Acrylamide-based copolymers bearing photoreleasable thiols for subsequent thiol-ene functionalization

Delaittre, G., Pauloehrl, T., Bastmeyer, M., & Barner-Kowollik, C. (2012) Acrylamide-based copolymers bearing photoreleasable thiols for subsequent thiol-ene functionalization. Macromolecules, 45(4).

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Abstract

A new set of monomers is presented in order to incorporate thiols into radical polymers using a protecting chemistry/photocleavage route. The (co)polymerization kinetics of an o-nitrobenzyl thioether-containing acrylamide derivative are reported. The presence of the o-nitrobenzyl moiety is found to strongly affect the polymerization. Nevertheless, water-soluble copolymers with N,N-dimethylacrylamide (DMAAm) as a comonomer are obtained either by free radical polymerization (10 000 ≤ M n ≤ 17 500 g mol -1; 1.5 ≤ PDI ≤ 1.8) or by reversible addition-fragmentation transfer (RAFT)-mediated controlled/living radical polymerization (2000 ≤ M n ≤ 5700 g mol -1; 1.1 ≤ PDI ≤ 1.2). Deprotection under UV light (λ = 366 nm) at ambient temperature is followed by UV/vis monitoring of the protecting group release, which proceeds to completion between 40 min and 2 h within the studied range of concentration as demonstrated by 1H NMR spectroscopy. Thiol-maleimide addition is subsequently carried out and found to proceed with a nearly quantitative yield (ca. 90%) as measured by 1H NMR. Different block copolymers (9400 ≤ M n ≤ 16 500 g mol -1; 1.3 ≤ PDI ≤ 1.4) with a PDMAAm water-soluble block, a polystyrene hydrophobic block, or a poly(N-isopropylacrylamide) thermosensitive block as the first segment and possessing the photoreleasable thiol moieties in the second block are subsequently synthesized by RAFT-mediated polymerization. We finally demonstrate the orthogonal sequential deprotection and reaction with benzyl maleimide of two different thiol species originating from the thiocarbonylthio functionality and the o-nitrobenzyl protected lateral groups, respectively. © 2012 American Chemical Society.

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ID Code: 99304
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :35
Export Date: 5 September 2016
CODEN: MAMOB
Correspondence Address: Barner-Kowollik, C.; Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstr. 18, 76128 Karlsruhe, Germany; email: christopher.barner-kowollik@kit.edu
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Keywords: Acrylamides, Co-monomer, Controlled/living radical polymerization, Deprotection, Functionalizations, H NMR spectroscopy, Hydrophobic blocks, Maleimides, N ,n-dimethylacrylamide, N-isopropylacrylamides, Polymerization kinetics, Protecting group, Quantitative yields, Radical polymers, RAFT-mediated polymerization, Reversible addition-fragmentation transfers, Thermo sensitive, Thiol species, Thiol-enes, Water soluble copolymers, Water-soluble block, Amides, Block copolymers, Free radical polymerization, Polystyrenes, Acrylic monomers
DOI: 10.1021/ma202670d
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: 04 Oct 2016 03:55

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