title: Degradable Polycaprolactone and Polylactide Homopolymer and Block Copolymer Brushes Prepared by Surface-Initiated Polymerization with Triazabicyclodecene and Zirconium Catalysts.
abstract: Surface-initiated ring-opening polymerization (SI-ROP) of polycaprolactone (PCL) and polylactide (PLA) polymer brushes with controlled degradation rates were prepared on oxide substrates. PCL brushes were polymerized from hydroxyl-terminated monolayers utilizing triazabicyclodecene (TBD) as the polymerization catalyst. A consistent brush thickness of 40 nm could be achieved with a reproducible unique crystalline morphology. The organocatalyzed PCL brushes were chain extended using lactide in the presence of zirconium n-butoxide to successfully grow PCL/PLA block copolymer (PCL-b-PLA) brushes with a final thickness of 55 nm. The degradation properties of "grafted from" PCL brush and the PCL-b-PLA brush were compared to "grafted to" PCL brushes, and we observed that the brush density plays a major role in degradation kinetics. Solutions of methanol/water at pH 14 were used to better solvate the brushes and increase the kinetics of degradation. This framework enables a control of degradation that allows for the precise removal of these coatings.
authors: Department of Chemistry, College of Engineering, and the Center for Nanoscale Science and Engineering, University of Georgia , Athens, Georgia 30602, United States.|Meredian Holdings Group - MHG, 140 Industrial Boulevard, Bainbridge, Georgia 39817, United States.
authors: Joe B
authors: JB
authors: Grubbs
authors: Meredian Holdings Group - MHG, 140 Industrial Boulevard, Bainbridge, Georgia 39817, United States.
authors: Rachelle M
authors: RM
authors: Arnold
authors: Department of Chemistry, College of Engineering, and the Center for Nanoscale Science and Engineering, University of Georgia , Athens, Georgia 30602, United States.
authors: Anandi
authors: A
authors: Roy
authors: Department of Chemistry, College of Engineering, and the Center for Nanoscale Science and Engineering, University of Georgia , Athens, Georgia 30602, United States.
authors: Karson
authors: K
authors: Durie
authors: Department of Chemistry, College of Engineering, and the Center for Nanoscale Science and Engineering, University of Georgia , Athens, Georgia 30602, United States.
authors: Jenna A
authors: JA
authors: Bilbrey
authors: Department of Chemistry, College of Engineering, and the Center for Nanoscale Science and Engineering, University of Georgia , Athens, Georgia 30602, United States.
authors: Jing
authors: J
authors: Gao
authors: Department of Chemistry, College of Engineering, and the Center for Nanoscale Science and Engineering, University of Georgia , Athens, Georgia 30602, United States.
authors: Jason
authors: J
authors: Locklin
mesh_terms: D053961:Azabicyclo Compounds / Q000737:chemistry*; D002384:Catalysis; D011091:Polyesters / Q000737:chemistry*; D058105:Polymerization; D011108:Polymers / Q000737:chemistry*; D015040:Zirconium / Q000737:chemistry*
chemical_list: D053961:Azabicyclo Compounds; D011091:Polyesters; D011108:Polymers; C526482:triazabicyclodecene; C016240:polycaprolactone; C033616:poly(lactide); D015040:Zirconium