Journal
ACS MACRO LETTERS
Volume 1, Issue 7, Pages 834-839Publisher
AMER CHEMICAL SOC
DOI: 10.1021/mz300196x
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Funding
- National Science Foundation [DMR-0906898]
- Joint-Hope Education Foundation
- Direct For Mathematical & Physical Scien
- Division Of Materials Research [906898] Funding Source: National Science Foundation
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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.
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