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Please use this identifier to cite or link to this item: http://hdl.handle.net/1942/19670

Title: Ligand switch in photoinduced copper-mediated polymerization: synthesis of methacrylate-acrylate block copolymers
Authors: Chuang, Ya-Mi
Wenn, Benjamin
Gielen, Sam
Ethirajan, Anitha
Junkers, Thomas
Issue Date: 2015
Publisher: ROYAL SOC CHEMISTRY
Citation: Polymer Chemistry, 6 (36), p. 6488-6497
Abstract: The use of photo-induced copper-mediated radical polymerization (photoCMP) to synthesize mixed acrylate/methacrylate (methyl acrylate, MA and methyl methacrylate, MMA) block copolymers is investigated. Reactions in which only one type of ligand (Me6TREN) is used lead to unsuccessful outcomes of polymerization due to a mismatch in reactivity of the two monomers. A ligand exchange to PMDETA for methacrylate is required to obtain good block structures. Due to insufficient re-initiation of polyacrylates, methyl methacrylate needs to be polymerized first, before acrylate can be added for chain extension. A halogen exchange with CuCl is found to be beneficial to increase the re-initiation behaviour of the polyacrylate with respect to the acrylate chain propagation, but inherently compromises the livingness of the polymerization. Successful synthesis of block copolymers is only observed when the PMMA block is polymerized first and if all PMDETA ligand and residual monomer are removed prior to acrylate chain extension. The batch-type photoreactions are then transferred to a continuous flow tubular photoreactor, which leads to a significant acceleration of polymerizations, concomitant reduction in product dispersity and largely simplified block copolymer synthesis conditions.
Notes: [Chuang, Ya-Mi; Wenn, Benjamin; Gielen, Sam; Junkers, Thomas] Hasselt Univ, Inst Mat Res IMO, Polymer React Design Grp, B-3590 Diepenbeek, Belgium. [Chuang, Ya-Mi; Ethirajan, Anitha] Hasselt Univ, Inst Mat Res, Organ & Biopolymer Chem, B-3590 Diepenbeek, Belgium. [Junkers, Thomas] Associated Lab IMOMEC, IMEC, B-3590 Diepenbeek, Belgium.
URI: http://hdl.handle.net/1942/19670
DOI: 10.1039/c5py00592b
ISI #: 000360482900006
ISSN: 1759-9954
Category: A1
Type: Journal Contribution
Validation: ecoom, 2016
Appears in Collections: Research publications

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