Novel tri- and tetrafunctional cholic acid-based initiators for the synthesis of star-shaped poly(L-lactide)s

Abstract

In this investigation, two novel multifunctional initiators for ring-opening polymerization were synthesized in three steps starting from cholic acid. Thus, cholic acid (1a) and its methyl ester (1b) were quantitatively transformed, via solvent-free reaction with succinic anhydride, to the corresponding 3, 7, 12-tri-hemisuccinate derivatives (3a-b). The polyacidic compounds (3a-b) were treated with thionyl chloride affording the corresponding acyl chlorides 4a-b which, in turn, were reacted with ethylene glycol to give the derivatives 2a-b having three and four primary alcohol end groups. These compounds, fully characterized by 1H, 13C NMR and mass spectrometry, have been assessed as initiators in the ring-opening polymerization of L-lactide using stannous octanoate as catalyst. The resulting three- and four-armed star-shaped poly(L-lactide)s, which were characterized by 1H NMR, SEC, DSC and TGA analysis, were amorphous, and their glass transition temperatures ranged from 13.7 to 36.5 °C. Additionally, some cholic acid-based star-shaped polylactic structures recently published have been critically reconsidered showing that these molecules, described as star polymers, were actually linear polymers.