Media type: E-Article Title: Synthesis, characterization, and star polymer assembly of boronic acid end‐functionalized polycaprolactone Contributor: Korich, Andrew L.; Walker, Amanda R.; Hincke, Christopher; Stevens, Caitlin; Iovine, Peter M. Published: Wiley, 2010 Published in: Journal of Polymer Science Part A: Polymer Chemistry, 48 (2010) 24, Seite 5767-5774 Language: English DOI: 10.1002/pola.24384 ISSN: 0887-624X; 1099-0518 Origination: Footnote: Description: AbstractBoronic acid end‐functionalized polycaprolactone (PCL) polymers were synthesized by ring‐opening polymerization using a pinacol boronate ester‐containing (Bpin) initiator. The polymerization provides access to boron‐terminated polymers (i.e. Bpin‐PCL‐OH) with narrow molecular weight distributions (PDI = 1.09). Postsynthetic manipulation of the polymer's terminal hydroxyl group by copper‐catalyzed azide‐alkyne cycloaddition chemistry provides a series of bis end‐functionalized polymers with significant structural diversity at the termini. Deprotection of the boronate ester end group was accomplished with an acidic solid phase DOWEX resin. The boronate ester deprotection methodology does not result in hydrolysis of the polymeric backbone. The boronic acid‐tipped polymers were converted into star polymer assemblies using thermal dehydration and ligand‐facilitated trimerization. Thermal dehydration of (HO)2B‐PCL‐OAc to the corresponding boroxine‐based star polymer assembly was inefficient and lead to degradation products. Ligand‐facilitated trimerization using either pyridine or 7‐azaindole as the Lewis base was efficient and mild. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010