Facile, Modular Transformations of RAFT Block Copolymers via Sequential Isocyanate and Thiol-ene Reactions

Document Type

Article

Publication Date

2011

Department

Polymers and High Performance Materials

Abstract

We describe a robust strategy utilizing reversible addition-fragmentation chain transfer (RAFT) polymerization and sequential transformations involving carbamate formation and thiol-ene click addition to synthesize well-defined functional block copolymers. The hydroxy-functional block copolymer scaffold, poly[(N,N-dimethylacrylamide)-b-(N-(2-hydroxyethyl)acrylamide)] (PDMAn-b-PHEAm) was first prepared via RAFT, requiring no protecting group chemistry. The hydroxyl groups of the HEA block were then reacted with 2-(acryloyloxy)ethylisocyanate (AOI) or allylisocyanate (AI) resulting in acrylate- and allyl-functionalized copolymer precursors, respectively. The efficiencies of both Michael and free radical-mediated thiol-ene addition reactions were investigated using model thiol compounds having alkyl, aryl, hydroxyl, carboxylic acid, amine and amino acid functionalities. The steps of RAFT polymerization, isocyanate-hydroxyl coupling and thiol-ene addition can be accomplished under mild conditions, thus offering a facile, modular route to the synthesis of functional copolymers from a single polymeric precursor.

Publication Title

Polymer Chemistry

Volume

2

Issue

9

First Page

1976

Last Page

1985

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