Assembly of Amphiphilic Hyperbranched Polymeric Ionic
Liquids in Aqueous Media at Different pH and Ionic Strength
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Abstract
We demonstrated the
assembly of amphiphilic hyperbranched protic
ionic liquids (HBP-ILs) based on aliphatic hyperbranched polyester
(HBP) in aqueous media in a wide range of pH and ionic conditions.
The series of new branched polyionic liquids with different terminal
groups, HBP-ILs, was synthesized by neutralization of carboxylic and
sulfonic terminal acid groups of hypebranched core with <i>N</i>-methylimidazole (Im) and 1,2,4-1<i>H</i>-triazole
(Tr). HBP-IL compounds with triazole and imidazole counterions form
12–16 nm core–corona micelles at pH 11.6. We found that
the introduction of long hydrophobic terminal groups such as <i>n</i>-octadecylurethane tails to initial hydrophobic HBP core
has larger effect on the size of micellar assemblies than the introduction
of ionic terminals groups. Furthermore, tuning the hydrophilic/hydrophobic
balance of HBP-ILs can be achieved by changing the degree of ionization
of terminal groups and counterions by reducing pH from 11.6 to 5.2
or ionic strength to 0.1 M. These changes caused the formation of
much larger micellar aggregates with the size of 150–200 nm
due to reduced ionization of carboxylic groups. At the same time,
for sulfonate-containing HBP-ILs the micelle size increased modestly
(to 25–40 nm) because of the higher degree of ionization of
sulfonate terminal groups. The diverse aggregation behavior of these
branched polymeric ionic liquids enables control over their micellar
morphologies in solution and bulk states