From nano to the macro: tuning hierarchical aggregation of thermoresponsive PEG/PCL-based polyurethanes via molar mass/composition control

Abstract Amphiphilic hyperbranched polyurethanes (HPUs) based on PEG and PCL are promising for several biomedical applications. However, the lack of control over the molar mass and composition hinders a deep understanding of the aqueous self-assembly of HPUs. In this paper, the control over the HPU molar mass and composition was provided by dynamic urea bond-mediated polymerization (DUBMP), enabling a careful evaluation of their aqueous self-assembly by 1 H NMR, DLS, and Cryo-TEM. HPUs containing a single PCL block per chain self-assemble into nanoaggregates ( R h ≈ 10 nm) in water up to its cloud-point temperature ( T cp ) of 34 °C. On the other hand, HPUs with more than one PCL block per chain self-assemble into nanoaggregates and their clusters below T cp . In this case, the solution behavior can be tuned by the HPU molar mass. Increasing $$\overline{{\mathrm{M} }_{\mathrm{w}}}$$ M w ¯ from 4 to 19 kDa, HPUs of similar composition can form colloidally stable cluster suspensions ( $$\overline{{\mathrm{M} }_{\mathrm{w}}}$$ M w ¯ = 4 kDa) and phase separate into a denser liquid aggregate–cluster phase ( $$\overline{{\mathrm{M} }_{\mathrm{w}}}$$ M w ¯ = 7 kDa) or into a highly viscous aggregate-network phase ( $$\overline{{\mathrm{M} }_{\mathrm{w}}}$$ M w ¯ = 19 kDa). This type of control over the hierarchical aggregation of HPUs was reported for the first time and is interesting for biomedical applications. Graphical abstract