Document Server@UHasselt >
Research >
Research publications >

Please use this identifier to cite or link to this item: http://hdl.handle.net/1942/15415

Title: Synthesis of Macromonomers from High-Temperature Activation of Nitroxide Mediated Polymerization (NMP)-made Polyacrylates
Authors: Vandenbergh, Joke
Junkers, Thomas
Issue Date: 2013
Citation: MACROMOLECULES, 46 (9), p. 3324-3331
Abstract: Macromonomers are synthesized from thermal reactivation of three different precursors, Poly(n-butyl acrylate) P(nBuA), Poly(tert-butyl acrylate) P(tBuA), and Poly(2-ethylhexyl acrylate) P(EHA), synthesized via nitroxide mediated polymerization (NMP). Reactivation of the polymer chains is carried out at 140 degrees C, whereby the polyacrylate macroradicals undergo chain transfer reactions forming midchain radicals, MCR, followed by beta-scission reactions leading to unsaturated macromonomers. Sou-ionization mass spectrometry of product samples reveals that in all cases predominantly macromonomers that carry a hydrogen end group on the other chain end are formed, which is also accompanied by small reductions in molecular weight (-200 g.mol(-1)) and slight increases in polydispersity (+0.2). Furthermore, we demonstrate that macromonomers under these reaction conditions are not only formed through simple backbiting/beta-scission via six-membered ring transition structures but also that complex addition fragmentation equilibria must play a considerable role. As observed before for macromonomers made from activation of atom transfer radical polymerization (ATRP)-made precursors, a size-selective reaction pathway is observed that favors the generation of macromonomers with only odd numbers of monomer units on the backbone, supporting an MCR migration mechanism, which allows MCRs to move along the backbone.
Notes: Univ Hasselt, Inst Mat Res Imo Imomec, Polymer React Design Grp, B-3590 Diepenbeek, Belgium.
URI: http://hdl.handle.net/1942/15415
DOI: 10.1021/ma400477t
ISI #: 000319185000015
ISSN: 0024-9297
Category: A1
Type: Journal Contribution
Validation: ecoom, 2014
Appears in Collections: Research publications

Files in This Item:

There are no files associated with this item.

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.