The long and the short of radical polymerization

Derboven, P., D'Hooge, D. R., Reyniers, M. F., Marin, G. B., & Barner-Kowollik, C. (2015) The long and the short of radical polymerization. Macromolecules, 48(3).

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Abstract

Precision functionality is the key feature of next-generation radical polymerization enabling the implementation of applications such as controlled drug delivery, self-healing material design, and optoelectronic materials. The incorporation of functionality is however diametrically opposed to diffusion-controlled growth-inhibiting termination reactions. The fundamental bottleneck remains the identification of a generic and flexible protocol to accurately map the short-long termination reactivity. Herein, we introduce a unique framework based on the reversible addition-fragmentation chain transfer-chain length dependent-termination (RAFT-CLD-T) method that encompasses an extension of state-of-the-art fundamental theories and a correction for possible polymer matrix effects. Applied to methyl methacrylate (MMA) polymerization, the short-long termination reactivity is accurately quantified for the first time. Data analysis reveals the deficiency of currently used simplified models to describe the true short-long termination reactivity and the dominance of short-chain diffusivity. The proposed framework and insights are a turnkey prerequisite for the fundamental understanding of radical polymerization processes and to complete current macromolecular diffusion theories. © 2015 American Chemical Society.

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12 citations in Web of Science®

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ID Code: 99427
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :12
Export Date: 5 September 2016
CODEN: MAMOB
Correspondence Address: D'Hooge, D.R.; Laboratory for Chemical Technology, Ghent University, Technologiepark 914, Belgium
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Keywords: Atom transfer radical polymerization, Chain length, Chains, Controlled drug delivery, Drug delivery, Esters, Free radical polymerization, Optoelectronic devices, Polymerization, Self-healing materials, Transfer matrix method, Chain length dependent terminations, Diffusion controlled growth, Fundamental theory, Methyl methacrylates, Opto-electronic materials, Polymerization process, Reversible addition fragmentation chain transfer, Termination reactions, Acrylic monomers
DOI: 10.1021/ma5017659
ISSN: 00249297
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 26 Sep 2016 05:26

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