Synthesis of Shape Amphiphiles Based on POSS Tethered with Two Symmetric/Asymmetric Polymer Tails via Sequential “Grafting-from” and Thiol–Ene “Click” Chemistry

A series of shape amphiphiles based on functionalized polyhedral oligomeric silsesquioxane (POSS) head tethered with two polymeric tails of symmetric or asymmetric compositions was designed and synthesized using sequential "grafting-from" and "click" surface functionalization. The monofunctionalization of octavinylPOSS was performed using thiol-ene chemistry to afford a dihydroxyl-functionalized POSS that was further derived into precisely defined homo- and heterobifunctional macroinitiators. Polymer tails, such as polycaprolactone and polystyrene, could then be grown from these POSS-based macroinitiators with controlled molecular weight via ring-opening polymerization and atom transfer radical polymerization (ATRP). The vinyl groups on POSS were found to be compatible with ATRP conditions. These macromolecular precursors were further modified by thiol-ene chemistry to install surface functionalities onto the POSS cage. The polymer chain composition and POSS surface chemistry can thus be tuned separately in a modular and efficient way.