Methylated
poly(vinyl amine) brushes generated on PS-DVB microspheres
were demonstrated as excellent macroligands, forming hydrophilic Co(II)
chelates capable of reversible molecular oxygen binding. The oxygenation
is extremely fast when counteranions of cobalt are replaced with hydroxyl
ions. The experiments carried out using oxygen sensor, FT-IR, TGA
techniques, and gas volumetric measurements showed that the polymer
complexes with either 4/1 or 2/1 [amine]/[Co] ratios form 1:1 molecular
oxygen adducts which are stable up to 110–120 °C. In order
to impart the chain extension effect, poly(vinyl amine-stat-DADMAC)
brushes were also generated on the microspheres by using DADMAC as
additional comonomer. Fast oxygenation, high oxygen binding capacity
(ca. 80 mL/g), and long-term stability of the oxygen adducts make
the polymeric complex superior to current systems. The cobalt complex
system presented can be considered as a high capacity solid matrix
for dissociation and chemical storage of the molecular oxygen from
air.
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<p>Acid catalyzed polymerization of phenyl ethane 1,2-diol is realized for the first
time via a novel one-pot coupling reaction to produce organosoluble poly(phenylene
vinylene). A variety of experimental conditions were investigated. PPV structure was
confirmed by 13C-NMR and 1H-NMR chemical shifts. Fluorescence spectra of the polymer showed emission in the visible range, as to be expected. Average PPV molecular
weights ranged from 670 to 6200 Da. The methanesulfonic acid (MesOH) catalyzed
syntheses were shown to produce higher molecular weight and purity PPV than the
sulfuric acid (H2SO4) counterparts, although both are able to produce organosoluble
products.
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Summary
Polymer microbeads consisting of 20% 2‐hydroxyethyl methacrylate (HEMA), 70% methyl methacrylate (MMA), and 10% ethylene glycol dimethacrylate (EGDMA) were methane sulfonated (mesylated) using equivalent methane sulfonyl chloride‐pyridine. The methane sulfonate surface groups generated were employed as cationic initiation sites for surface initiated polymerization (SIP) of 2‐methyl 2‐oxazoline. The acetyl groups of resulting poly‐oxazoline brushes were hydrolyzed to polyethylene imines. This methane sulfonated group was also used for substitution of triethylenetetramine (TETA) by direct action. The resulting multi amine ligands on the surfaces were demonstrated to bind Cu(II), Ni(II), and Co(II) ions reversibly.
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