Development of Thermal and Photochemical Strategies for Thiol−Ene Click Polymer Functionalization

Luis M. Campos, Kato L. Killops, Ryosuke Sakai, Jos Marie Johannes Paulusse, Denis Damiron, Eric Drockenmuller, Benjamin W. Messmore, Craig J. Hawker

Research output: Contribution to journalArticleAcademic

370 Citations (Scopus)

Abstract

A series of alkene-functional polymers were synthesized by controlled polymerization techniques in order to investigate and compare the efficiency and orthogonality of both photochemically and thermally initiated thiol−ene click coupling reactions. The copolymers were designed to have single or multiple alkene-functional groups along the backbone, and to evaluate the robustness of these procedures, functionalization reactions with a library of mercaptans were studied. In comparing the photoinitiated reaction to its thermal counterpart, the thiol−ene photocoupling was found to proceed with higher efficiency, require shorter reaction times for complete conversion, and displayed a higher tolerance to various backbones and functional groups. To examine the orthogonality of the thiol−ene click reaction, an asymmetric telechelic polymer based on PS was designed with alkene functionality at one end and an azide at the other. The thermally initiated thiol−ene coupling was found to be completely orthogonal with the traditional azide/alkyne click reaction allowing the individual chain ends to be quantitatively functionalized without the need for protection/deprotection strategies. From these studies, the demonstrated efficiency and orthogonality of thiol−ene chemistry shows it to be a practical addition to the family of click reactions that are suitable for polymer functionalization.
Original languageEnglish
Pages (from-to)7063-7070
Number of pages8
JournalMacromolecules
Volume41
Issue number19
DOIs
Publication statusPublished - 2008

Keywords

  • IR-99607

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