Synthesis of diblock copolymers by combination of organocatalyzed ring-opening polymerization and atom transfer radical polymerization using trichloroethanol as a bifunctional initiator

• Published in: Journal of polymer science. Part A, Polymer chemistry Vol. 54; no. 4; pp. 563 - 569
• Main Authors: Piunova, Victoria A., Horn, Hans W., Jones, Gavin O., Rice, Julia E., Miller, Robert D.
• Format: Journal Article
• Language: English
• Published: Hoboken Blackwell Publishing Ltd 15-02-2016; Wiley Subscription Services, Inc
• Subjects: atom transfer radical polymerization (ATRP); Block copolymers; Computation; Formations; Gel permeation chromatography; Initiators; molecular modeling; Polymerization; Radicals; ring-opening polymerization; Synthesis
• ISSN: 0887-624X; 1099-0518
• DOI: 10.1002/pola.27807

ABSTRACT
This study reports an application of trichloroethanol (TCE) as a bifunctional initiator for the synthesis of block copolymers (BCPs) by organocatalyzed ring‐opening polymerization (OROP) and atom transfer radical polymerization (ATRP). TCE was employed to synthesize a low dispersity poly (valerolactone) macroinitiator, which was subsequently used for the ATRP of tert‐butyl methacrylate. While it is known that TCE can serve as an initiator in ATRP, the ability to induce polymerization under OROP is reported for the first time. The formation of well‐defined BCPs was confirmed by gel permeation chromatography and 1H NMR. Computational studies were performed to obtain a molecular‐level understanding of the ring‐opening polymerization mechanism involving TCE as initiator. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 563–569
Trichloroethanol (TCE) was employed for the synthesis of block copolymers (BCPs) by the combination of organocatalyzed ring‐opening polymerization and atom transfer radical polymerization. The formation of well‐defined BCPs was confirmed by gel permeation chromatography and 1H NMR. Computational studies were performed to obtain a molecular‐level understanding of the ring‐opening polymerization mechanism involving TCE as initiator.