moisture.H owever,e xploration of high-surface-area fluorinated MOFs as adsorbents for fluorocarbons and CFCs has thus far not been possible because of the synthetic inaccessibility of the appropriately fluorinated ligands.H erein, we report the synthesis of two mesoporous,e xtensively fluorinated MOFs (MOFFs);o ne of these materials is the highest surface-area fluorinated MOF ever prepared.…”

“…Single-crystal synchrotron diffraction analysis [12] revealed athree-dimensional network with alarge cubic unit cell a = b = c = 47.326 (5) , in which pairs of Cu atoms form paddlewheel-shaped Cu 2 (COO) 4 clusters that are capped with one molecule of H 2 Oa te ach Cu center (Figure 2A). After 4days at 60 8 8C, greenish-blue crystals of MOFF-4 were isolated.…”

Precise Synthesis of Ultra‐High‐Molecular‐Weight Fluoropolymers Enabled by Chain‐Transfer‐Agent Differentiation under Visible‐Light Irradiation

“…Thestrong and selective fluorine-fluorine interaction has been exploited as apowerful strategy for selective separation of fluorinated components in organic synthesis, [16] aqueous purification, [17] and nano-objects design. [18] While these studies are based on interactions between pre-synthesized fluorinated materials and small molecules,w ee nvisaged that fluoropolymers generated during polymerization would be able to separate fluorinated monomers from reaction mixtures,w hich could provide ad istinct chain-growth mode.I n this new mode,CTAscould differentiate into two groups,one propagating group (PG) taking charge of chain growth, and the other supporting group (SG) remaining dormant, being responsible for the reversible-deactivation of propagating chains to maintain the livingness of polymerization (Scheme 1), ap rocess similar to the stem cell differentiation in nature.…”

Facile one‐shot synthesis of functional star‐shaped polymers by domino‐type living cationic copolymerization

“…Functional core cross‐linked star‐shaped (CCS) polymers, which consist of multiple linear arm chains radiating from a central microgel core, have enormous potential as intelligent materials for a wide range of applications, including biomedical imaging, as drug carriers, environmental protectors, nanocatalysts, and smart films . Substantial progress has been made by the recent advance in controlled/living radical polymerization, which has allowed the synthesis of a range of functional CCS polymers.…”