Research Summary:
Living Radical Polymerization (LRP) is used as the central technique in the synthesis of advanced macromolecular architectures. Self-assembly of these architectures and heterogeneous polymerization processes are used to create ordered structures on a larger length scale. In order to optimize the degree of control in LRP processes, mechanistic studies are conducted to increase the understanding of the fundamental processes involved.
Research Description:
Advanced Macromolecular Architectures: In this research line we design, synthesize and characterize complex macromolecular structures. The main emphasis is on molecular brushes and polymer-protein conjugates. Densely grafted alternating copolymers are among the target structures. Next to the chemical characterization of the structures we will increasingly focus on their solution properties. From a synthetic point of view, the emphasis will be on living radical polymerization techniques, where complementary techniques will be used when required.
Morphological control: Self-assembly of the advanced macromolecular architectures leads to interesting 2D and 3D morphologies. Alternatively we look into the use of heterogeneous polymerization processes in order to encapsulate active compounds. These compounds can vary from reactants for self-healing coatings to biologically active compounds in controlled drug release.

Mechanistic and kinetic studies: In recent years we focused strongly on mechanistic studies of the early stages of RAFT-mediated polymerization. A selective initialization process was discovered in which the original RAFT-agent is converted into its single monomer adduct. This work is expanded in various directions. We will use nitroxide-mediated polymerization in order to determine relevant kinetic constants. A stronger focus will be on copolymerization reactions, and selectivity issues in these systems. The synthetic use of the initialization process will be further investigated in the synthesis of end-functional polymer chains. |
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Selected Publications:
- Pound, G.; McLeary, J.B.; McKenzie, J.; Sanderson, R.D.; Klumperman, B. – Probing the efficiency of RAFT agents with in situ NMR spectroscopy – Macromolecules 2006, 39, 7796-7797
- McLeary, J.B.; Klumperman, B. – RAFT mediated polymerisation in heterogeneous media – Soft Matter 2006, 2, 45-53
Venkatesh, R.; Staal, B.; Klumperman, B – Olefin copolymerization via reversible addition-fragmentation chain transfer – Chem. Comm. 2004, 13, 1554-1555
- Kelemen, P.; Klumperman, B. – Determination of the free radical concentration ratio in the copolymerization of methyl acrylate and styrene. Application of radical trapping and 15N NMR spectroscopy – Macromolecules 2004, 37(25), 9338-9344
- McLeary, J.B.; McKenzie, J. M.; Tonge, M. P.; Sanderson, R. D.; Klumperman, B. – Initialisation in RAFT - mediated polymerisation of methyl acrylate – Chem. Comm. – 2004, 17, 1950-1951
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