Authors Thibault, R.J. ; Malkoch, M. ; Drockenmuller, E. ; Messerschmidt, M. ; Voit, B. ; Hawker, C.J.
Title Combination of LFRP and click chemistry for orthogonal modification of well-defined terpolymers
Date 29.04.2005
Number 13098
Abstract Living/controlled free radical polymerization (LFRP) techniques such as Atom Transfer Radical Polymerization (ATRP), Radical Addition Fragmentation Transfer (RAFT), and Nitroxide-Mediated Polymerization (NMP) have generated considerable interest in recent years owing to the ability to construct well-defined, functional polymeric scaffolds necessary for nanotechnology applications. Unlike anionic polymerizations, which also yield very well-defined polymers, monomers subjected to LFRP techniques are often done so under mild conditions without the need for ultrapure reaction conditions. Also, LFRP is tolerant to a variety of functional groups while still providing tunable molecular weight and low polydispersity. Research in the field of polymer chemistry has made available a large variety of monomers capable of forming a variety of specialty polymers with customizable properties. However, post-polymerization modification is often required to fine-tune the end properties ensuring that the polymer fits the targeted application. Complex reaction conditions dictates optimization of variables such as temperature, stoichiometric ratio, concentration, and reaction time to ensure complete modification. As one attempts to optimize these parameters, issues such as solubility, steric hindrance, and competing side reactions all contribute to incomplete conversion. A concept recently introduced by B. Sharpless, called Click Chemistry, is gaining popularity due to its quantitative yields, solvent independence, and regiospecific conversion under very mild reaction conditions with non-chromatographic work-up. The best known and most widely used "click" reaction is the copper(I)-catalyzed 1,3 dipolar cycloaddition developed by Huisgen of terminal acetylenes and azides. In addition to the advantages of the click reaction described above, the 1,3 dipolar cycloaddition is extremely tolerant to many functional groups and procedes with high fidelity. With this information in mind, we introduce a new bio-inspired concept to post-polymerization modification where multiple independent reactions occur in parallel in a single system without interfering with each other.
Publisher Polymer Preprints
Citation Polymer Preprints 46 (2005) S.10
Tags terpolymers; free radical polymerization; copolymerization; functional groups; reaction mechanisms

Back to list