Summary
Tri-armed amphiphilic block polymers (\(\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle\thicksim}$}}{5} \) and \(\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle\thicksim}$}}{6} \)) of isobutyl and 2-hydroxyethyl vinyl ethers (IBVE and HOVE, respectively) were prepared. The synthesis was based on the sequential living cationic polymerization of IBVE and 2-acetoxyethyl vinyl ether (AcOVE) initiated with a trifunctional initiating system that consisted of a tris(trifluoroacetate) [CH3-C(-C6H4OCH2CH2OCHMeOCOCF3)3; \(\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle\thicksim}$}}{1} \)] and ethylaluminum dichloride (EtAlCl2) coupled with an exess of 1,4-dioxane as a carbocation-stabilizing Lewis base. The subsequent hydrolysis of the ester pendant groups in the resulting poly(AcOVE) segments led to the target IBVE-HOVE amphiphilic triarmed polymers. Depending on the polymerization sequence of IBVE and AcOVE, the hydrophilic poly(HOVE) chain could be placed either inner or outer segment of the tri-armed architecture. The solubility of these polymers (\(\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle\thicksim}$}}{5} \) and \(\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle\thicksim}$}}{6} \)) was apparently determined by the nature of the outer segments.
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References
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Shohi, H., Sawamoto, M. & Higashimura, T. Tri-armed star polymers by living cationic polymerization. Polymer Bulletin 25, 529–536 (1991). https://doi.org/10.1007/BF00293510
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DOI: https://doi.org/10.1007/BF00293510