Issue 89, 2014

Synthesis, characterization, and computational study of potential itaconimide-based initiators for atom transfer radical polymerization

Abstract

Atom transfer radical polymerization (ATRP) has been a promising technique to provide polymers with well-defined composition, architecture, and functionality. In most of the ATRP processes, alkyl halides are used as an initiator. We report the synthesis of three possible potential initiators, N-phenyl(3-bromo-3-methyl)succinimide, N-phenyl(3-bromo-4-methyl)succinimide, and N-phenyl(3-bromomethyl)succinimide for ATRP of N-phenylitaconimide (PI) and methyl methacrylate (MMA). These functionalized alkyl halides, having structural similarity with PI, were characterized by FTIR, HRMS, 1H, 13C NMR spectroscopy, and elemental analysis. The equilibrium constants for the ATRP activation/deactivation process (KATRP) of these alkyl halides as well as a commercial ATRP initiator (ethyl-α-bromoisobutyrate) were determined using UV-Vis-NIR and DOSY NMR spectroscopy. Alternatively, these compounds and similar alkyl halides (R-X) were investigated using density functional theory for their possible chain initiation activity for the ATRP process. The B3LYP functional and 6-31+G(d)/LanL2DZ basis set was used for the prediction of geometries and energetics associated with the homolytic R–X bond dissociation. The relative value of KATRP and its variation with system parameters (such as substituent, temperature, and solvent) was investigated. We found a good agreement between the experimentally determined and theoretically calculated KATRP values. Our experiments show that the newly synthesized initiator N-phenyl(3-bromo-3-methyl)succinimide performs better than the commercially available initiator ethyl-α-bromoisobutyrate for the atom transfer radical copolymerization of PI and MMA.

Graphical abstract: Synthesis, characterization, and computational study of potential itaconimide-based initiators for atom transfer radical polymerization

Supplementary files

Article information

Article type
Paper
Submitted
20 Aug 2014
Accepted
02 Sep 2014
First published
08 Sep 2014

RSC Adv., 2014,4, 48163-48176

Author version available

Synthesis, characterization, and computational study of potential itaconimide-based initiators for atom transfer radical polymerization

C. Deoghare, C. Baby, V. S. Nadkarni, R. N. Behera and R. Chauhan, RSC Adv., 2014, 4, 48163 DOI: 10.1039/C4RA08981B

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