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Photoinduced conjugation of Dithioester- and Trithiocarbonate-Functional RAFT polymers with alkenes

Gruendling, Till, Kaupp, Michael, Blinco, James P., & Barner-Kowollik, Christopher (2011) Photoinduced conjugation of Dithioester- and Trithiocarbonate-Functional RAFT polymers with alkenes. Macromolecules, 44(1), pp. 166-174.

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Abstract

We report the photoinduced conjugation of polymers synthesized via reversible addition−fragmentation chain transfer (RAFT) polymerization with a number of low molecular weight (functional) olefins. Upon irradiation of a solution of an aliphatic alkene and the benzyl dithioacetic acid ester (CPDA) or dodecyl trithiocarbonate (DoPAT) functional poly(alkyl acrylate) at the absorption wavelength of the thiocarbonyl group (315 nm), incorporation of the alkene at the polymer chain-end occurred. The most efficient systems identified with regard to the rate of reaction and yield were poly(butyl acrylate)/CPDA/ethyl vinyl ether (78% monoinsertion product after 1 h) and poly(butyl acrylate)/CPDA/1-pentene (73% insertion product after 7 h) at ambient temperature. An in-depth analysis of the reaction mechanism by 1H NMR and online size-exclusion chromatography-electrospray ionization tandem mass spectrometry (SEC/ESI−MSn) revealed that a possible [2 + 2] photoaddition mechanism of conjugation does not take place. Instead, fast β-cleavage of the photoexcited RAFT-end group with subsequent radical addition of an alkene was observed for all employed systems. The presented reaction thus provides a means of spatial and temporal control for the conjugation of alkenes to thiocarbonyl thio-capped macromolecules via the use of UV radiation.

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15 citations in Scopus
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8 citations in Web of Science®

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ID Code: 45920
Item Type: Journal Article
Keywords: RAFT , Synthesis of Poly(butyl acrylate), Time Series Reactions
DOI: 10.1021/ma101893u
ISSN: 0024-9297
Subjects: Australian and New Zealand Standard Research Classification > CHEMICAL SCIENCE (030000) > MACROMOLECULAR AND MATERIALS CHEMISTRY (030300)
Australian and New Zealand Standard Research Classification > CHEMICAL SCIENCE (030000) > MACROMOLECULAR AND MATERIALS CHEMISTRY (030300) > Synthesis of Materials (030306)
Divisions: Past > Schools > Chemistry
Past > QUT Faculties & Divisions > Faculty of Science and Technology
Deposited On: 13 Sep 2011 08:41
Last Modified: 27 Jun 2014 11:49

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